(12) Patent Application Publication (10) Pub. No.: US 2006/0102871 A1 Wang Et Al

US 200601 02871 A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2006/0102871 A1 Wang et al. (43) Pub. Date: May 18, 2006

(54) NOVELCOMPOSITION 25, 2004, and which is a continuation-in-part of application No. 10/780,045, filed on Feb. 17, 2004, (76) Inventors: Xingwu Wang, Wellsville, NY (US); and which is a continuation-in-part of application No. Howard Greenwald, Rochester, NY 10/747,472, filed on Dec. 29, 2003, and which is a (US); Michael L. Weiner, Webster, NY continuation-in-part of application No. 10/744.543, (US) filed on Dec. 22, 2003, now abandoned, and which is a continuation-in-part of application No. 10/442.420, Correspondence Address: filed on May 21, 2003, now Pat. No. 6,914,412, and Nanoset LLC which is a continuation-in-part of application No. Suite 2490 10/409,505, filed on Apr. 8, 2003, now Pat. No. 349 West Commercial Street 6,815,609. East Rochester, NY 14445 (US) (60) Provisional application No. 60/559,555, filed on Apr. (21) Appl. No.: 11/048,297 5, 2004. (22) Filed: Jan. 31, 2005 Publication Classification Related U.S. Application Data (51) Int. Cl. HOIF I/00 (2006.01) (63) Continuation-in-part of application No. 10/923,579, (52) U.S. Cl...... 252A62.51 R filed on Aug. 20, 2004, which is a continuation-in part of application No. 10/914.691, filed on Aug. 9. (57) ABSTRACT 2004, and which is a continuation-in-part of applica tion No. 10/887,521, filed on Jul. 7, 2004, and which A nancomposite material containing nanomagnetic material is a continuation-in-part of application No. 10/867, disposed within a matrix. The nanomagnetic material has a 517, filed on Jun. 14, 2004, and which is a continu saturation magentization of from about 2 to about 3000 ation-in-part of application No. 10/810,916, filed on electromagnetic units per cubic centimeter and contains Mar. 26, 2004, now Pat. No. 6,846,985, and which is nanomagnetic particles with an average particle size of less a continuation-in-part of application No. 10/808,618, than about 100 nanometers; the average coherence length filed on Mar. 24, 2004, and which is a continuation between adjacent nanomagnetic particles is less than 100 in-part of application No. 10/786,198, filed on Feb. nanometerS.

SUBSTRATE 23 1. Patent Application Publication May 18, 2006 Sheet 1 of 25 US 2006/01 02871 A1

w r Patent Application Publication May 18, 2006 Sheet 2 of 25 US 2006/01 02871 A1

T TT I I I I I I I IT IN IT

TATMTV2E N T N T W A NT INF Sa TS 52

Patent Application Publication May 18, 2006 Sheet 3 of 25 US 2006/01 02871 A1

Patent Application Publication May 18, 2006 Sheet 4 of 25 US 2006/01 02871 A1

o O N

SN s Patent Application Publication May 18, 2006 Sheet 5 of 25 US 2006/01 02871 A1

O O. s O O O O O O

O O O. O. O. O. O. O O. O. O. O. O. O. O. O.

cooo.O O

Patent Application Publication May 18, 2006 Sheet 6 of 25 US 2006/01 02871 A1

CO O V

Patent Application Publication May 18, 2006 Sheet 7 of 25 US 2006/01 02871 A1

552 554 546 SUBSTRATE 548 | COANG

556 562 MAGNEIC FIELD GENERATOR

544 SSO 54O. 542

533 N. 2533 536 S38

S25

529 527- 527 S29 531

515 A 517 51

509 N 53

FIG.8 Patent Application Publication May 18, 2006 Sheet 8 of 25 US 2006/01 02871 A1

0/9 (JEITTOHINOO 22 V n N Vad O 999 9/9 Vo SONUNCIONONONOSTNUTNINININOEKONOKOK 999 -|(No.No.TZZ9#99099 No.en

Patent Application Publication May 18, 2006 Sheet 9 of 25 US 2006/01 02871 A1

?y V ym s

is Sy S S- L rthis isr isr S.r S.lir LL.nu

in f on n t na

O t N t t ym

- - m in H I N. inN. N. N. N. In N /

g?R2s. f / sV s Patent Application Publication May 18, 2006 Sheet 10 of 25 US 2006/01 02871 A1

Patent Application Publication May 18, 2006 Sheet 11 of 25 US 2006/01 02871 A1

OO1 1020 / 1010

XXXXXXX§§ &&&&&&&& }&&&&&&& &&&&&&&& ????&&&& $3&&3&&3333333 §§ §§ ž

FIG.16

- 100.or

FIG 17

Patent Application Publication May 18, 2006 Sheet 12 of 25 US 2006/01 02871 A1

1045-ooooooooooooooooooO so o o

1025 1020

FIG. 18

/1 OO3 1O3O 1040 1050 O70 1055 1045 1021

FIG.19 Patent Application Publication May 18, 2006 Sheet 13 of 25 US 2006/01 02871 A1

1090

110 107 100 1055 Ng...' ... so...s.. 'e','....d.o.o...a... .o.o 1045-ooooooooooooooooooooo a O

21025 1021 FIG.2O

1030. 1080 105.5 1045 O23 ŽYZ

FIG.21 Patent Application Publication May 18, 2006 Sheet 14 of 25 US 2006/01 02871 A1

1025 1023

FIG.22

FIG23 Patent Application Publication May 18, 2006 Sheet 15 of 25 US 2006/01 02871 A1

OO /1 1102

102 1106 Patent Application Publication May 18, 2006 Sheet 16 of 25 US 2006/01 02871 A1

/ Patent Application Publication May 18, 2006 Sheet 17 of 25 US 2006/01 02871 A1

ZOTIT 8Z75TH Patent Application Publication May 18, 2006 Sheet 18 of 25 US 2006/01 02871 A1

Patent Application Publication May 18, 2006 Sheet 19 of 25 US 2006/01 02871 A1

Patent Application Publication May 18, 2006 Sheet 20 of 25 US 2006/01 02871 A1

8IZI DINE5DOARIO dW?ld

RIEINAOd EORITMOS 0IZI 00ZI

ZOZT Patent Application Publication May 18, 2006 Sheet 21 of 25 US 2006/01 02871 A1

Patent Application Publication May 18, 2006 Sheet 22 of 25 US 2006/01 02871 A1

RIENWOd EOHITOS SOINES)OÅRIOZOZI Patent Application Publication May 18, 2006 Sheet 23 of 25 US 2006/01 02871 A1

AONETOBH+

#78."5DI Patent Application Publication May 18, 2006 Sheet 24 of 25 US 2006/01 02871 A1

S. Patent Application Publication May 18, 2006 Sheet 25 of 25 US 2006/01 02871 A1

US 2006/01 02871 A1 May 18, 2006

NOVEL COMPOSITION material and a second material selected from the group consisting of a polymeric material, an elastomeric material, CROSS-REFERENCE TO RELATED PATENT a ceramic material, and mixtures thereof. APPLICATIONS 0008. In another embodiment, the mixture also contains 0001. This application is a continuation-in-part of appli halloysite. The nanomagnetic material contains particles cants’ U.S. patent application Ser. No. 10/923,579, filed on with a particle size of from about 3 to about 100 nanometers: Aug. 20, 2004, which in turn was a continuation-in-part of and said particles are at least triatomic, being comprised, of each of applicants copending patent application Ser. No. a first distinct atom, a second distinct atom, and a third 10/914,691 (filed on Aug. 8, 2004), Ser. No. 10/887,521 distinct atom. (filed on Jul. 7, 2004), Ser. No. 10,867.517 (filed on Jun. 14, 2004), Ser. No. 10/810,916 (filed on Mar. 26, 2004), Ser. No. BRIEF DESCRIPTION OF THE DRAWINGS 10/808,618 (filed on Mar. 24, 2004), Ser. No. 10/786,198 (filed on Feb. 25, 2004), Ser. No. 10/780,045 (filed on Feb. 0009. Applicants’ inventions will be described by refer 17, 2004), Ser. No. 10/747,472 (filed on Dec. 29, 2003), Ser. ence to the specification and the drawings, in which like No. 10/744.543 (fled on Dec. 22, 2003), Ser. No. 10/442,420 numerals refer to like elements, and wherein: (filed on May 21, 2003), and Ser. No. 10/409,505 (flied on 0010 FIG. 1 is a schematic illustration, not drawn to Apr. 8, 2003). The entire disclosure of each of these patent scale, of a coated substrate assembly 10 comprised of a applications is hereby incorporated by reference into this Substrate 12 and, disposed thereon, a coating 14 comprised specification. of a multiplicity of nanomagnetic particles 16: 0002 This patent application also claims priority based upon provisional patent application 60/559,555, filed on 0011 FIGS. 2 and 3 schematically illustrate the porosity Apr. 5, 2004, the entire disclosure of which is hereby of the side of coating 14, and the top of the coating 14. incorporated by reference into this specification. depicted in FIG. 1; 0012 FIG. 4 is a schematic illustration of a coated stent FIELD OF THE INVENTION assembly 100: 0003. A mixture comprised of nanomagnetic material and 0013 FIG. 5 is a partial schematic view of a coated stent a second material selected from the group consisting of a assembly 200; polymeric material, an elastomeric material, a ceramic mate rial, and mixtures thereof. 0014 FIG. 6 is a schematic of one preferred sputtering process; BACKGROUND OF THE INVENTION 0.015 FIG. 7 is a partial schematic of one preferred 0004 Applicants have been awarded several United particle collection process; States patents that describe nanomagnetic material. These include U.S. Pat. No. 6,506.972 (“Magnetically shielded 0016 FIG. 8 is a schematic of a plasma deposition conductor”), U.S. Pat. No. 6,673,999 (“Magnetically process; shielded assembly”), U.S. Pat. No. 6,713,671 (“Magneti 0017 FIG. 9 is a schematic of one preferred forming cally shielded assembly”), U.S. Pat. No. 6,765,144 (“Mag netic resonance imaging coated assembly'), U.S. Pat. No. process; 6,768,053 (“Optical fiber assembly”), and U.S. Pat. No. 0018 FIGS. 10, 11, 12, 13, and 14 are schematic illus 6,815,609 (“Nanomagnetic composition'). The entire dis trations of preferred particles of the invention; closure of each of these United States patents is hereby 0019 FIG. 15 is a phase diagram showing various com incorporated by reference into this specification. positions that may contain moieties E, F, and G; 0005. In addition, applicants have published several United States patent applications that relate to nanomagnetic 0020 FIG. 16 is a cross-sectional view of a preferred material including, published United States patent applica stent of this invention; tions US20040210289 (“Novel nanomagnetic particles”), 0021 FIG. 17 is a cross-sectional view of a coated strut US20040211580 (“Magnetically shielded assembly”), 1020 of the stent of FIG. 16; US20040225213 (“Magnetic resonance imaging coated assembly”), US20040226603 (“Optical fiber assembly”), 0022 FIG. 18 shows the effect on the coated strut 1020 20040230271 (“Magnetically shielded assembly”), when a patient is exposed to an electromagnetic field 1090; US2004024.9428(“Magnetically shielded assembly”), US2004O254419 (“Therapeutic assembly”), and 0023 FIG. 19 is a cross-sectional view of another coated US2004025.6131 (“Nanomagnetically shielded assembly”). strut 1021; The entire disclosure of each of these published United 0024 FIG. 20 shows the effect on the coated strut 1021 States patent applications when a patient is exposed to an electromagnetic field 1090; 0006. It is an object of this invention to provide improved 0025 FIG. 21 is a cross-sectional view of another coated compositions that comprise Such nanomagnetic material and strut 1023; one or more other materials. 0026 FIG. 22 shows the effect on the coated strut 1023 SUMMARY OF THIS INVENTION when a patient is exposed to an electromagnetic field 1090; 0007. In accordance with one embodiment of this inven 0027 FIG. 23 is a cross-sectional view of a coated strut tion, there is provided a mixture comprised of nanomagnetic 1027; US 2006/01 02871 A1 May 18, 2006

0028 FIG. 24 is a schematic illustration of an inorganic The Magnetic Permeability of the Nanomagnetic Material tubular mineral composition; 0043. In one preferred embodiment, the nanomagnetic 0029 FIG. 25 is a sectional view of the inorganic tubular material of this invention has a magnetic permeability of mineral composition of FIG. 24; from about 0.7 to about 2.0. As used in this specification, the term “magnetic permeability” refers to “ . . . a property of 0030 FIG. 26 is a schematic view of an inorganic tubular materials modifying the action of magnetic poles placed mineral composition comprised of nanomagnetic material on therein and modifying the magnetic induction resulting the exterior surfaces of the tubules; when the material is subjected to a magnetic field of mag netizing force. The permeability of a Substance may be 0031 FIG. 27 is a schematic view of an inorganic tubular defined as the ratio of the magnetic induction in the Sub mineral composition comprised of nanomagnetic material stance to the magnetizing field to which it is Subjected. The on the interior surfaces of the tubulues; permeability of a vacuum is unity.’ See, e.g., page F-102 of 0032 FIG. 28 is a schematic diagram of a flexed inor -Robert E. Weast et al.’s “Handbook of Chemistry and ganic tubules comprised of a film of nanomagnetic material Physics,” 63" Edition (CRC Press, Inc., Boca Raton, Fla., on its exterior Surface; 1982-1983 edition). Reference may also be had, e.g., to U.S. Pat. No. 4,007,066 (material having a high magnetic per 0033 FIG. 29 is a a graph illustrating how the suscep meability), U.S. Pat. No. 4.340,770 (enhancement of the tibility of the nanomagentic coatings of the invention varies magnetic permeability in glass metal shielding), U.S. Pat. in the presence of an alternating current electromagnetic No. 4,482.397 (method for improving the magnetic perme field; and ability of grain oriented silicon steel), U.S. Pat. No. 4,702, 935 (high magnetic permeability alloy film), U.S. Pat. No. 0034 FIG. 30 is a graph illustrating how the suscepti 4.725.490 (high magnetic permeability composites contain bility of the nanomagnetic coatings of the invention varies in ing fibers with ferrite fill), U.S. Pat. No. 5,073,211 (method the presence of botah a direct current magnetic field and an for manufacturing steel article having high magnetic per alternating current electromagnetic field; meability and low coercive force), U.S. Pat. No. 5,099,518 0035 FIG. 31 is a schematic illustration of a preferred (electrical conductor of high magnetic permeability mate process for preparing particles of nanomagneic material; rial), U.S. Pat. No. 5,645,774 (method for establishing a target magnetic permeability in a ferrite), U.S. Pat. No. 0036 FIG. 32 is is a schematic of a press die and 5,691.645 (process for determining intrinsic magnetic per assembly that may be used to prepare pellets of halloysite meability of elongated ferromagnetic elements), U.S. Pat. material that may thereafter be coated with nanomagnetic No. 5,691,645 (process for determining intrinsic magnetic material; permeability of elongated ferromagnetic elements), U.S. Pat. No. 6,020,741 (wellbore imaging using magnetic per 0037 FIG. 33 is a schematic illustration of a preferred meability measurements), U.S. Pat. No. 6,176,944 (method process for preparing a coating of nanomagnetic material on for making low magnetic permeability cobalt sputter tar pellets of inorganic mineral material. Such as halloysite; gets), U.S. Pat. No. 6,190.516 (high magnetic flux sputter 0038 FIG. 34 is a schematic of a graph of the amplituide targets with varied magnetic permeability in selected of the spin echo response vesus frequency; regions), U.S. Pat. No. 6,233,126 (thin film magnetic head having low magnetic permeability layer), U.S. Pat. No. 0039 FIG. 35 is a schematic of a coated substrate 6,472,836 (magnetic permeability position detector), and the wherein the coating has a specified ferromagnetic resonance like. The entire disclosure of each of these United States frequency; patents is hereby incorporated by reference into this speci fication. 0040 FIG. 36 is a schematic illustration for heating a stent with the coating of FIG. 35 by exposing the stent to a 0044) Reference may also be had to page 1399 of Sybil Source of electromagnetic radiation and P. Parker’s “McGraw-Hill Dictionary of Scientific and Tech nical Terms. Fourth Edition (McGraw Hill Book Company, 0041 FIG. 37 is a schematic illustration of a nanocom New York, 1989). As is disclosed on this page 1399, posite material comprised of a matrix and a tubule disposed permeability is “...a factor, characteristic of a material, that therein, wherein the tubule is filled with biologically active is proportional to the magnetic induction produced in a material. material divided by the magnetic field strength; it is a tensor when these quantities are not parallel. DESCRIPTION OF THE PREFERRED Nanomagnetic Particles in the Nanomagnetic Material EMBODIMENTS 0045. In one embodiment of this invention, there is 0042. In the first portion of this specification, the prop provided a multiplicity of nanomagnetic particles that may erties of applicants preferred nanomagnetic material are be in the form of a film, a powder, a solution, etc. This described. In the second portion of this specification, appli multiplicity of nanogmentic particles is hereinafter referred cants describe a preferred process for preparing Such nano to as a collection of nanomagnetic particles. magnetic material. In the third part of this specification, 0046) The collection of nanomagnetic particles of this applicants describe certain preferred devices that comprise embodiment of the invention is generally comprised of at the preferred nanomagnetic material. In the fourth part of least about 0.05 weight percent of Such nanomagnetic par this specification, applicants describe a composition com ticles and, preferably, at least about 5 weight percent of such prised of Such nanomagnetic material and one or more nanomagnetic particles. In one embodiment, such collection minerals. is comprised of at least about 50 weight percent of such US 2006/01 02871 A1 May 18, 2006 magnetic particles. In another embodiment. Such collection conducting inclusions 22 so that the average particle dis consists essentially of Such nanomagnetic particles. tance . . . between the Superconducting inclusions 22 0047. When the collection of nanomagnetic particles approaches the coherence length as much as possible. An consists essentially of nanomagnetic particles, the term average particle distance comparable to the coherence length “compact will be used to refer to such collection of between the Superconducting inclusions 22 is necessary in nanomagnetic particles. order to achieve significant enhancement through the proX imity effect and high critical currents for the matrix 10.), Particle Size of the Nanomagnetic Particles U.S. Pat. No. 5,998.336 (“The ceramic particles 2 have physical dimensions larger than the Superconducting coher 0.048. In general, the nanomagnetic particles of this ence length of the ceramic. Typically, the coherence length invention are smaller than about 100 nanometers. In one of high T ceramic materials is 1.5 nm.”), U.S. Pat. No. embodiment, these nano-sized particles have a particle size 6,420.318 (“The particles 22 preferably have dimensions distribution such that at least about 90 weight percent of the larger than the Superconducting coherence length of the particles have a maximum dimension in the range of from Superconducting material.”), and the like. The entire disclo about 1 to about 100 nanometers. sure of each of these United States patents is hereby incor 0049. In one embodiment, the average size of the nano porated by reference into this specification. The coherence magnetic particles is preferably less than about 50 nanom length (L) between adjacent magnetic particles is, on aver eters. In one embodiment, the nanomagnetic particles have age, preferably from about 10 to about 200 nanometers and, an average size of less than about 20 nanometers. In another more preferably, from about 50 to about 150 nanometers. In embodiment, the nanomagnetic particles have an average one preferred embodiment, the coherence length (L) size of less than about 15 nanometers. In yet another between adjacent nanomagnetic particles is from about 75 to embodiment, such average size is less than about 11 nanom about 125 nanometers. eters. In yet another embodiment, Such average size is less than about 3 nanometers. 0052. In one embodiment, x is preferably equal to from about 0.00001 times L to about 100 times L. In one Coherence Length of the Nanomagnetic Particles embodiment, the ratio of X/L is at least 0.5 and, preferably, 0050. As is used in this specification, the term “coherence at least 1.5. length” refers to the distance between adjacent nanomag Ratio of the Coherence Length Between Nanomagnetic netic moieties, and it has the meaning set forth in applicants Particles to Their Particle Size published international patent document W003061755A2, the entire disclosure of which is hereby incorporated by 0053. In one preferred embodiment, the ratio of the reference into this specification. As is disclosed in Such coherence length between adjacent nanomagnetic particles published international patent document, “Referring to FIG. to their particle size is at least 2 and, preferably, at least 3. 38, and in the preferred embodiment depicted therein, it will In one aspect of this embodiment, Such ratio is at least 4. In be seen that A moieties 5002, 5004, and 5006 are separated another aspect of this embodiment. Such ratio is at least 5. from each other either at the atomic level and/or at the The Saturation Magnetization of the Nanomagnetic Particles nanometer level. The A moieties may be, e.g., A atoms, of the Invention clusters of A atoms. A compounds, A Solid solutions, etc.; 0054 The nanomagnetic particles of this invention pref regardless of the form of the A moiety, it has the magnetic erably have a saturation magnetization (“magnetic properties described hereinabove . . . Thus, referring . . . to moment”) of from about 2 to about 3,000 electromagnetic FIG. 38, the normalized magnetic interaction between adja units (emu) per cubic centimeter of material. As is known to cent A moieties 5002 and 5004, and also between 5004 and those skilled in the art, Saturation magnetization is the 5006, is preferably described by the formula M=exp(-X/L). maximum possible magnetization of a material. Reference wherein M is the normalized magnetic interaction, eXp is the may be had, e.g., to U.S. Pat. No. 3,901,741 (saturation base of the natural logarithm (and is approximately equal to magnetization of cobalt, Samarium, and gadolinium alloys), 2.71828), X is the distance between adjacent A moieties, and U.S. Pat. No. 4,134,779 (iron-boron solid solution alloys L is the coherence length. . . . In one embodiment, and having high saturation magnetization), U.S. Pat. No. 4.390. referring again to FIG.38, X is preferably measured from the 853 (microwave transmission devices having high Saturation center 5001 of A moiety 5002 to the center 5002 of A moiety magnetization and low magnetostriction), U.S. Pat. No. 5004; and X is preferably equal to from about 0.00001XL to 4.532.979 (iron-boron solid solution alloys having high about 100xL. . . . In one embodiment, the ratio of X/L is at saturation magnetization and low magnetostriction), U.S. least 0.5 and, preferably, at least 1.” Pat. No. 4,631,613 (thin film head having improved satura 0051) With regard to the term “coherence length,” refer tion magnetization), U.S. Pat. Nos. 4,705,613, 4,782.416 ence also may be had to U.S. Pat. No. 4,411,959 (which (magnetic head having two legs of predetermined Saturation discloses that “ . . . the spherical particle diameter, phi. magnetization for a recording medium to be magnetized preferably is to exceed the Ginzburg-Landau coherence vertically), U.S. Pat. No. 4,894,360 (method of using a lengths, Xi.GL, to avoid any significant degradation of Tc. ferromagnet material having a high permeability and Satu The spacing between adjacent particles is to be much less ration magnetization at low temperatures), U.S. Pat. No. than Xi.GL to ensure strong coupling while the diameter of 5.543,070 (magnetic recording powder having low curie voids between dense-packed spheres should be comparable temperature and high Saturation magnetization), U.S. Pat. to Xi.GL in order to ensure maximum flux pinning . . . ), No. 5,761,011 (magnetic head having a magnetic shield film U.S. Pat. No. 5,098,178 (which discloses that “In addition, with a lower saturation magnetization than a magnetic the anisotropic shrinkage of the Sol-Gel during polymeriza response film of an MR element), U.S. Pat. No. 5,922,442 tion is utilized to increase the concentration of the Super (magnetic recording medium having a cobalt/chromium US 2006/01 02871 A1 May 18, 2006

alloy interlayer of a low Saturation magnetization), U.S. Pat. cobalt, boron, and fluoride, and the like. These and other No. 6,492,035 (magneto-optical recording medium with materials are described in a book by J. Douglas Adam et al. intermediate layer having a controlled Saturation magneti entitled “Handbook of Thin Film Devices” (Academic zation), and the like. The entire disclosure of each of these Press, San Diego, Calif., 2000). Chapter 5 of this book, United States patents is hereby incorporated by reference beginning at page 185, describes “magnetic films for planar into this specification. As will be apparent to those skilled in inductive components and devices;” and Tables 5.1 and 5.2 the art, especially upon studying the aforementioned patents, in this chapter describe many magnetic materials. the Saturation magnetization of thin films is often higher than the saturation magnetization of bulk objects. The Coercive Force of the Nanomagnetic Particles 0.055 Saturation magnetization may be measured by con 0061. In one preferred embodiment, the nanomagnetic ventional means. Reference may be had, e.g., to U.S. Pat. particles of this invention have a coercive force of from No. 5,068.519 (magnetic document validator employing about 0.01 to about 5,000 Oersteds. The term coercive force remanence and Saturation measurements), U.S. Pat. Nos. refers to the magnetic field, H, which must be applied to a 5,581,251, 6,666,930, 6,506,264 (ferromagnetic powder), magnetic material in a symmetrical, cyclicly magnetized U.S. Pat. Nos. 4,631,202, 4,610,911, 5,532,095, and the like. fashion, to make the magnetic induction, B. vanish; this term The entire disclosure of each of these United States patents often is referred to as magnetic coercive force. Reference is hereby incorporated by reference into this specification. may be had, e.g., to U.S. Pat. Nos. 3,982.276, 4,003,813 (method of making a magnetic oxide film with a high 0056. In one embodiment, the saturation magnetization coercive force), U.S. Pat. No. 4,045,738 (variable reluctance of the nanomagnetic particles of this invention is preferably speed sensor using a shielded high coercive force rare earth measured by a SQUID (Superconducting quantum interfer magnet), U.S. Pat. Nos. 4,061824, 4,115,159 (method of ence device). Reference may be had, e.g., to U.S. Pat. No. increasing the coercive force of pulverized rare earth-cobalt 5,423.223 (fatigue detection in Steel using Squid mangetom alloys) U.S. Pat. No. 4,277.552 (toner containing high etry), U.S. Pat. No. 6,496.713 (ferromagnetic foreign body coercive force magnetic powder), U.S. Pat. No. 4.396,441 detection with background canceling), U.S. Pat. Nos. 6,418, (permanent magnet having ultra-high coercive force), U.S. 335, 6,208.884 (noninvasive room temperature instrument Pat. No. 4,465,526 (high coercive force permanent magnet), to measure magnetic Susceptibility variations in body tis U.S. Pat. No. 4,481,045 (high-coercive-force permanent sue), U.S. Pat. No. 5,842.986 (ferromagnetic foreign body magnet), U.S. Pat. No. 4,485,163 (triron tetroxide having screening method), U.S. Pat. Nos. 5.471,139, 5.408,178, and specified coercive force), U.S. Pat. No. 4,675,170 (prepara the like. The entire disclosure of each of these United States tion of finely divided acicular hexagonal ferrites having a patents is hereby incorporated by reference into this speci high coercive force), U.S. Pat. Nos. 4,741,953, 4,816.933 fication. (magnetic recording medium of particular coercive force), 0057. In one preferred embodiment, the saturation mag U.S. Pat. No. 4,863,530 (Fc-Pt Nb magnet with ultra netization of the nanomagnetic particle of this invention is at high coercive force), U.S. Pat. Nos. 4,939.210, 5,073,211 least 100 electromagnetic units (emu) per cubic centimeter (method for manufacturing steel article having high mag and, more preferably, at least about 200 electromagnetic netic permeability and low coercive force), U.S. Pat. No. units (emu) per cubic centimter. In one aspect of this 5.211.770 (magnetic recording powder having a high coer embodiment, the saturation magnetization of such nanomag cive force at room temperatures and a low curie point), U.S. netic particles is at least about 1,000 electromagnetic units Pat. No. 5,329,413 (magnetoresistive sensor magnetically per cubic centimeter. coupled with high-coercive force film at two end regions), U.S. Pat. No. 5,596,555 (magnetooptical recording medium 0.058. In another embodiment, the nanomagnetic material having magnetic layers that satisfy predetermined coercive of this invention is present in the form a film with a force relationships), U.S. Pat. No. 5,686,137 (method of saturization magnetization of at least about 2,000 electro providing hexagonal ferrite magnetic powder with enhanced magnetic units per cubic centimeter and, more preferably, at coercive force stability), U.S. Pat. No. 5,742,458 (giant least about 2,500 electromagnetic units per cubic centimeter. magnetoresistive material film which includes a free layer, a In this embodiment, the nanomagnetic material in the film pinned layer, and a coercive force increasing layer), U.S. preferably has the formula A.A.(B),C(C), whereiny is 1. Pat. Nos. 5,967,223, 6,189,791 (magnetic card reader and the C moieties are oxygen and nitrogen, respectively, and the method for determining the coercive force of a magnetic A moieties and the B moiety are as described elsewhere in card therein), U.S. Pat. Nos. 6.257.512, 6.295,186, 6,637, this specification. 653 (method of measuring coercive force of a magnetic 0059. Without wishing to be bound to any particular card), U.S. Pat. No. 6,449,122 (thin-film magnetic head theory, applicants believe that the saturation magnetization including soft magnetic film exhibiting high Saturation mag of their nanomagnetic particles may be varied by varying the netic flux density and low coercive force), U.S. Pat. No. concentration of the "magnetic' moiety A in Such particles, 6,496.338 (spin-valve magnetoresistive sensor including a and/or the concentrations of moieties B and/or C. first antiferromagnetic layer for increasing a coercive force), U.S. Pat. No. 6,667,119 (magnetic recording medium com 0060. In one embodiment, in order to achieve the degree prising magnetic layers, the coercive force thereof specifi degree of Saturation magnetization, the nanomagnetic par cally related to saturation magnetic flux density), U.S. Pat. ticles used typically comprise one or more of iron, cobalt, No. 6,687,009 (magnetic head with conductors formed on nickel, gadolinium, and Samarium atoms. Thus, e.g., typical endlayers of a multilayer film having magnetic layer coer nanomagnetic materials include alloys of iron and nickel cive force difference), and the like. The entire disclosure of (permalloy), cobalt, niobium, and Zirconium (CNZ), iron, each of these United States patents is hereby incorporated by boron, and nitrogen, cobalt, iron, boron, and silica, iron, reference into this specification. US 2006/01 02871 A1 May 18, 2006

0062. In one embodiment, the nanomagnetic particles different Curie temperatures), and the like. The entire dis have a coercive force of from about 0.01 to about 3,000 closure of each of these United States patents is hereby Oersteds. In yet another embodiment, the nanomagnetic incorporated by reference into this specification. particles have a coercive force of from about 0.1 to about 10. 0066. As used herein, the term “Curie temperature' refers The Phase Transition Temperature of the Nanomagnetic to the temperature marking the transition between ferromag Particles netism and paramagnetism, or between the ferroelectric phase and paraelectric phase. This term is also sometimes 0063. In one embodiment of this invention, the nanomag referred to as the “Curie point.” netic particles have a phase transition temperature is from about 40 degrees Celsius to about 200 degrees Celsius. As 0067. As used herein, the term “Neel temperature” refers used herein, the term phase transition temperature refers to to a temperature, characteristic of certain metals, alloys, and temperature in which the magnetic order of a magnetic salts, below which spontaneous magnetic ordering takes particle transitions from one magnetic order to another. place so that they become antiferromagnetic, and above Thus, for example, when a magnetic particle transitions which they are paramagnetic; this is also known as the Neel from the ferromagnetic order to the paramagnetic order, the point. Reference may be had, e.g., to U.S. Pat. Nos. 3,845, phase transition temperature is the Curie temperature. Thus, 306; 3,883,892; 3,946,372; 3,971,843; 4,103,315; 4,396, e.g., when the magnetic particle transitions from the anti 886; 5,264,980; 5,492,720; 5,756, 191; 6,083,632: 6,181, ferromagnetic order to the paramagnetic order, the phase 533, 3,883,892, 3,845,306; 6,020,060; 6,083,632, 4,396, transition temperature is known as the Neel temperature. 886, 4,438,462; 4,621,030; 5,923,504; 6,020,060; 6,146, 752; 6,483,674; 6,631,057; 6,534,204; 6,534,205; 6,754, 0064. For a discussion of phase transition temperature, 720; and the like. The entire disclosure of each of these reference may be had, e.g., to U.S. Pat. No. 4,804.274 United States patents is hereby incorporated by refernec into (method and apparatus for determining phase transition this specification. temperature using laser attenuation), U.S. Pat. No. 5,758, 968 (optically based method and apparatus for detecting a 0068 Neel temperature is also disussed at page F-92 of phase transition temperature of a material of interest), U.S. the “Handbook of Chemistry and Physics, 63" Edition Pat. Nos. 5,844,643, 5,933,565 (optically based method and (CRC Press, Inc., Boca Raton, Fla., 1982-1983). As is apparatus for detecting a phase transition temperature of a disclosed on Such page, ferromagnetic materials are “those material of interest), U.S. Pat. No. 6,517,235 (using refrac in which the magnetic moments of atoms or ions tend to tory metal silicidation phase transition temperature points to assume an ordered but nonparallel arrangement in Zero control and/or calibrate RTP low temperature operation), applied field, below a characteristic temperature called the and the like. The entire disclosure of each of these United Neel point. In the usual case, within a magnetic domain, a States patents is hereby incorporated by reference into this Substantial net mangetization results form the antiparallel specification. alignment of neighboring nonequivalent Subslattices. The macroscopic behavior is similar to that in ferromagnetism. 0065 For a discussion of Curie temperature, reference Above the Neel point, these materials become paramag may be had, e.g., to U.S. Pat. No. 3,736,500 (liquid identi netic.” fication using magnetic particles having a preselected Curie 0069. Without wishing to be bound to any particular temperature), U.S. Pat. No. 4,229.234 (passivated, particu theory, applicants believe that the phase temperature of their late high Curie temperature magnetic alloys), U.S. Pat. Nos. nanomagnetic particles can be varied by varying the ratio of 4,771.238, 4,778,867 (ferroelectric copolymers of vinylidene fluoride and trifluoroethyelene), U.S. Pat. No. the A, B, and C moieties described hereinabove as well as 5,108,191 (method and apparatus for determining Curie the particle sizes of the nanoparticles. temperatures of ferromagnetic materials), U.S. Pat. No. 0070. In one embodiment, the phase transition tempera 5.229,219 (magnetic recording medium having a Curie ture of the nanomagnetic particles of is higher than the temperature up to 180 degrees C.), U.S. Pat. No. 5,325,343 temperature needed to kill cancer cells but lower than the (magneto-optical recording medium having two RE-TM temperature needed to kill normal cells. AS is disclosed in, layers with the same Curie temperature), U.S. Pat. No. e.g., U.S. Pat. No. 4,776,086 (the entire disclosure of which 5,420,728 (recording medium with several recording layers is hereby incorporated by reference into this specification), having different Curie temperatures), U.S. Pat. No. 5.487, “The use of elevated temperatures, i.e., hyperthermia, to 046 (magneto-optical recording medium having two mag repress tumors has been under continuous investigation for netic layers with the same Curie temperature), U.S. Pat. No. many years. When normal human cells are heated to 41-43 5.543,070 (magnetic recording powder having low Curie C., DNA synthesis is reduced and respiration is depressed. temperature and high Saturation magnetization), U.S. Pat. At about 45° C., irreversible destruction of structure, and Nos. 5.563,852, 601,742 (heating device for an internal thus function of chromosome associated proteins, occurs. combustion engine with PTC elements having different Autodigestion by the cells digestive mechanism occurs at Curie temperatures), U.S. Pat. No. 5,679,474 (overwritable lower temperatures in tumor cells than in normal cells. In optomagnetic recording medium having a layer with a Curie addition, hyperthermia induces an inflammatory response temperature that varies in the thickness direction), U.S. Pat. which may also lead to tumor destruction. Cancer cells are No. 5,764,601 (magneto-optical recording medium with a more likely to undergo these changes at a particular tem readout layer of varying composition and Curie tempera perature. This may be due to intrinsic differences, between ture), U.S. Pat. Nos. 5,949,743, 6,125,083 (magneto-optical normal cells and cancerous cells. More likely, the difference recording medium containing a middle layer with a lower is associated with the lop pH (acidity), low oxygen content Curie temperature than the other layers), U.S. Pat. No. and poor nutrition in tumors as a consequence of decreased 6.731,111 (magnetic ink containing magnetic powders with blood flow. This is confirmed by the fact that recurrence of US 2006/01 02871 A1 May 18, 2006 tumors in animals, after hyperthermia, is found in the tumor 0075 U.S. Pat. No. 6,765,144 also discloses that “The margins; probably as a consequence of better blood Supply moiety A also preferably has a saturation magnetization of to those areas.” from about 1 to about 36,000 Gauss, and a coercive force of from about 0.01 to about 5,000 Oersteds. . . . The moiety A 0071. In one embodiment of this invention, the phase may be present in the nanomagnetic material either in its transition temperature of the nanomagnetic particles is less elemental form, as an alloy, in a solid solution, or as a than about 50 degrees Celsius and, preferably, less than compound . . . It is preferred at least about 1 mole percent about 46 degrees Celsius. In one aspect of this embodiment, of moiety A be present in the nanomagnetic material (by Such phase transition temperature is less than about 45 total moles of A, B, and C), and it is more preferred that at degrees Celsius. least 10 mole percent of such moiety A be present in the The Diverse Atomic Nature of the Nanomagnetic Particles nanomagnetic material (by total moles of A, B, and C). In 0072. In one embodiment, the nanomagnetic particles are one embodiment, at least 60 mole percent of such moiety A depicted by the formula A.A.(B),C(C), wherein each of is present in the nanomagnetic material, (by total moles of A and A are separate magnetic A moieties, as described A, B, and C.).” below; B is as defined elsewhere in this specification; x is an 0.076 U.S. Pat. No. 6,765,144 also discloses that “In integer from 0 to 1; each of C and C is as descried addition to moiety A, it is preferred to have moiety B be elsewhere in this specification; and y is an integer from 0 to present in the nanomagnetic material. In this embodiment, 1. moieties A and B are admixed with each other. The mixture 0073. The composition of these preferred nanomagnetic may be a physical mixture, it may be a solid solution, it may particles may be depicted by a phase diagram Such as, e.g., be comprised of an alloy of the A/B moieties, etc. the phase diagram depicted in FIG. 37 et seq. of U.S. Pat. 0077. In one embodiment, the magnetic material A is No. 6,765,144, the entire disclosure of which is hereby dispersed within nonmagnetic material B. This embodiment incorporated by reference into this specification. As is dis is depicted schematically in FIG. 38.” closed in such United States patent, “Referring to FIG. 37. 0078 U.S. Pat. No. 6,765,144 also discloses that “Refer and in the preferred embodiment depicted therein, a phase ring to FIG. 38, and in the preferred embodiment depicted diagram 5000 is presented. As is illustrated by this phase therein, it will be seen that A moieties 5002, 5004, and 5006 diagram 5000, the nanomagnetic material used in the com are separated from each other either at the atomic level position of this invention preferably is comprised of one or and/or at the nanometer level. The A moieties may be, e.g., more of moieties A, B, and C. . . . The moiety A depicted in A atoms, clusters of A atoms. A compounds, A Solid solu phase diagram 5000 is comprised of a magnetic element tions, etc.; regardless of the form of the A moiety, it has the selected from the group consisting of a transition series magnetic properties described hereinabove . . . In the metal, a rare earth series metal, or actinide metal, a mixture embodiment depicted in FIG. 38, each A moiety produces thereof, and/or an alloy thereof. . . . As is known to those an independent magnetic moment. The coherence length (L) skilled in the art, the transition series metals include chro mium, manganese, iron, cobalt, nickel. One may use alloys between adjacent A moieties is, on average, from about 0.1 or iron, cobalt and nickel Such as, e.g., iron-aluminum, to about 100 nanometers and, more preferably, from about 1 iron-carbon, iron-chromium, iron-cobalt, iron—nickel, to about 50 nanometers . . . the normalized magnetic iron nitride (Fe3 N), iron phosphide, iron-silicon, iron interaction between adjacent A moieties 5002 and 5004, and Vanadium, nickel-cobalt, nickel-copper, and the like. One also between 5004 and 5006, is preferably described by the may use alloys of manganese such as, e.g., manganese formula M=exp(-X/L), wherein M is the normalized mag aluminum, manganese-bismuth, MnAS, MnSb, MnTe, man netic interaction, eXp is the base of the natural logarithm ganese-copper, manganese-gold, manganese-nickel, manga (and is approximately equal to 2.71828), X is the distance nese-Sulfur and related compounds, manganese-antimony, between adjacent A moieties, and L is the coherence length.” manganese-tin, manganese-zinc, Heusler alloy, and the like. 0079 U.S. Pat. No. 6,765,144 also discloses that “In one One may use compounds and alloys of the iron group, embodiment, and referring again to FIG. 38, X is preferably including oxides of the iron group, halides of the iron group, measured from the center 5001 of A moiety 5002 to the borides of the transition elements, sulfides of the iron group, center 5003 of A moiety 5004; and X is preferably equal to platinum and palladium with the iron group, chromium from about 0.00001xL to about 100xL. . . . In one embodi compounds, and the like.’ ment, the ratio of X/L is at least 0.5 and, preferably, at least 0074 U.S. Pat. No. 6,765,144 also discloses that: “One 15. may use a rare earth and/or actinide metal Such as, e.g., Ce, 0080 U.S. Pat. No. 6,765,144 also discloses that “Refer Pr, Nd, Pm, Sm, Eu, Gd, Th, Dy, Ho, Er, Tm, Yb, Lu, La, ring again to FIG. 37, the nanomagnetic material may be mixtures thereof, and alloys thereof. One may also use one comprised of 100 percent of moiety A, provided that such or more of the actinides such as, e.g., Th, Pa, U, Np, Pu, Am, moiety A has the required normalized magnetic interaction Cm, Bk. Cf. Es, Fm, Md, No, Lr, Ac, and the like.... These (M). Alternatively, the nanomagnetic material may be com moieties, compounds thereof, and alloys thereof are well prised of both moiety A and moiety B. . . . When moiety B known and are described, e.g., in the aforementioned text of is present in the nanomagnetic material, in whatever form or R. S. Tebble et al. entitled “Magnetic Materials . . . In one forms it is present, it is preferred that it be present at a mole preferred embodiment, moiety A is selected from the group ratio (by total moles of A and B) of from about 1 to about consisting of iron, nickel, cobalt, alloys thereof, and mix 99 percent and, preferably, from about 10 to about 90 tures thereof. In this embodiment, the moiety A is magnetic, percent. . . . The B moiety, in whatever form it is present, is i.e., it has a relative magnetic permeability of from about 1 nonmagnetic, i.e., it has a relative magnetic permeability of to about 500,000. . . . . 1.0; without wishing to be bound to any particular theory, US 2006/01 02871 A1 May 18, 2006 applicants believe that the B moiety acts as buffer between be present by mole percent of total moles of iron and cobalt adjacent A moieties. One may use, e.g., Such elements as present in the ABC moiety. In another embodiment, from silicon, aluminum, boron, platinum, tantalum, palladium, about 50 to about 90 mole percent of iron is present. In yet yttrium, Zirconium, titanium, calcium, beryllium, barium, another embodiment, from about 60 to about 90 mole silver, gold, indium, lead, tin, antimony, germanium, gal percent of iron is present. In yet another embodiment, from lium, tungsten, bismuth, strontium, magnesium, Zinc, and about 70 to about 90 mole percent of iron is present. the like . . . In one embodiment, and without wishing to be bound to any particular theory, it is believed that B moiety 0087. In one preferred embodiment, moiety A is selected provides plasticity to the nanomagnetic material that it from the group consisting of iron, nickel, cobalt, alloys would not have but for the presence of B. . . . . thereof, and mixtures thereof. 0081 U.S. Pat. No. 6,765,144 also discloses that “The 0088. The moiety A may be present in the nanomagnetic use of the B material allows one to produce a coated material either in its elemental form, as an alloy, in a solid Substrate with a springback angle of less than about 45 Solution, or as a compound. degrees. AS is known to those skilled in the arty all materials 0089. In one embodiment, it is preferred at least about 1 have a finite modulus of elasticity; thus, plastic deformations mole percent of moiety A be present in the nanomagnetic followed by some elastic recovery when the load is material (by total moles of A, B, and C), and it is more removed. In bending, this recovery is called springback. See, preferred that at least 10 mole percent of such moiety Abe e.g., page 462 of S. Kalparjian’s “Manufacturing Engineer present in the nanomagnetic material (by total moles of A, ing and Technology.” Third Edition (Addison Wesley Pub B, and C). In one embodiment, at least 60 mole percent of lishing Company, New York, N.Y., 1995). . . . FIG. 39 Such moiety A is present in the nanomagnetic material, (by illustrates how springback is determined in accordance with total moles of A, B, and C.) this invention. Referring to FIG. 39, a coated substrate 5010 is subjected to a force in the direction of arrow 5012 that 0090. In one embodiment, the nanomagnetic material has bends portion 5014 of the substrate to an angle 5016 of 45 the formula A.A.(B),C(C), wherein each of A and As degrees, preferably in a period of less than about 10 seconds. are separate magnetic A moieties, as described above; B is Thereafter, when the force is released, the bent portion 5014 as defined elsewhere in this specification; X is an integer springs back to position 5018. The springback angle 5020 is from 0 to 1; each of C and C is as descried elsewhere in preferably less than 45 degrees and, preferably, is less than this specification; and y is an integer from 0 to 1. about 10 degrees.” 0091. In this embodiment, there are always two distinct A 0082) U.S. Pat. No. 6,765,144 also discloses that “Refer moieties, such as, e.g., nickel and iron, iron and cobalt, etc. ring again to FIG. 37, and in one embodiment, the nano The A moieties may be present in equimolar amounts; or magnetic material is comprised of moiety A, moiety C, and they may be present in non-equimolar amount. optionally moiety B. The moiety C is preferably selected from the group consisting of elemental oxygen, elemental 0092. In one aspect of this embodiment, either or both of nitrogen, elemental carbon, elemental fluorine, elemental the A and A moieties are radioactive. Thus, e.g., either or chlorine, elemental hydrogen, and elemental helium, both of the A and A moieties may be selected from the elemental neon, elemental argon, elemental krypton, group consisting of radioactive cobalt, radioactive iron, elemental xenon, and the like . . . It is preferred, when the radioactive nickel, and the like. These radioactive isotopes C moiety is present, that it be present in a concentration of are well known. Reference may be had, e.g., to U.S. Pat. from about 1 to about 90 mole percent, based upon the total Nos. 3,894,584; 3,936,440 (method of labeling coplex metal number of moles of the A moiety and/or the B moiety and chelates with radioactive metal isotopes); U.S. Pat. Nos. C moiety in the composition.” 4,031,387; 4,282,092; 4,572,797:4,642, 193; 4,659,512; 4,704.245; 4,758,874 (minimization of radioactive material 0083. In one embodiment, the aforementioned moiety A deposition in water-cooled nuclar reactors); U.S. Pat. No. is preferably comprised of a magnetic element selected from 4.950.449 (inhibition of radioactive cobalt deposition); U.S. the group consisting of a transition series metal, a rare earth Pat. No. 4,647.585 (method for separating cobalt, nickel, series metal, or actinide metal, a mixture thereof, and/or an and the like from alloys), U.S. Pat. Nos. 4,759,900; 4,781, alloy thereof. In one embodiment, the moiety A is iron. In 198 (biopsy tracer needle); U.S. Pat. Nos. 4,876.449; 5,035, another embodiment, moiety A is nickel. In yet another 858; 5,196,113: 5,205,167: 5,222,065; 5,241,060 (base moi embodiment, moiety A is cobalt. In yet another embodiment, ety-labeled detectable nucleotide); U.S. Pat. No. 6,314,153: moiety A is gadolinium. In another embodiment, the A and the like. The entire disclosure of each of these United moiety is selected from the group consisting of Samarium, States patents is herey incorporated by reference into this holmium, neodymium, and one or more other member of the specification. Lanthanide series of the periodic table of elements. 0093. In one preferred embodiment, at least one of the A 0084. In one preferred embodiment, two or more A and A moieties is radioactive cobalt. This radioisotope is moieties are present, as atoms. In one aspect of this embodi discussed, e.g., in U.S. Pat. No. 3,936,440, the entire dis ment, the magnetic susceptibilities of the atoms so present closure of which is hereby incorporated by reference into are both positive. this specification. 0085. In one embodiment, two or more A moieties are 0094) In one embodiment, at least one of the A and A present, at least one of which is iron. In one aspect of this is radioactive iron. This radioisotope is also well known as embodiment, both iron and cobalt atoms are present. is evidenced, e.g., by U.S. Pat. No. 4,459,356, the entire 0.086 When both iron and cobalt are present, it is pre disclosure of which is also hereby incorporated by reference ferred that from about 10 to about 90 mole percent of iron into this specification. Thus, and as is disclosed in Such US 2006/01 02871 A1 May 18, 2006

patent, “In accordance with the present invention, a radio yttrium, Zirconium, titanium, calcium, beryllium, barium, active stain composition is developed as a result of intro silver, gold, indium, lead, tin, antimony, germanium, gal duction of a radionuclide (e.g., radioactive iron isotope 59 lium, tungsten, bismuth, strontium, magnesium, Zinc, cop Fe, which is a strong gamma emitter having peaks of 1.1 and per, cesium, cerium, hafnium, iodine, iridium, lanthanum, 1.3 MeV) into BPS to form ferrous BPS. . . . In order to lithium, lutetium, manganese, molybdenum, potassium, prepare the radioactive stain composition, sodium batho Sodium, strontium, praseodymium, rhenium, rhodium, phenanthroline sulfonate (BPS), ascorbic acid and Tris rubidium, ruthenium, Scandium, selenium, tantalum, tech buffer salts were obtained from Sigma Chemical Co. (St. netium, tellurium, chromium, thallium, thorium, thulium, Louis, Mo.). Enzymes grade acrylamide, N.N. methylenebi titanium, Vanadium, Zinc, yttrium, ytterbium, Zirconium, and sacrylamide and N.N.N',N'-tetramethylethylenediamine the like. Reference may be had, e.g., to pages E-118 through (TEMED) are products of and were obtained from Eastman E 123 of the aforementioned CRC Handbook of Chemistry Kodak Co. (Rochester, N.Y.). Sodium dodecylsulfate (SDS) and Physics. was obtained from Pierce Chemicals (Rockford, Ill.). The 0101. In one embodiment, the nanomagnetic particles radioactive isotope (59 FeCl3 in 0.05M HCl, specific activ may be represented by the formula A,B,C, wherein x+y+Z ity 15.6 mC/mg) was purchased from New England Nuclear is equal to 1. In this embodiment the ratio of x/y is at least (Boston, Mass.), but was diluted to 10 ml with 0.5N HCl to 0.1 and preferably at least 0.2; and the ratio of Z/x is from yield an approximately 0.1 mM Fe(III) solution.” 0.001 to about 0.5. 0.095. In the nanomagnetic particles, there may be, but 0102) In one preferred embodiment, the B material is need not be, a B moiety (Such as, e.g., aluminum). There aluminum and the C material is nitrogen, whereby an AlN preferably are at least two C moieties Such as, e.g., oxygen moiety is formed. Without wishing to be bound to any and nitrogen. The A moieties, in combination, comprise at particular theory, applicants believe that aluminum nitride least about 80 mole percent of Such a composition; and they (and comparable materials) are both electrically insulating preferably comprise at least 90 mole percent of such com and thermally conductive, thus providing a excellent com position. bination of properties for certain end uses. 0096. When two C moieties are present, and when the 0103) In one embodiment, the nanomagnetic material is two C moieties are oxygen and nitrogen, they preferably are comprised of moiety A, moiety C, and optionally moiety B. present in a mole ratio such that from about 10 to about 90 The moiety C is preferably selected from the group consist mole percent of oxygen is present, by total moles of oxygen ing of elemental oxygen, elemental nitrogen, elemental and nitrogen. It is preferred that at least about 60 mole carbon, elemental fluorine, elemental chlorine, elemental percent of oxygen be present. In one embodiment, at least hydrogen, and elemental helium, elemental neon, elemental about 70 mole percent of oxygen is so present. In yet another argon, elemental krypton, elemental Xenon, elemental fluo embodiment, at least 80 mole percent of oxygen is so rine, elemental Sulfur, elemental hydrogen, elemental present. helium, the elemental chlorine, elemental bromine, elemen tal iodine, elemental boron, elemental phosphorus, and the 0097. One may measure the surface of the nanomagnetic like. In one aspect of this embodiment, the C moiety is material, measuring the first 8.5 nanometers of material. selected from the group consisting of elemental oxygen, When such surface is measured, it is preferred that at least elemental nitrogen, and mixtures thereof. 50 mole percent of oxygen, by total moles of oxygen and nitrogen, be present in Such surface. It is preferred that at 0104. In one embodiment, the C moiety is chosen from least about 60 mole percent of oxygen be present. In one the group of elements that, at room temperature, form gases embodiment, at least about 70 mole percent of oxygen is so by having two or more of the same elements combine. Such present. In yet another embodiment, at least 80 mole percent gases include, e.g., hydrogen, the halide gases (fluorine, of oxygen is so present. chlorine, bromine, and iodine), inert gases (helium, neon, argon, krypton, Xenon, etc.), etc. 0098. Without wishing to be bound to any particular 0105. In one embodiment, the C moiety is chosen from theory, applicants believe that the presence of two distinct A the group consisting of oxygen, nitrogen, and mixtures moieties in their composition, and two distinct C moieties thereof. In one aspect of this embodiment, the C moiety is (such as, e.g., oxygen and nitrogen), provides better mag a mixture of oxygen and nitrogen, wherein the oxygen is netic properties for applicants' nanomagmetic materials. present at a concentration from about 10 to about 90 mole 0099] The B moiety, in one embodiment, in whatever percent, by total moles of oxygen and nitrogen. form it is present, is preferably nonmagnetic, i.e., it has a 0106. It is preferred, when the C moiety (or moieties) is relative magnetic permeability of about 1.0; without wishing present, that it be present in a concentration of from about to be bound to any particular theory, applicants believe that 1 to about 90 mole percent, based upon the total number of the B moiety acts as buffer between adjacent A moieties. moles of the A moiety and/or the B moiety and the C moiety One may use, e.g., such elements as silicon, aluminum, in the composition. In one embodiment, the C moiety is both boron, platinum, tantalum, palladium, yttrium, Zirconium, oxygen and nitrogen. titanium, calcium, beryllium, barium, silver, gold, indium, 0.107 The molar ratio of A/(A and B and C) generally is lead, tin, antimony, germanium, gallium, tungsten, bismuth, from about 1 to about 99 molar percent and, preferably, from strontium, magnesium, Zinc, and the like. about 10 to about 90 molar percent. In one embodiment, 0100. In one embodiment, the B moiety has a relative such molar ratio is from about 30 to about 60 molar percent. magnetic permeability that is about equal to 1 plus the 0108. The molar ratio of B/(A plus B plus C) generally is magnetic susceptilibity. The relative magnetic susceptilities from about 1 to about 99 mole percent and, preferably, from of silicon, aluminum, boron, platinum, tantalum, palladium, about 10 to about 40 mole percent. US 2006/01 02871 A1 May 18, 2006

0109 The molar ratio of C/(A plus B plus C) generally is 20 nanometers. It is preferred that, regardless of the coher from about 1 to about 99 mole percent and, preferably, from ence length used, it be at least 2 times as great as the about 10 to about 50 mole percent. maximum dimension of the particles 16. 0110. In one embodiment, the B moiety is added to the The Mass Density of the Nanomagnetic Particles nanomagnetic A moiety, preferably with a B/A molar ratio of 0116. In one embodiment, the nanomagnetic material from about 5:95 to about 95:5 (see FIG. 3). In one aspect of preferably has a mass density of at least about 0.001 grams this embodiment, the resistivity of the mixture of the B per cubic centimeter, in one aspect of this embodiment, Such moiety and the A moiety is from about 1 micro-ohm-cm to mass density is at least about 1 gram per cubic centimeter. about 10,000 micro-ohm-cm. As used in this specification, the term mass density refers to 0111. In one particularly preferred embodiment, the A the mass of a give Substance per unit volume. See, e.g., page moiety is iron, the B moiety is aluminum, and the molar ratio 510 of the aforementioned “McGraw-Hill Dictionary of of A/B is about 70:30; the resistivity of this mixture is about Scientific and Technical Terms.” In another embodiment, the 8 micro-ohms-cm. material has a mass density of at least about 3 grams per The Squareness of the Nanomagnetic Particles of the Inven cubic centimeter. In another embodiment, the nanomagnetic tion material has a mass density of at least about 4 grams per cubic centimeter. 0112 As is known to those skilled in the art, the square ness of a magnetic material is the ratio of the residual The Thickness of the Coating 14 magnetic flux and the saturation magnetic flux density. 0.117 Referring again to FIG. 1, and to the preferred Reference may be had, e.g., to U.S. Pat. Nos. 6,627.313, embodiment depicted therein, the coating 14 may be com 6,517,934, 6,458,452, 6,391,450, 6,350,505, 6,248,437, prised of one layer of material, two layers of material, or 6,194,058, 6,042,937, 5,998,048, 5,645,652, and the like. three or more layers of material. Regardless of the number The entire disclosure of such United States patents is hereby of coating layers used, it is preferred that the total thickness incorporated by reference into this specification. Reference 22 of the coating 14 be at least about 400 nanometers and, may also be had to page 1802 of the McGraw-Hill Dictio preferably, be from about 400 to about 4,000 nanometers. In nary of Scientific and Techical Terms, Fourth Edition one embodiment, thickness 22 is from about 600 to about (McGraw-Hill Book Company, New York, N.Y., 1989). At 1,000 nanometers. In another embodiment, thickness 22 is such page 1802, the “squareness ratio' is defined as “The from about 750 to about 850 nanometers. magnetic induction at Zero magnetizing force divided by the maximum magnetic indication, in a symmetric cyclic mag 0118. In the embodiment depicted, the substrate 12 has a netization of a material.” thickness 23 that is substantially greater than the thickness 22. As will be apparent, the coated substrate 10 is not drawn 0113. In one embodiment, the squareness of applicants to Scale. nanomagnetic particles is from about 0.05 to about 1.0. In one aspect of this embodiment, such squareness is from 0119). In general, the thickness 22 is preferably less than about 0.1 to about 0.9. In another aspect of this embodiment, about 5 percent of thickness 23 and, more preferably, less the squareness is from about 0.2 to about 0.8. In applications than about 2 percent. In one embodiment, the thickness 22 where a large residual magnetic moment is desired, the is no greater than about 1.5 percent of the thickness 23. squareness is preferably at least about 0.8. The Flexibility of Coated Substrate 10 0114 FIG. 1 is a schematic illustration, not drawn to 0120 Referring to FIG. 1, and in one preferred embodi scale, of a coated substrate assembly 10 comprised of a ment thereof, substrate 12 is a conductor that preferably has Substrate 12 and, disposed thereon, a coating 14 comprised a resistivity at 20 degrees Centigrade of from about 1 to of a multiplicity of nanomagnetic particles 16. Similar about 100-microohom-centimeters. In this embodiment, dis coated substrate assemblies are illustrated and described in posed above the conductor 12 is a film 14 comprised of applicants’ United States patents. Reference may be had, nanomagnetic particles 16 that preferably have a maximum e.g., to U.S. Pat. No. 6,506.972 (magnetically shielded dimension of from about 10 to about 100 nanometers. The conductor), U.S. Pat. No. 6,700,472 (magnetic thin film film 114 also preferably has a saturation magnetization of inductors), U.S. Pat. No. 6,713,671 (magnetically shielded from about 200 to about 26,000 Gauss and a thickness of less assembly), U.S. Pat. No. 6,765,144 (magnetic resonance than about 2 microns. imaging coated assembly), and the like. The entire disclo sure of each of these United States patents is hereby incor 0.121. In one aspect of this embodiment, conductor porated by reference into this specification. assembly 10 is flexible, having a bend radius of less than 2 centimeters. Reference may be had, e.g., to U.S. Pat. No. 0115 Referring to FIG. 1, and to the preferred embodi 6,506.972, the entire disclosure of which is hereby incor ment depicted therein, it will be seen that the nanomagnetic porated by reference into this specification. A similar device particles 16 are preferably comprised of the “ABC atoms is depicted in FIG. 5 of U.S. Pat. No. 6,713,671; the entire described elsewhere in this specification. With regard to disclosure of such United States patent is hereby incorpo such “ABC particles, the term “coherence length” refers to rated by reference into this specification. the smallest distance 18 between the surfaces 20 of any particles 16 that are adjacent to each other. In one aspect of 0.122. As used in this specification, the term flexible this embodiment, it is preferred that Such coherence length, refers to an assembly that can be bent to form a circle with with regard to such ABC particles, be less than about 100 a radius of less than 2 centimeters without breaking. Put nanometers and, preferably, less than about 50 nanometers. another way, the bend radius of the coated assembly is In one embodiment, such coherence length is less than about preferably less than 2 centimeters. Reference may be had, US 2006/01 02871 A1 May 18, 2006

e.g., to U.S. Pat. Nos. 4,705.353, 5,946,439, 5,315,365, thus deposited often interact with each other to form nano 4,641,917, 5,913,005, and the like. The entire disclosure of sized moieties that are less than 100 nanometers in size. each of these United States patents is hereby incorporated by reference into this specification. The Surface Roughness of the Coating 14 0.130. In one embodiment, the coating 14 (see FIG. 1) has 0123. Without wishing to be bound to any particular an average Surface roughness of less than about 100 nanom theory, applicants believe that the use of nanomagnetic eters and, more preferably, less than about 10 nanometers. particles in their coatings and their articles of manufacture As is known to those skilled in the art, the average surface allows one to produce a flexible device that otherwise could roughness of a thin film is preferably measured by an atomic not be produced were not the materials so used nano-sized force microscope (AFM). Reference may be had, e.g., to (less than 100 nanometers). U.S. Pat. No. 5,420.796 (method of inspecting planarity of 0.124. In another embodiment, not shown, the assembly wafer surface), U.S. Pat. Nos. 6,610,004, 6,140,014, 6,548, 10 is not flexible. 139, 6,383,404, 6,586,322, 5,832,834, and 6,342,277. The entire disclosure of each of these United States patents is The Morphological Density of the Coating 14 hereby incorporated by reference into this specification. 0125. In one preferred embodiment, and referring to FIG. 0131 Alternatively, or additionally, one may measure 1, the coating 14 has a morphological density of at least Surface roughness by a laser interference technique. This about 98 percent. In the embodiment depicted, the coating technique is well known. Reference may be had, e.g., to U.S. 14 has a thickness 22 of from about 400 to about 2,000 Pat. No. 6,285,456 (dimension measurement using both nanometers and, in one embodiment, has a thickness 22 of coherent and white light interferometers), U.S. Pat. Nos. from about 600 to about 1200 nanometers. 6,136,410, 5,843,232 (measuring deposit thickness), U.S. Pat. No. 4,151,654 (device for measuring axially symmetric 0126. As is known to those skilled in the art, the mor aspherics), and the like. The entire disclosure of these United phological density of a coating is a function of the ratio of States patents are hereby incorporated by reference into this the dense coating material on its Surface to the pores on its specification. Surface; and it is usually measured by Scanning electron Hydrophobic and Hydrophilic Coatings microscopy. By way of illustration, e.g., published United States patent application US 2003/0102222A1 contains a 0.132. By varying the surface roughness of the coating 14 FIG. 3A that is a scanning electron microscope (SEM) (see FIG. 1), one may make the surface 17 of such coating image of a coating of “long single-walled carbon nanotubes either hydrophobic or hydrophilic. on a substrate. Referring to this SEM image, it will be seen 0.133 As is known to those skilled in the art, a hydro that the white areas are the areas of the coating where pores phobic material is antagonistic to water and incapable of OCCU. dissolving in water. Inasuch as the average water droplet has 0127. The technique of making morphological density a minimum cross-sectional dimension of at least about 3 measurements also is described, e.g., in a M.S. thesis by nanometers, the water droplets will tend not to bond to a Raymond Lewis entitled “Process study of the atmospheric coated Surface 17 which, has a Surface roughness of, e.g., 1 RF plasma deposition system for oxide coatings' that was nanometer. deposited in the Scholes Library of Alfred University, 0.134 One may vary the average surface roughness of Alfred, N.Y. in 1999 (call Number TP2 a75 1999 vol 1, no. coated surface 17 by varying the pressure used in the 1.). sputtering process described elsewhere in this specification. In general, the higher the gas pressure used, the rougher the 0128. The scanning electron microscope (SEM) images Surface. obtained in making morphological density measurements can be divided into a matrix, as is illustrated in FIGS. 2 and 0.135) If, on the other hand, one modifies the sputtering 3 which schematically illustrate the porosity of the side of process to allow a Surface roughness of at about, e.g., 20 coating 14, and the top of the coating 14. The SEM image nanometers, the water droplets then have an opportunity to depicted shows two pores 34 and 36 in the cross-sectional bond to the surface 17 which, in this embodiment, will tend area 38, and it also shows two pores 40 and 42 in the top 44. to be hydrophilic. As will be apparent, the SEM image can be divided into a Durable Properties of the Coated Substrate 10 matrix whose adjacent lines 46/48, and adjacent lines 50/52 define a square portion with a Surface area of 100 square 0.136. In one embodiment, the coated substrate of this nanometers (10 nanometersx10 nanometers). Each Such invention has durable magnetic properties that do not vary square portion that contains a porous area is counted, as is upon extended exposure to a saline Solution. If the magnetic each Such square portion that contains a dense area. The ratio moment of a coated substrate is measured at “time Zero” of dense areas?porous areas, x 100, is preferably at least 98. (i.e., prior to the time it has been exposed to a saline Put another way, the morphological density of the coating 14 Solution), and then the coated Substrate is then immersed in is at least 98 percent. In one embodiment, the morphological a saline solution comprised of 7.0 mole percent of sodium density of the coating 14 is at least about 99 percent. In chloride and 93 mole percent of water, and if the substrate/ another embodiment, the morphological density of the coat saline Solution is maintained at atmospheric pressure and at ing 14 is at least about 99.5 percent. temperature of 98.6 degrees Fahrenheit for 6 months, the coated Substrate, upon removal from the saline solution and 0129. One may obtain such high morphological densities drying, will be found to have a magnetic moment that is by atomic size deposition, i.e., the particles sizes deposited within plus or minus 5 percent of its magnetic moment at on the Substrate are atomic scale. The atomic scale particles time Zero. US 2006/01 02871 A1 May 18, 2006

0137 In another embodiment, the coated substrate of this terminable magnetic susceptibility), U.S. Pat. No. 5,300,886 invention has durable mechanical properties when tested by (method to enhance the susceptibilityt of MRI for magnetic the saline immersion test described above. susceptibility effects), U.S. Pat. No. 6,208.884 (noninvasive room temperature instrument to measure magnetic suscep 0138 Thus, e.g., the substrate 12, prior to the time it is tibiolity variations in body tissue), U.S. Pat. No. 6,477,398 coated with coating 14, has a certain flexural strength, and (resonant magnetic Susceptibility imaging), and the like. The a certain spring constant. entire disclosure of each of these United States patents is 0.139. The flexural strength is the strength of a material in hereby incorporated by reference into this specification. bending, i.e., its resistance to fracture. As is disclosed in 0144. In one aspect of this embodiment, and referring ASTM C-790, the flexural strength is a property of a solid again to FIG. 1, the substrate 12 is a stent that is comprised material that indicates its ability to withstand a flexural or of wire mesh constructed in Such a manner as to define a transverse load. As is known to those skilled in the art, the spring constant is the constant of proportionality k which multiplicity of openings. The mesh material is preferably a appears in Hooke's law for springs. Hooke's law states that: metal or metal alloy, Such as, e.g., stainless steel, Nitinol (an F=-kX, wherein F is the applied force and x is the displace alloy of nickel and titanium), niobium, copper, etc. ment from equilibrium. The spring constant has units of 0145 Typically the materials used in stents tend to cause force per unit length. current flow when exposed to a radio frequency field. When the field is a nuclear magnetic resonance field, it generally 0140 Means for measuring the spring constant of a has a direct current component, and a radio-frequency material are well known to those skilled in the art. Reference component. For MRI (magnetic resonance imaging) pur may be had, e.g., to U.S. Pat. No. 6,360.589 (device and poses, a gradient component is added for spatial resolution. method for testing vehicle shock absorbers), U.S. Pat. No. 4,970,645 (suspension control method and apparatus for 0146 The material or materials used to make the stent vehicle), U.S. Pat. Nos. 6,575,020, 4,157,060, 3,803,887, itself have certain magnetic properties such as, e.g., mag 4,429,574, 6,021,579, and the like. The entire disclosure of netic susceptibility. Thus, e.g., niobium has a magnetic each of these United States patents is hereby incorporated by susceptibility of 1.95x10 centimeter-gram-second units. reference into this specification. Nitonol has a magnetic susceptibility of from about 2.5 to about 3.8x10 centimeter-gram-second units. Copper has a 0141 Referring again to FIG. 1, the flexural strength of magnetic susceptibility of from -5.46 to about -6.16x10' the uncoated substrate 10 preferably differs from the flexural centimeter-gram-second units. strength of the coated substrate 10 by no greater than about 5 percent. Similarly, the spring constant of the uncoated 0147 The total magnetic susceptibility of an object is substrate 10 differs from the spring constant of the coated equal to the mass of the object times its succeptibility. Thus, substrate 10 by no greater than about 5 percent. assuming an object has equal parts of niobium, Nitinol, and copper, its total susceptibility would be equal to (+1.95+ 0142. In one embodiment, the coating 14 biocompatible 3.15')x10 cgs, or about 0.36x10 cgs. with biological organisms. As used herein, the term biocom patible refers to a coating whose chemical composition does 0.148. In a more general case, where the masses of not change Substantially upon exposure to biological fluids. niobium, Nitinol, and copper are not equal in the object, the Thus, when the coating 14s immersed in a 7.0 mole percent Susceptibility, in c.g.S. units, would be equal to 1.95 saline solution for 6 months maintained at a temperature of Mn+3.15 Mini-5.46Mc, wherein Mn is the mass of niobium, 98.6 degrees Fahrenheit, its chemical composition (as mea Mini is th mass of Nitinol, and Mc is the mass of copper. sured by, e.g., energy dispersive X-ray analysis EDS, or 0.149 Referring again to FIG. 1, and in one preferred EDAX) is substantially identical to its chemical composi embodiment thereof, the coated substrate assembly 10 pref tion at “time Zero.' erably materials that will provide the desired mechanical properties generally do not have desirable magnetic and/or The Susceptibility of the Coated Substrate 10 electromagnetic properties. In an ideal situation, the stent 0143. In one preferred embodiment (see FIG. 1), the 500 will produce no loop currents and no surface eddy coated Substrate 10 has a direct current (d.c.) magnetic currents when exposed to magnetic resonance imaging Susceptibility within a specified range. As is known to those (MRI) radiation and, in such situation, has an effective zero skilled in the art, magnetic susceptibility is the ratio of the magnetic susceptibility. Put another way, ideally the direct magnetization of a material to the magnetic field strength; it current magnetic Susceptibility of an ideal coated Substrate is a tensor when these two quantities are not parallel; that is exposed to MRI radiation should be about 0. otherwise it is a simple number. Reference may be had, e.g., to U.S. Pat. No. 3,614,618 (magnetic susceptibility tester), 0150. A d.c. (“direct current’) magnetic susceptibility of U.S. Pat. No. 3,644,823 (nulling coil for magnetic suscep precisely Zero is often difficult to obtain. In general, it is tibility logging), U.S. Pat. No. 3,758,848 (method and sufficient if the d.c. susceptibility of the coated substrate 10 system with Voltage cancellation for measuring the magnetic is plus or minus 1x10 centimeter-gram-seconds (cgs) and, susceptibility of a subsurface earth formation), U.S. Pat. No. more preferably, plus or minus 1x10 centimeter-gram 3,879,658 (apparatus for measuring magnetic susceptibil seconds. In one embodiment, the d.c. Susceptibility of the ity), U.S. Pat. No. 3,980,076 (method for measuring exter coated substrate 10 is equal to plus or minus 1x10 centi nally of the human body magnetic susceptibility changes), meter-gram-seconds. In another embodiment, the d.c. Sus U.S. Pat. No. 4,277,750 (induction probe for the measure ceptibility of the coated substrate 10 is equal to plus or ment of magnetic susceptibility), U.S. Pat. No. 4,662.359 minus 1x10 centimeter-gram-seconds. (use of magnetic Susceptibility probes in the treatment of 0151. In one embodiment, and referring again to FIG. 1, cancer), U.S. Pat. No. 4,985,165 (material having a prede the coated substrate assembly 10 is in contact with biologi US 2006/01 02871 A1 May 18, 2006 cal tissue 11. In FIG. 1, only a portion of the biological 0.156. In one embodiment, the desired correction for the tissue 11 actually contiguous with assembly 10 is shown for slope of the copper graph may be obtained by coating the the sake of simplicity of representation. In Such an embodi copper with a coating comprised of both nanomagnetic ment, it is preferred that such biological tissue 11 be taken material and nanodielectric material. into account when determining the net Susceptibility of the assembly, and that such net susceptibility of the assembly 10 0157. In one aspect of this embodiment, the nanomag in contact with bodily fluid is plus or minus plus or minus netic material preferably has an average particle size of less 1x10 centimeter-gram-seconds (cgs), or plus or minus than about 20 nanometers and a saturation magnetization of 1x10 centimeter-gram-seconds, or plus or minus 1x10 from 10,000 to about 26,000 Gauss. In another aspect of this centimeter-gram-seconds, or plus or minus 1x10 centime embodiment, the nanomagnetic material used is iron. In ter-gram-seconds. In this embodiment, the materials com another aspect of this embodiment, the nanomagentic mate prising the nanomagnetic coating 14 on the Substrate 12 are rial used is FeAIN. In yet another aspect of this embodiment, chosen to have susceptibility values that, in combination the nanomagnetic material is FeAl. Other suitable materials with the susceptibility values of the other components of the will be apparent to those skilled in the art and include, e.g., assembly, and of the bodily fluid, will yield the desired nickel, cobalt, magnetic rare earth materials and alloys, values. thereof, and the like. 0158. In this embodiment, the nanodielectric material 0152 The prior art has heretofore been unable to provide used preferably has a resistivity at 20 degrees Centigrade of such an implantable stent that will have the desired degree from about 1x10 ohm-centimeters to about 1x10" ohm of net magnetic susceptibility. Applicants invention allows centimeters. one to compensate for the deficiencies of the current stents, and/or of the current stents in contact with bodily fluid, by 0159 Referring again to FIG. 4, and in the preferred canceling the undesirable effects due to their magnetic embodiment depicted therein, a coated stent assembly 100 Susceptibilities, and/or by compensating for Such undesir that is comprised of a stent 104 on which is disposed a able effects. coating 103 is illustrated. The coating 103 is comprised of nanomagnetic material 120 that is preferably homoge 0153. When different objects are subjected to an electro neously dispersed within nanodielectric material 122, which magnetic field (such as an MRI field), they will exhibit acts as an insulating matrix. different magnetic responses at different field strengthes. Thus, e.g., copper, at a d.c. field strength of 1.5 Tesla, 0.160 In general, the amount of nanodielectric material changes its magnetization as a function of the composite 122 in coating 103 exceeds the amount of nanomagnetic field strength (including the d.c. field strength, the rf field material 120 in such coating 103. strength, and the gradient field strength) at a rate (defined by 0.161 In one embodiment, the coating 103 is comprised delta-magnetization/delta composite field strength) that is of at least about 70 mole percent of such nanodielectric decreasing. With regard to ther.f. field and the gradient field, material (by total moles of nanomagnetic material and it should be understood that the order of magnitude of these nanodielectric material). In another embodiment, the coating fields is relatively small compared to the d.c. field, which is 103 is comprised of less than about 20 mole percent of the usually about 1.5 Tesla. The slope of the graph of magne nanomagnetic material 120, by total moles of nanomagnetic tization versus field strength for copper is negative; this material and nanodielectric material. In one embodiment, negative slope indicates that copper, in response to the the nanodielectric material used is aluminum nitride. applied fields, is opposing the applied fields. Because the applied fields (including rif fields, and the gradient fields), 0162 Referring again to FIG. 4, one may optionally are required for effective MRI imaging, the response of the include nanoconductive material 424 in the coating 103. copper to the applied fields tends to block the desired This nanoconductive material 124 generally has a resistivity imaging. The d.c. Susceptibility of copper is equal to the at 20 degrees Centigrade of from about 1x10 ohm-centi mass of the copper present in the device 10 times its meters to about 1x10 ohm-centimeters; and it generally magnetic Susceptibility. has an average particle size of less than about 100 nanom eters. In one aspect of this embodiment, the nanoconductive 0154 By comparison to copper, the ideal magnetization material used is aluminum. response of a composite assembly (such as, e.g., assembly 0.163 Referring again to FIG. 4, and in the embodiment 10) will be a line whose slope is substantially zero. As used depicted, it will be seen that two layers 105/107 are pref herein, the term “substantially Zero' includes a slope will erably used to obtain the desired correction. In one embodi produce an effective magnetic susceptibility of from about ment, three or more such layers are used. Regardless of the 1x10 to about 1x10 centimeters-gram-second (cgs). number of such layers 105/107 used, it is preferred that the 0155 One means of correcting negative slope the graph thickness 110 of coating 103 be from about 400 to about for copper is by coating the copper with a coating which 4000 nanometers produces a magnetization response with a positive slope so that the composite material produces the desired effective 0164. In the embodiment depicted in FIG. 4, the direct magnetic susceptibility of from about 1x107 to about 1x10 current susceptibility of the assembly depicted is equal to the centimeters-gram-second (cgs) units. In order to do so, the sum of the (mass)x(susceptibility) for each individual layer following equation must be satisfied: (magnetic Susceptibil 1057107 and for the Substrate 104. ity of the uncoated device) (mass of uncoated device)+ 0.165. As will be apparent, it may be difficult with only (magnetic Susceptibility of copper) (mass of copper)=from one layer of coating material to obtain the desired correction about 1x107 to about 1x10 centimeters-gram-second for the material comprising the stent assembly 400. With a (cgs). multiplicity of layers comprising the coating 103, which US 2006/01 02871 A1 May 18, 2006

may have the same and/or different thicknesses, and/or the for the conventional assay methods since they require that same and/or different masses, and/or the same and/or dif magnetic micro-particles used for labeling be efficiently ferent compositions, and/or the same and/or different mag guided even when a weak magnetic force is applied. netic susceptibilities, more flexibility is provided in obtain 0.172. The preparation of these superparamagnetic mate ing the desired correction. rials is discussed at columns 6 et seq. of U.S. Pat. No. 0166 Without wishing to be bound to any particular 5,238,811, wherein it is disclosed that: “The ferromagnetic theory, applicants believe that, in the assembly 100 depicted Substances can be selected appropriately, for example, from in FIG. 4, each of the different species 120/122/124 within various compound magnetic Substances such as magnetite the coatings 105/107 retains its individual magnetic charac and gamma-ferrite, metal magnetic Substances such as iron, teristics. These species are preferably not alloyed with each nickel and cobalt, etc. The ferromagnetic Substances can be other, when Such species are alloyed with each other, each converted into ultramicro particles using conventional meth of the species does not retain its individual magnetic char ods excepting a mechanical grinding method, i.e., various acteristics. gas phase methods and liquid phase methods. For example, an evaporation-in-gas method, a laser heating evaporation 0167. An alloy, as that term is used in this specification, method, a coprecipitation method, etc. can be applied. The is a substance having magnetic properties and consisting of ultramicro particles produced by the gas phase methods and two or more elements, which usually are metallic elements. liquid phase methods contain both Superparamagnetic par The bonds in the alloy are usually metallic bonds, and thus ticles and ferromagnetic particles in admixture, and it is the individual elements in the alloy do not retain their therefore necessary to separate and collect only those par individual magnetic properties because of the Substantial ticles which show Superparamagnetic property. For the sepa “crosstalk” between the elements via the metallic bonding ration and collection, various methods including mechani process. cal, chemical and physical methods can be applied, examples of which include centrifugation, liquid chroma 0168 By comparison, e.g., materials that are covalently tography, magnetic filtering, etc. The particle size of the bond to each other are more likely to retain their individual Superparamagnetic ultramicro particles may vary depending magnetic characteristics; it is such materials whose behavior upon the kind of the ferromagnetic Substance used but it is illustrated in FIG. 4. Each of the “magnetically distinct must be below the critical size of single domain particles. materials may be, e.g., a material in elemental form, a Preferably, it is not larger than 10 nm when the ferromag compound, an alloy, etc. netic Substance used is magnetite or gamma-ferrite and it is 0169. In one embodiment, and referring again to FIG. 4. not larger than 3 nm when pure iron is used as a ferromag one may mix "positively magnetized materials” with “nega netic Substance, for example.” tively magnetized materials” to obtain the desired degree of 0173 Ferromagnetic materials may also be used as the net magnetization. As is known to those skilled in the art, the positively magnetized species. AS is known to those skilled positively magnetized species include, e.g., those species in the art, ferromagnetism is a property, exhibited by certain that exhibit paramagetism, Superparamagnetism, ferromag metals, alloys, and compounds of the transition (iron group), netism, and/or ferrimagnetism. rare-earth, and actinide elements, in which the internal 0170 Paramagnetism is a property exhibited by sub magnetic moments spontaneously organize in a common stances which, when placed in a magnetic field, are mag direction; this property gives rise to a permeability consid netized parallel to the field to an extent proportional to the erably greater than that of a cuum, and also to magnetic field (except at very low temperatures or in extremely large hysteresis. Reference may be had, e.g., to U.S. Pat. Nos. magnetic fields). Paramagnetic materials are well known to 6,475,650; 6.299,990; 6,690.287 (ferromagnetic material those skilled in the art. Reference may be had, e.g., to U.S. having improved impedance matching); U.S. Pat. No. 6,366, Pat. No. 5,578.922 (paramagnetic material in solution), U.S. 083 (crud layer containing ferromagnetic material on Pat. No. 4,704.871 (magnetic refrigeration apparatus with nuclear fuel rods); U.S. Pat. No. 6,011,674 (magnetoreis belt of paramagnetic material), U.S. Pat. No. 4,243,939 stance effect multilayer film with ferromagnetic film sub (base paramagnetic material containing ferromagnetic impu layers of different ferromagnetic material compositions); rity), U.S. Pat. No. 3,917,054 (articles of paramagnetic U.S. Pat. No. 5,648,015 (process for preparing ferromag material), U.S. Pat. No. 3,796,4999 (paramagnetic material netic materials); U.S. Pat. Nos. 5,382.304: 5,272.238 disposed in a gas mixture), and the like. The entire disclo (organo-ferromagnetic material); U.S. Pat. No. 5,247,054 sure of each of these United States patents is hereby incor (organic polymer ferromagnetic material); U.S. Pat. No. porated by reference into this specification. 5,030,371 (acicular ferromagnetic material consisting essen tially of iron-containing chromium dioxide); U.S. Pat. No. 0171 Superparamagnetic materials are also well known 4.917,736 (passive ferromagnetic material); U.S. Pat. No. to those skilled in the art. Reference may be had, e.g., to U.S. 4,863,715 (contrast agent comprising particles of ferromag Pat. No. 5,238,811, the entire disclosure of which is hereby netic material); U.S. Pat. No. 4,835,510 (magnetoresistive incorporated by reference into this specification, it is dis element of ferromagnetic material); U.S. Pat. No. 4,739,294 closed (at column 5) that: “In one embodiment, the super (amorphous and non-amorphous ferromagnetic material); paramagnetic material used is a Substance which has a U.S. Pat. No. 4,289.937 (fine grain ferromagnetic material); particle size Smaller than that of a ferromagnetic material U.S. Pat. No. 4,023,412 (the Curie point of a ferromagnetic and retains no residual magnetization after disappearance of material); U.S. Pat. No. 4,015,030 (stabilized ferromagnetic the external magnetic field. The Superparamagnetic material material); U.S. Pat. No. 4,004,997 (a polymerizable com and ferromagnetic material are quite different from each postion containing a magnetized powdered ferromagnetic other in their hysteresis curve, susceptibility, Mesbauer material); U.S. Pat. No. 3,851.375 (sintered oxidic ferro effect, etc. Indeed, ferromagnetic materials are most Suited magnetic material); U.S. Pat. No. 3,850,706 (ferromagnetic US 2006/01 02871 A1 May 18, 2006

materials comprised of transition metals); and the like. The 6,159.271 (diamagnetic liquid); U.S. Pat. No. 5,408,178 entire disclosure of each of these United States patents is (diamagnetic and paramagnetic objects); U.S. Pat. No. hereby incorporated by reference into this specification. 5.315.997 (method of magnetic resonance imaging using 0174 Ferrimagnetic materials may also be used as the diamagnetic contrast); U.S. Pat. Nos. 5,162.301; 5,047,392 positively magnetized specifies. AS is known to those skilled (diamagnetic colloids); U.S. Pat. Nos. 5,043,101: 5,026,681 in the art, ferrimagnetism is a type of magnetism in which (diamagnetic colloid pumps); U.S. Pat. No. 4,908,347 (dia the magnetic moments of neighboring ions tend to align magnetic flux shield); U.S. Pat. Nos. 4,778,594; 4,735,796: nonparallel, usually antiparallel, to each other, but the 4,590,922; 4,290,070; 3,899,758; 3,864,824; 3,815,963 moments are of different magnitudes, so there is an appre (pseudo-diamagnetic suspension); U.S. Pat. Nos. 3,597,022; ciable, resultant magnetization. Reference may be had, e.g., 3,572.273; and the like. The entire disclosure of each of to U.S. Pat. Nos. 6,538,919; 6,056,890 (ferrimagnetic mate these United States patents is hereby incorporated by refer rials with temperature stability); U.S. Pat. Nos. 4,649,495; ence into this specification. 4,062.920 (lithium-containing ferrimagnetic materials); 0179. By way of further illustration, the diamagnetic U.S. Pat. Nos. 4,059,664; 3,947,372 (ferromagnetic mate material used may be an organic compound with a negative rial); U.S. Pat. No. 3,886,077 (garnet structure ferromag suspceptibility. Referring to pages E-123 to pages E-134 of netic material); U.S. Pat. Nos. 3,765,021; 3,670,267; and the the aforementioned CRC Handbook, such compounds like. The entire disclosure of each of these United States include, e.g.: alanine; allyl alcohol; amylamine; aniline; patents is hereby incorporated by reference into this speci asparagines; aspartic acid; butyl alcohol; chloresterol; cou fication. marin; diethylamine; erythritol; eucalyptol; fructose; galac 0175. By way of yet further illustration, and not limita tose; glucose: D-glucose; glutamic acid; glycerol, glycine; tion, some Suitable positively magnetized species include, leucine; isoleucine; mannitol; mannose; and the like. e.g., iron; iron/aluminum; iron/aluminum oxide; iron/alumi 0180 Referring again to FIG. 4, when a positively mag num nitride; iron?tantalum nitride; iron?tantalum oxide; netized species is mixed with a negatively magnetized nickel; nickel/cobalt, cobalt/iron; cobalt; Samarium; gado species, and assuming that each species retains its magnetic linium; neodymium, mixtures thereof nano-sized particles properties, the resulting magnetic properties exhibit Substan of the aforementioned mixtures, where Super-paramagnetic tially Zero magnetization. In this embodiment, one must properties are exhibited; and the like. insure that the positively magnetized species does not lose 0176). By way of yet further illustration, other suitable its magnetic properties, as often happens when one material positively magnetized species are listed in the “CRC Hand is alloyed with another. The magnetic properties of alloys book of Chemistry and Physics.” 63" Edition (CRC Press, and compounds containing different species are known, and Inc., Boca-Raton, Fla., 1982-1983). As is discussed on pages thus it readily ascertainable whether the different species E-118 to E-123 of such CRC Handbook, materials with that make up such alloys and/or compounds have retained positive Susceptibility include, e.g., aluminum, americium, their unqiue magnetic characteristics. cerium (beta form), cerium (gamma form), cesium, com 0181. Without wishing to be bound to any particular pounds of cobalt, dysprosium, compounds of dysprosium, theory, applicants believe that, when a positively magnetized europium, compounds of europium, gadolium, cmpounds of species is mixed with a negatively magnetized species, and gadolinium, hafnium, compounds of holmium, iridium, assuming that each species retains its magnetic properties, compounds of iron, lithium, magnesium, manganese, the desired magnetization plot (Substantially Zero slope) will molybdenum, neodymium, niobium, osmium, palladium, be achieved when the volume of the positively magnetized plutonium, potassium, praseodymium, rhodium, rubidium, species times its positive Susceptibility is substantially equal ruthenium, Samarium, Sodium, strontium, tantalum, techni to the Volume of the negatively magnetized Speices times its cium, terbium, thorium, thulium, titanium, tungsten, ura negative susceptibility For this relationship to hold, how nium, Vanadium, ytterbium, yttrium, and the like. ever, each of the positively magnetized species and the 0177. In addition to using positively magnetized species negatively magnetized species must retain the distinctive in coating 103 (see FIG. 4), one may also use negatively magnetic characteristics when mixed with each other. magnetized species. The negatively magnetized species 0182. Thus, for example, if element A has a positive include those materials with negative Susceptibilities that are magnetic susceptibility, and element B has a negative mag listed on such pages E-118 to E-123 of the CRC Handbook. netic Susceptibility, the alloying of A and B in equal pro By way of illustration and not limitation, such species portions may not yield a Zero magnetization compact. include, e.g.: antimony; argon, arsenic; barium; beryllium; 0183 Without wishing to be bound to any particular bismuth; boron; calcium; carbon (dia); chromium; copper, theory, nano-sized particles, or micro-sized particles (with a gallium; germanium; gold; indium, krypton; lead; mercury; size of at least about 0.5 nanometers) tend to retain their phosphorous; selenium; silicon; silver, Sulfur, tellurium; magnetic properties as long as they remain in particulate thallium; tin (gray); Xenon; Zinc, and the link. form. On the other hand, alloys of such materials often do 0178 Many diamagnetic materials also are suitable nega not retain Such properties. tively magnetized species. AS is known to those skilled in the art, diamagnetism is that property of a material that is Nullification of the Susceptibility Contribution Due to the repelled by magnets. The term "diamagnetic susceptibility” Substrate refers to the Susceptibility of a diamagnetic material, which 0.184 As will be apparent by reference, e.g., to FIG. 4. is always negative. Diamagnetic materials are well known to when the substrate 104 is a copper stent, the copper substrate those skilled in the art. Reference may be had, e.g., to U.S. 104 depicted therein has a negative susceptibility, the coat Pat. No. 6,162.364 (diamagnetic objects); U.S. Pat. No. ing 103 depicted therein preferably has a positive suscepti US 2006/01 02871 A1 May 18, 2006 bility, and the coated substrate 100 thus has a substantially ceptibilities for various elements are -9.0 for beryllium, Zero Susceptibility. As will also be apparent, some Substrates -280.1 for bismuth(s), -10.5 for bismuth (l), -6.7 for boron, (such niobium, nitinol, stainless steel, etc.) have positive -56.4 for bromine (l), -73.5 for bromine(g), -19.8 for Susceptibilities. In Such cases, and in one preferred embodi cadmium(s), -18.0 for cadmium.(1), -5.9 for carbon(dia), ment, the coatings should preferably be chosen to have a -6.0 for carbon (graph), -5.46 for copper(s), -6.16 for negative Susceptibility so that, under the conditions of the copper(1), -76.84 for germanium, -28.0 for gold(s), -34.0 MRI radiation (or of any other radiation source used), the net for gold(1), -25.5 for indium, -88.7 for iodine(s), -23.0 for susceptibility of the coated object is still substantially zero. lead(s), -15.5 for lead(1), -19.5 for silver(s), -24.0 for As will be apparent, the contribution of each of the materials silver(1), -15.5 for sulfur(alpha), -14.9 for sulfur(beta), in the coating(s) is a function of the mass of Such material -15.4 for sulfur(1), -39.5 for tellurium(s), -6.4 for telluri and its magnetic Susceptibility. um.(1), -37.0 for tin(gray), -31.7 for tin(gray), -4.5 for tin(1), -11.4 for Zinc(s), -7.8 for Zinc(1), and the like. As will be 0185. The magnetic susceptibilities of various substrate apparent, each of these values is expressed in units equal to materials are well known. Reference may be had, e.g., to the number in questionx10 centimeter-gram seconds at a pages E-118 to E-123 of the “Handbook of Chemistry and temperature at or about 293 degrees Kelvin. As will also be Physics, 63rd edition (CRC Press, Inc., Boca Raton, Fla., apparent, those materials which have a negative suscepti 1974). bility value are often referred to as being diamagnetic. 0186 Once the susceptibility of the substrate 104 mate 0193 By way of further reference, a listing of organic rial is determined, one can use the following equation: compounds that are diamagnetic is presented on pages E123 X+X=0, wherein X is the Susceptibility of the Sub strate, and X is the susceptibility of the coating, when to E134 of the aforementioned “Handbook of Chemistry and each of these is present in a 1/1 ratio. As will be apparent, Physics, 63rd edition (CRC Press, Inc., Boca Raton, Fla., the aforementioned equation is used when the coating and 1974). substrate are present in a 1/1 ratio. When other ratios are 0194 In one embodiment, and referring again to the used other than a 1/1 ratio, the volume percent of each aforementioned “Handbook of Chemistry and Physics.” component (or its mass) must be taken into consideration in 63rd edition (CRC Press, Inc., Boca Raton, Fla., 1974), one accordance with the equation: (volume percent of Substratex or more of the following magnetic materials described Susceptibility of the Substrate)+(Volume percent of coatingx below are preferably incorporated into the coating. Susceptibility of the coating)=0. One may use a comparable 0195 The desired magnetic materials, in this embodi formula in which the weight percent of each component is ment, preferably have a positive susceptibility, with values substituted for the volume percent, if the susceptibility is ranging from +1x10 centimeter-gram seconds at a tem measured in terms of the weight percent. perature at or about 293 degrees Kelvin, to about 1x107 0187. By way of illustration, and in one embodiment, the centimeter-gram seconds at a temperature at or about 293 uncoated Substrate 104 may either comprise or consist degrees Kelvin. essentially of niobium, which has a susceptibility of +195.0x 0196. Thus, by way of illustration and not limitation, one 10 centimeter-gram seconds at 298 degrees Kelvin. may use materials such as Alnicol (see page E-112 of the 0188 In another embodiment, the substrate 104 may CRC handbook), which is an alloy containing nickel, alu contain at least 98 molar percent of niobium and less than 2 minum, and other elements such as, e.g., cobalt and/or iron. molar percent of Zirconium. Zirconium has a Susceptibility Thus, e.g., one my use silicon iron (see page E 113 of the of -122x0x10 centimeter-gram seconds at 293 degrees CRC handbook), which is an acid resistant iron containing Kelvin. As will be apparent, because of the predominance of a high percentage of silicon. Thus, e.g., one may use steel niobium, the net susceptibility of the uncoated substrate will (see page 117 of the CRC handbook). Thus, e.g., one may be positive. use elements such as dyprosium, erbium, europium, gado linium, hafnium, holmium, manganese, molybdenum, 0189 The substrate may comprise Nitinol. Nitinol is a neodymium, nickel-cobalt, alloys of the above, and com paramagnetic alloy, an intermetallic compound of nickel and pounds of the above Such as, e.g., their oxides, nitrides, titanium; the alloy preferably contains from 50 to 60 percent carbonates, and the like. of nickel, and it has a permeability value of about 1.002. The susceptibility of Nitinol is positive. Nullification of the Reactance of the Uncoated Substrate 104 0190. Nitinols with nickel content ranging from about 53 0197). In one preferred embodiment, and referring again to 57 percent are known as “memory alloys’ because of their to FIG. 4, the uncoated substrate 104 has an effective ability to “remember or return to a previous shape upon inductive reactance at a d.c. field of 1.5 Tesla that exceeds being heated which is an alloy of nickel and titanium, in an its capacitative reactance, whereas the coating 103 has a approximate 1/1 ratio. The susceptibility of Nitinol is posi capacitative reatance that exceeds its inductive reactance. The coated (composite) substrate 100706 has a net reactance tive. that is preferably substantially zero. 0191 The substrate 104 may comprise tantalum and/or titanium, each of which has a positive Susceptibility. See, 0198 As will be apparent, the effective inductive reac tance of the uncoated stent 104 may be due to a multiplicity e.g., the CRC handbook cited above. of factors including, e.g., the positive magnetic Susceptibil 0192 When the uncoated substrate has a positive sus ity of the materials which it is comprised of it, the loop ceptibility, the coating to be used for such a substrate should currents produced, the Surface eddy produced, etc. Regard have a negative Susceptibility. Referring again to said CRC less of the source(s) of its effective inductive reactance, it handbook, it will be seen that the values of negative sus can be “corrected by the use of one or more coatings which US 2006/01 02871 A1 May 18, 2006 provide, in combination, an effective capacitative reactance gram-seconds. In another embodiment, the d.c. Susceptibil that is equal to the effective inductive reactance. ity of the assembly 13 is equal to plus or minus 1x10 centimeter-gram-seconds. Imaging of Restenosis 0207 As will be apparent, there may be other materials/ 0199 Referring again to FIG. 4, and in the embodiment components in the assembly 13 whose values of positive or depicted, plaque particles 130,132 are disposed on the inside negative Susceptibility, and/or their mass, may be chosen of substrate 104. When the net reactance of the coated Such that the total magnetic susceptibility of the assembly is substrate 104 is essentially Zero, the imaging field 140 can plus or minus 1xx10 centimeter-gram-seconds (cgs) and, pass Substantially unimpeded through the coating 103 and more preferably, plus or minus 1x10 centimeter-gram the substrate 104 and interact with the plaque particles seconds. Similarly, the configuration of the Substrate may be 130/132 to produce imaging signals 141. varied in order to vary its magnetic susceptibility properties 0200. The imaging signals 141 are able to pass back and/or other properties. through the substrate 104 and the coating 103 because the Cancellation of the Positive Susceptibility of a Nitinol Stent net reactance is Substantially Zero. Thus, these imaging signals are able to be received and processed by the MRI 0208. In one preferred embodiment, illustrated in FIG. 5, apparatus. a stent 200 constructed form Nitinol is comprised of struts 202, 204, 206, and 208 coated with a layer of elemental 0201 Thus, by the use of applicants technology, one bismuth. As is known to those skilled in the art, Nitinol is a may negate the negative Substrate effect and, additionally, paramagnetic alloy that was developed by the Naval Ord provide pathways for the image signals to interact with the nance Laboratory; it is an intermetallic compound of nickel desired object to be imaged (such as, e.g., the plaque and titanium. See, e.g., page 552 of George S. Brady et al.'s particles) and to produce imaging signals that are capable of “Materials Handbook.” Thirteenth Edition (McGraw-Hill escaping the Substrate assembly and being received by the Company, New York, N.Y., 1991). MRI apparatus. 0209 Referring again to FIG. 5, and to the preferred 0202 Referring again to FIG. 4, and in one preferred embodiment depicted therein, the stent 200 is preferably embodiment, when an MRI MRI field is present, the entire cylindrical with a diameter (not shown) of less than 1 assembly 13, including the biological material 130/132, centimeter and a length 210 of about 3 centimeters. Each preferably presents a direct current magnetic Susceptibility Strut, such as strut 202, is preferably arcuate, having an that is plus or minus 1x10 centimeter-gram-seconds (cgs) effective diameter 212 of less than about 1 millimeter. and, more preferably, plus or minus 1x10 centimeter gram-seconds. In one embodiment, the d.c. Susceptibility of 0210. As is known to those skilled in the art, the magnetic the assembly 13 is equal to plus or minus 1x10 centimeter permeability of the Nitinol material is about 1.003; and its gram-seconds. In another embodiment, the d.c. Susceptibil Susceptibility is about 0.03 centimeter-grams-seconds (cgs). ity of the assembly 13 is equal to plus or minus 1x10 In order to nullify the susceptibility, one can introduce a centimeter-gram-seconds. diamagnetic material. Such as bismuth, that has a negative Susceptibility. In one embodiment, a bismuth coating with a 0203 Referring again to FIG. 4, each of the components thickness of form about 10 to about 20 microns is deposited of assembly 13 has its own value of magnetic susceptibility. upon each of the struts 202. Thus, the biological material 130/132 has a magnetic sus ceptibility of S. Thus, the substrate 104 has a magnetic 0211 Thus, and as will be apparent from the discussions Susceptibility of S. Thus, the coating 103 has a magnetic presented in other parts of this specification, the Suscepti susceptibility of S. bility for these struts 202 becomes substantially zero, whereby there is no Substantial direct current (d.c.) Suscep 0204 Each of the components of the assembly 13 makes tibility distortion in the MRI field. As used herein, the term a contribution to the total magnetic Susceptibility of Such “substantially Zero” refers to a net susceptibility of from assembly, depending upon (a) whether its magnetic Suscep about 0.9 to about 1.1. tibility is positive or negative, (b) the amount of its positive or negative Susceptibility value, and (c) the percentage of the 0212. As will be apparent, when applicant’s nanomag netic coating 103 is added to such stent 210, the amount and total mass that the individual coponenent represents. type of the coating is chosen Such that the net Susceptibility 0205. In determining the total susceptibility of the assem for the struts is still preferably substantially Zero, bly 13, one can first determine the product of Mc and Sc, 0213 As will be also be apparent, susceptibility varies wherein Mc is the weight fraction of that component (the with both direct current and alternating current. It is desired weight of that component divided by the total weight of all that, with the composite coating 103 described hereinabove, components in the assembly 6000). the susceptibility at a direct current field of about 1.5 Tesla 0206. In one preferred process, the McSc values for the (which is also the slope of the plot of magnetization versus nanomagentic material 120 are chosen to, when appropriate, the applied magnetic field), should preferably be from about correct for the total McSc values of all of the other compo 0.9 to about 1.1. nents (including the biological material 130/132) such that, after such correction(s), the total susceptibility of the assem Incorporation by Reference of U.S. Pat. No. 6,713,671 bly 13 is plus or minus 1xx10 centimeter-gram-seconds 0214 United States patent application U.S. Ser. No. (cgs) and, more preferably, plus or minus 1x10 centimeter 10/303.264 (and also U.S. Pat. No. 6,713,671) discloses a gram-seconds. In one embodiment, the d.c. Susceptibility of shielded assembly comprised of a Substrate and, disposed the assembly 13 is equal to plus or minus 1x10 centimeter above a Substrate, a shield comprising from about 1 to about US 2006/01 02871 A1 May 18, 2006

99 weight percent of a first nanomagnetic material, and from process of Such FIG. 2 describes disposing insulating mate about 99 to about 1 weight percent of a second material with rial between the coated conductors 14 and 16. This step may a resistivity of from about 1 microohm-centimeter to about be done simultaneously with step 40; and it may be done 1x1025 microohm centimeters; the nanomagnetic material thereafter. comprises nanomagnetic particles, and these nanomagnetic particles respond to an externally applied magnetic field by 0221 Referring again to such FIG. 2, and to the preferred realigning to the externally applied field. Such a shielded embodiment depicted therein, the insulating material 42, the assembly and/or the substrate thereof and/or the shield insulating material 44, and the insulating material 46 each thereof may be used in the processes, compositions, and/or generally has a resistivity of from about 1,000,000,000 to constructs of this invention. about 10,000,000,000,000 ohm-centimeters. 0215. As is disclosed in U.S. Pat. No. 6,713,617, the 0222 Referring again to FIG. 2 of U.S. Pat. No. 6,713, entire disclosure of which is hereby incorporated by refer 671, after the insulating material 42/44/46 has been depos ence into this specification, in one embodiment the Substrate ited, and in one embodiment, the coated conductor assembly used may be, e.g., comprised of one or more conductive is preferably heat treated in step 50. This heat treatment material(s) that have a resistivity at 20 degrees Centigrade of often is used in conjunction with coating processes in which from about 1 to about 100 microohm-centimeters. Thus, e.g., the heat is required to bond the insulative material to the the conductive material(s) may be silver, copper, aluminum, conductors 14/16. alloys thereof, mixtures thereof, and the like. 0223 The heat-treatment step may be conducted after the 0216) In one embodiment, the substrate consists consist deposition of the insulating material 42/44/46, or it may be essentially of Such conductive material. Thus, e.g., it is conducted simultaneously therewith. In either event, and preferred not to use, e.g., copper wire coated with enamel in when it is used, it is preferred to heat the coated conductors 14/16 to a temperature of from about 200 to about 600 this embodiment. degrees Centigrade for from about 1 minute to about 10 0217. In the first step of the process preferably used to minutes. make this embodiment of the invention, (see step 40 of FIG. 1 of U.S. Pat. No. 6,713,671), conductive wires are coated 0224) Referring again to FIG. 1A of U.S. Pat. No. with electrically insulative material. Suitable insulative 6,713,671 and in step 52 of the process, after the coated materials include nano-sized silicon dioxide, aluminum conductors 14/16 have been subjected to heat treatment step oxide, cerium oxide, yttrium-stabilized zirconia, silicon car 50, they are allowed to cool to a temperature of from about bide, silicon nitride, aluminum nitride, and the like. In 30 to about 100 degrees Centigrade over a period of time of general, these nano-sized particles will have a particle size from about 3 to about 15 minutes. distribution such that at least about 90 weight percent of the 0225. One need not invariably heat treat and/or cool. particles have a maximum dimension in the range of from Thus, referring to such FIG. 1A, one may immediately coat about 10 to about 100 nanometers. nanomagnetic particles onto to the coated conductors 14/16 0218. In such process, the coated conductors may be in step 54 either after step 48 and/or after step 50 and/or after prepared by conventional means such as, e.g., the process step 52. described in U.S. Pat. No. 5,540,959, the entire disclosure of 0226 Referring again to FIG. 1A of U.S. Pat. No. which is hereby incorporated by reference into this specifi 6,713,671 in step 54, nanomagnetic materials are coated cation. Alternatively, one may coat the conductors by means onto the previously coated conductors 14 and 16. This is best of the processes disclosed in a text by D. Satas on “Coatings shown in FIG. 2 of Such patent, wherein the nanomagnetic Technology Handbook” (Marcel Dekker, Inc., New York, particles are identified as particles 24. N.Y., 1991). As is disclosed in such text, one may use cathodic arc plasma deposition (see pages 229 et seq.), 0227. In general, and as is known to those skilled in the chemical vapor deposition (see pages 257 et seq.), sol-gel art, nanomagnetic material is magnetic material which has coatings (see pages 655 et seq.), and the like. an average particle size less than 100 nanometers and, preferably, in the range of from about 2 to 50 nanometers. 0219 FIG. 2 of U.S. Pat. No. 6,713,671 is a sectional Reference may be had, e.g., to U.S. Pat. No. 5,889,091 view of the coated conductors 14/16. In the embodiment (rotationally free nanomagnetic material), U.S. Pat. Nos. depicted in such FIG. 2, it will be seen that conductors 14 5,714,136, 5,667,924, and the like. The entire disclosure of and 16 are separated by insulating material 42. In order to each of these United States patents is hereby incorporated by obtain the structure depicted in such FIG. 2, one may reference into this specification. simultaneously coat conductors 14 and 16 with the insulat ing material so that Such insulators both coat the conductors 0228. In general, the thickness of the layer of nanomag 14 and 16 and fill in the distance between them with netic material deposited onto the coated conductors 14/16 is insulation. less than about 5 microns and generally from about 0.1 to about 3 microns. 0220 Referring again to such FIG. 2 of U.S. Pat. No. 6,713,671, the insulating material 42 that is disposed 0229) Referring again to FIG. 2 of U.S. Pat. No. 6,713, between conductors 14/16, may be the same as the insulating 671, after the nanomagnetic material is coated in step 54, the material 44/46 that is disposed above conductor 14 and coated assembly may be optionally heat-treated in step 56. below conductor 16. Alternatively, and as dictated by the In this optional step 56, it is preferred to subject the coated choice of processing steps and materials, the insulating conductors 14/16 to a temperature of from about 200 to material 42 may be different from the insulating material 44 about 600 degrees Centigrade for from about 1 to about 10 and/or the insulating material 46. Thus, step 48 of the minutes. US 2006/01 02871 A1 May 18, 2006

0230. In one embodiment, illustrated in FIG. 3 of U.S. 0238 Thus, e.g., one may make a thin film in accordance Pat. No. 6,713,671, one or more additional insulating layers with the procedure described at page 156 of Nature, Volume 43 are coated onto the assembly depicted in FIG. 2 of such 407, Sep. 14, 2000, that describes a multilayer thin film has patent. This is conducted in optional step 58 (see FIG. 1A a saturation magnetization of 24,000 Gauss. of Such patent). 0239 Referring again to FIG. 6 of U.S. Pat. No. 6,713, 0231 FIG. 4 of U.S. Pat. No. 6,713,671 is a partial 671, the film 104 is adapted to reduce the magnetic field schematic view of the assembly 11 of FIG. 2 of such patent, strength at point 108 (which is disposed less than 1 centi illustrating the current flow in such assembly. Referring meter above film 104) by at least about 50 percent. Thus, if again to FIG. 4 of U.S. Pat. No. 6,713,671, it will be seen one were to measure the magnetic field strength at point 108, that current flows into conductor 14 in the direction of arrow and thereafter measure the magnetic field strength at point 60, and it flows out of conductor 16 in the direction of arrow 110 (which is disposed less than 1 centimeter below film 62. The net current flow through the assembly 11 is zero; and 104), the latter magnetic field strength would be no more the net Lorentz force in the assembly 11 is thus zero. than about 50 percent of the former magnetic field strength. Consequently, even high current flows in the assembly 11 do Put another way, the film 104 has a magnetic shielding factor not cause Such assembly to move. of at least about 0.5. 0232 Referring again to FIG. 4 of U.S. Pat. No. 6,713, 0240 Referring again to FIG. 6 of U.S. Pat. No. 6,713, 671 conductors 14 and 16 are substantially parallel to each 671, in one embodiment, the film 104 has a magnetic other. As will be apparent, without such parallel orientation, shielding factor of at least about 0.9, i.e., the magnetic field there may be some net current and some net Lorentz effect. strength at point 10 is no greater than about 10 percent of the 0233. In the embodiment depicted in such FIG. 4, and in magnetic field strength at point 108. Thus, e.g., the static one preferred aspect thereof, the conductors 14 and 16 magnetic field strength at point 108 can be, e.g., one Tesla, preferably have the same diameters and/or the same com whereas the static magnetic field strength at point 110 can positions and/or the same length. be, e.g., 0.1 Tesla. Furthermore, the time-varying magnetic 0234 Referring again to FIG. 4 of U.S. Pat. No. 6,713, field strength of a 100 milliTesla would be reduced to about 671, the nanomagnetic particles 24 are present in a density 10 milliTesla of the time-varying field. Sufficient so as to provide shielding from magnetic flux lines An MRI Imaging Process 64. Without wishing to be bound to any particular theory, applicant believes that the nanomagnetic particles 24 trap 0241. In one embodiment of the invention, best illus and pin the magnetic lines of flux 64. trated in FIG. 4, a coated stent 100 is imaged by an MRI imaging process. As will be apparent to those skilled in the 0235. In order to function optimally, the nanomagnetic art, the process depicted in FIG. 4 can be used with particles 24 preferably have a specified magnetization. As is reference to other medical devices such as, e.g., a coated known to those skilled in the art, magnetization is the brachytherapy seed. magnetic moment per unit volume of a Substance. Reference may be had, e.g., to U.S. Pat. Nos. 4,169.998, 4,168,481, 0242. In the first step of this process, the coated stent 100 4,166,263, 5,260,132, 4,778,714, and the like. The entire is contacted with the radio-frequency, direct current, and disclosure of each of these United States patents is hereby gradient fields normally associated with MRI imaging pro incorporated by reference into this specification. cesses; these fields are discussed elsewhere in this specifi 0236 Referring again to FIG. 4 of U.S. Pat. No. 6,713, cation. They are depicted as an MRI imaging signal 140 in 671, the entire disclosure of which is hereby incorporated by FIG. 4 reference into this specification, the layer of nanomagnetic 0243 In the second step of this process, the MRI imaging particles 24 preferably has a Saturation magnetization, at 25 signal 140 penetrates the coated stent 100 and interacts with degrees Centigrade, of from about 1 to about 36,000 Gauss, material disposed on the inside of Such stent, Such as, e.g., or higher. In one embodiment, the Saturation magnetization plaque particles 130 and 132. This interaction produces a at room temperature of the nanomagentic particles is from signal best depicted as arrow 141 in FIG. 4. about 500 to about 10,000 Gauss. For a discussion of the saturation magnetization of various materials, reference may 0244. In one embodiment, the signal 440 is substantially be had, e.g., to U.S. Pat. Nos. 4,705,613, 4,631,613, 5,543, unaffected by its passage through the coated stent 100. Thus, 070, 3,901,741 (cobalt, samarium, and gadolinium alloys), in this embodiment, the radio-frequency field that is dis and the like. The entire disclosure of each of these United posed on the outside of the coated stent 100 is substantially States patents is hereby incorporated by reference into this the same as the radio-frequency field that passes through and specification. is disposed on the inside of the coated stent 100. 0237. In one embodiment, it is preferred to utilize a thin 0245. By comparison, when the stent (not shown) is not film with a thickness of less than about 2 microns and a coated with the coatings of this invention, the characteristics saturation magnetization in excess of 20,000 Gauss. The of the signal 140 are substantially varied by its passage thickness of the layer of nanomagentic material is measured through the uncoated Stent. Thus, with Such uncoated Stent, from the bottom surface of the layer that contains such the radio-frequency signal that is disposed on the outside of material to the top Surface of Such layer that contains such the stent (not shown) differs substantially from the radio material; and Such bottom surface and/or Such top surface frequency field inside of the uncoated Stent (not shown). In may be contiguous with other layers of material (such as Some cases, because of Substrate effects, Substantially none insulating material) that do not contain nanomagnetic par of Such radio-frequency signal passes through the uncoated ticles. stent (not shown). US 2006/01 02871 A1 May 18, 2006

0246. In the third step of this process, and in one embodi 24 and 28 are shown. The configuration of target 12 with ment thereof, the MRI field(s) interact with material dis magnets 26, 28 comprises a magnetron Sputter source 29 posed on the inside of coated Stent 100 Such as, e.g., plaque known in the prior art, such as the Torus-1OE system particles 130 and 132. This interaction produces a signal 141 manufactured by K. Lesker, Inc. A sputter power supply 30 by means well known to those in the MRI imaging art. (DC or RF) is connected by a line 32 to the sputter target 12. 0247. In the fourth step of the preferred process of this A RF supply 34 provides power to RF coil 16 by a line 36 invention, the signal 141 passes back through the coated and through a matching network 37. Variable impedance 38 stent 100 in a manner such that it is substantially unaffected is connected in series with the cold end 17 of coil 16. A by the coated stent 100. Thus, in this embodiment, the second sputter power supply 39 is connected by a line 40 to radio-frequency field that is disposed on the inside of the cylindrical sputter target 14. A bias power supply 42 (DC or coated stent 100 is substantially the same as the radio RF) is connected by a line 44 to chuck 18 in order to provide frequency field that passes through and is disposed on the electrical bias to substrate 19 placed thereon, in a manner outside of the coated stent 100. well known in the prior art.” 0248. By comparison, when the stent (not shown) is not 0251. By way of yet further illustration, other conven coated with the coatings of this invention, the characteristics tional sputtering systems and processes are described in U.S. of the signal 141 are substantially varied by its passage Pat. No. 5,569,506 (a modified Kurt Lesker sputtering through the uncoated Stent. Thus, with Such uncoated Stent, system), U.S. Pat. No. 5,824,761 (a Lesker Torus 10 sputter the radio-frequency signal that is disposed on the inside of cathode), U.S. Pat. Nos. 5,768,123, 5,645,910, 6,046,398 the stent (not shown) differs substantially from the radio (sputter deposition with a Kurt J. Lesker Co. Torus 2 sputter frequency field outside of the uncoated stent (not shown). In gun), U.S. Pat. Nos. 5,736,488, 5.567,673, 6,454,910, and Some cases, because of Substrate effects, Substantially none the like. The entire disclosure of each of these United States of Such signal 141 passes through the uncoated Stent (not patents is hereby incorporated by reference into this speci shown). fication. 0252) By way of yet further illustration, one may use the A Process for Preparation of an Iron-Containing Thin Film techniques described in a paper by Xingwu Wang et al. 0249. In one preferred embodiment of the invention, a entitled “Technique Devised for Sputtering AIN. Thin sputtering technique is used to prepare an AlFe thin film or Films,” published in “the Glass Researcher. Volume 11, No. particles, as well as comparable thin films containing other 2 (Dec. 12, 2002). atomic moieties, or particles, such as, e.g., elemental nitro 0253) In one preferred embodiment, a magnetron sput gen, and elemental oxygen. Conventional sputtering tech tering technique is utilized, with a Lesker Super System III niques may be used to prepare Such films by Sputtering. See, system The vacuum chamber of this system is preferably for example, R. Herrmann and G. Brauer, “D. C. and R. F. cylindrical, with a diameter of approximately one meter and Magnetron Sputtering,” in the “Handbook of Optical Prop a height of approximately 0.6 meters. The base pressure used erties: Volume I Thin Films for Optical Coatings,” edited is from about 0.001 to 0.0001 Pascals. In one aspect of this by R. E. Hummel and K. H. Guenther (CRC Press, Boca process, the target is a metallic FeAl disk, with a diameter Raton, Fla., 1955). Reference also may be had, e.g., to M. of approximately 0.1 meter. The molar ratio between iron Allendorf, “Report of Coatings on Glass Technology Road and aluminum used in this aspect is approximately 70/30. map Workshop.” Jan. 18-19, 2000, Livermore, Calif.; and Thus, the starting composition in this aspect is almost also to U.S. Pat. No. 6,342,134, "Method for producing non-magnetic. See, e.g., page 83 (FIG. 3.1aii) of R. S. piezoelectric films with rotating magnetron sputtering sys Tebble et al’s “Magnetic Materials” (Wiley-Interscience, tem.” The entire disclosure of each of these prior art docu New York, N.Y., 1969); this Figure discloses that a bulk ments is hereby incorporated by reference into this specifi composition containing iron and aluminum with at least 30 cation. mole percent of aluminum (by total moles of iron and 0250 One may utilize conventional sputtering devices in aluminum) is substantially non-magnetic. this process. By way of illustration and not limitation, a 0254. In this aspect, to fabricate FeAl films, a DC power typical sputtering system is described in U.S. Pat. No. source is utilized, with a power level of from about 150 to 5,178,739, the entire disclosure of which is hereby incor about 550 watts (Advanced Energy Company of Colorado, porated by reference into this specification. As is disclosed model MDX Magnetron Drive). The sputtering gas used in in this patent, “ . . . a sputter system 10 includes a vacuum this aspect is argon, with a flow rate of from about 0.0012 chamber 20, which contains a circular end sputter target 12, to about 0.0018 standard cubic meters per second. To a hollow, cylindrical, thin, cathode magnetron target 14, a fabricate FeAIN films in this aspect, in addition to the DC RF coil 16 and a chuck 18, which holds a semiconductor Source, a pulse-forming device is utilized, with a frequency substrate 19. The atmosphere inside the vacuum chamber 20 of from about 50 to about 250 MHZ (Advanced Energy is controlled through channel 22 by a pump (not shown). The Company, model Sparc-lle V). One may fabricate FeAlO vacuum chamber 20 is cylindrical and has a series of films in a similar manner but using oxygen rather than permanent, magnets 24 positioned around the chamber and nitrogen. in close proximity therewith to create a multiple field configuration near the interior surface 15 of target 12. 0255 In this aspect, a typical argon flow rate is from Magnets 26, 28 are placed above end sputter target 12 to also about (0.9 to about 1.5)x10 standard cubic meters per create a multipole field in proximity to target 12. A singular second; a typical nitrogen flow rate is from about (0.9 to magnet 26 is placed above the center of target 12 with a about 1.8)x10 standard cubic meters per second; and a plurality of other magnets 28 disposed in a circular forma typical oxygen flow rate is from about. (0.5 to about 2)x10 tion around magnet 26. For convenience, only two magnets standard cubic meters per second. During fabrication, the US 2006/01 02871 A1 May 18, 2006 20 pressure typically is maintained at from about 0.2 to about described hereinafter with reference to one of the preferred 0.4 Pascals. Such a pressure range has been found to be ABC moieties, i.e., aluminum nitride doped with magne Suitable for nanomagnetic materials fabrications. In one sium. embodiment, it is preferred that both gaseous nitrogen and gaseous oxygen are present during the Sputtering process. 0264 FIG. 6 is a schematic of a deposition system 300 comprised of a power supply 302 operatively connected via 0256 In this aspect, the substrate used may be either flat line 304 to a magnetron 306. Disposed on top of magnetron or curved. A typical flat substrate is a silicon wafer with or 306 is a target 308. The target 308 is contacted by gas 310 without a thermally grown silicon dioxide layer, and its and gas 312, which cause sputtering of the target 308. The diameter is preferably from about 0.1 to about 0.15 meters. material so sputtered contacts substrate 314 when allowed to A typical curved Substrate is an aluminum rod or a stainless do so by the absence of shutter 316. steel wire, with a length of from about 0.10 to about 0.56 meters and a diameter of from (about 0.8 to about 3.0)x10 0265. In one preferred embodiment, the target 308 is meters The distance between the substrate and the target is mixture of aluminum and magnesium atoms in a molar ratio preferably from about 0.05 to about 0.26 meters. of from about 0.05 to about 0.5 Mg/(A1+Mg). In one aspect of this embodiment, the ratio of Mg/(Al-Mg) is from about 0257. In this aspect, in order to deposit a film on a wafer, 0.08 to about 0.12. These targets are commercially available the wafer is fixed on a substrate holder. The substrate may and are custom made by companies such as, e.g., Kurt or may not be rotated during deposition. In one embodiment, Lasker and Company of Pittsburgh, Pa. to deposit a film on a rod or wire, the rod or wire is rotated at a rotational speed of from about 0.01 to about 0.1 0266 The power supply 302 preferably provides pulsed revolutions per second, and it is moved slowly back and direct current. Generally, power supply 302 provides power forth along its symmetrical axis with a maximum speed of in excess of 300 watts, preferably in excess of 500 watts, and about 0.01 meters per second. more preferably in excess of 1,000 watts. In one embodi ment, the power supplied by power supply 302 is from about 0258. In this aspect, to achieve a film deposition rate on 1800 to about 2500 watts. the flat wafer of 5x10" meters per second, the power required for the FeAl film is 200 watts, and the power 0267 The power supply preferably provides rectangular required for the FeAlN film is 500 watts The resistivity of shaped pulses with a duration (pulse width) of from about 10 the FeAlN film is approximately one order of magnitude nanoseconds to about 100 nanoseconds. In one embodiment, larger than that of the metallic FeA1 film. Similarly, the the pulse width is from about 20 to about 40 nanoseconds. resistivity of the FeAlO film is about one order of magnitude 0268. In between adjacent pulses, preferably substan larger than that of the metallic FeAl film. tially no power is delivered. The time between adjacent 0259 Iron containing magnetic materials, such as FeAl, pulses is generally from about 1 microsecond to about 10 FeAIN and FeAIO, FeAINO, FeCoAINO, and the like, may microseconds and is generally at least 100 times greater than be fabricated by sputtering. The magnetic properties of those the pulse width. In one embodiment, the repetition rate of the materials vary with Stoichiometric ratios, particle sizes, and rectangular pulses is preferably about 150 kilohertz. fabrication conditions; see, e.g., R. S. Tebble and D. J. Craik, “Magnetic Materials, pp. 81-88, Wiley-Interscience, New 0269. One may use a conventional pulsed direct current York, 1969 As is disclosed in this reference, when the iron (d.c.) power Supply. Thus, e.g., one may purchase Such a molar ratio in bulk FeAl materials is less than 70 percent or power Supply from Advanced Energy Company of Colo So, the materials will no longer exhibit magnetic properties. rado, and/or from ENI Company of Rochester, N.Y. 0260. However, it has been discovered that, in contrast to 0270. The pulsed d.c. power from power supply 302 is bulk materials, a thin film material often exhibits different delivered to a magnetron 306, that creates an electromag properties. netic field near target 308. In one embodiment, a magnetic field has a magnetic flux density of from about 0.01 Tesla to A Preferred Sputtering Process about 0.1 Tesla. 0261) On Dec. 29, 2003, applicants filed U.S. patent 0271 As will be apparent, because the energy provided to application Ser. No. 10/747,472, for “Nanoelectrical Com magnetron 306 preferably comprises intermittent pulses, the positions.” The entire disclosure of this United States patent resulting magnetic fields produced by magnetron 306 will application is hereby incorporated by reference into this also be intermittent. Without wishing to be bound to any specification. particular theory, applicants believe that the use of Such intermittent electromagnetic energy yields better results than 0262 U.S. Ser. No. 10/747,472, at pages 10-15 thereof those produced by continuous radio-frequency energy. (and by reference to its FIG. 9), described the “ . . . preparation of a doped aluminum nitride assembly.” This 0272 Referring again to FIG. 6, it will be seen that the portion of U.S. Ser. No. 10/747,472 is specifically incorpo process depicted therein preferably is conducted within a rated by reference into this specification. It is also described vacuum chamber 318 in which the base pressure is from below, by reference to FIG. 6, which is similar to the FIG. about 1x10, Torr to about 0.000005 Torr. In one embodi 9 of U.S. Ser. No. 10/747,472 but utilizes different reference ment, the base pressure is from about 0.000001 to about numerals. OOOOOO3 Torr. 0263. The system depicted in FIG. 6 may be used to 0273. The temperature in the vacuum chamber 318 gen prepare an assembly comprised of moieties A, B, and C that erally is ambient temperature prior to the time sputtering are described elsewhere in this specification. FIG. 5 will be OCCU.S. US 2006/01 02871 A1 May 18, 2006

0274. In one aspect of the embodiment illustrated in FIG. may be accomplished by sensing the gas outflow via sensor 6, argon gas is fed via line 310, and nitrogen gas is fed via 332 and, as appropriate, varying the extent to which the line 312 so that both impact target 308, preferably in an shutter 328 is open or partially closed. ionized state. In another embodiment of the invention, argon 0286. Without wishing to be bound to any particular gas, nitrogen gas, and oxygen gas are fed via target 312. theory, applicants believe that the use of a substantially 0275. The argon gas, and the nitrogen gas, are fed at flow constant gas outflow rate insures a Substantially constant rates such that the flow rate of the argon gas divided by the deposition of sputtered nitrides. flow rate of the nitrogen gas preferably is from about 0.6 to 0287 Referring again to FIG. 6, and in one embodiment about 1.2. thereof, it is preferred to clean the substrate 314 prior to the 0276. In one aspect of this embodiment, such ratio of time it is utilized in the process. Thus, e.g., one may use argon to nitrogen is from about 0.8 to about 0.95. Thus, for detergent to clean any grease or oil or fingerprints off the example, the flow rate of the argon may be 20 standard cubic Surface of the Substrate. Thereafter, one may use an organic centimeters per minute, and the flow rate of the nitrogen may Solvent such as acetone, isopropryl alcohol, toluene, etc. be 23 standard cubic feet per minute. 0288. In one embodiment, the cleaned substrate 314 is 0277. The argon gas, and the nitrogen gas, contact a presputtered by Suppressing sputtering of the target 308 and target 308 that is preferably immersed in an electromagnetic sputtering the surface of the substrate 314. field. This field tends to ionize the argon and the nitrogen, 0289. As will be apparent to those skilled in the art, the providing ionized species of both gases. It is such ionized process depicted in FIG. 6 may be used to prepare coated species that bombard target 308. substrates 314 comprised of moieties other than doped 0278 In one embodiment, target 308 may be, e.g., pure aluminum nitride. aluminum. In one preferred embodiment, however, target A Preferred Process for Preparing Nanomagnetic Particles 308 is aluminum doped with minor amounts of one or more of the aforementioned moieties B. 0290. In one embodiment, illustrated in FIG. 7, a sub strate is cooled so that nanomagnetic particles are collected 0279. In the latter embodiment, the moieties B are pref on such substrate. Referring to FIG. 7, and in the preferred erably present in a concentration of from about 1 to about 40 embodiment depicted therein, a precursor 400 that prefer molar percent, by total moles of aluminum and moieties B. ably contains moieties A, B, and C (which are described It is preferred to use from about 5 to about 30 molar percent elsewhere in this specification) are charged to reactor 402. of such moieties B. 0291. The reactor 402 may be a plasma reactor. Plasma 0280 The ionized argon gas, and the ionized nitrogen reactors are described in applicants’ U.S. Pat. No. 5,100,868 gas, after impacting the target 308, creates a multiplicity of (process for preparing Superconducting films), U.S. Pat. No. sputtered particles 320. In the embodiment illustrated in 5.120.703 (process for preparing oxide Superconducting FIG. 8 the shutter 316 prevents the sputtered particles from films by radio-frequency generated aerosol-plasma deposi contacting Substrate 314. tion in atmosphere), U.S. Pat. No. 5,157.015 (process for 0281) When the shutter 316 is removed, however, the preparing Superonducting films by radio-frequency gener sputtered particles 320 can contact and coat the substrate ated aerosol-plasma deposition in atmosphere), U.S. Pat. 314. No. 5.213,851 (process for preparing ferrite films by radio frequency generated aerosol plasma deposition in atmo 0282. In one embodiment, illustrated in FIG. 6 the tem sphere), U.S. Pat. No. 5,260,105 (aerosol plasma deposition perature of substrate 314 is controlled by controller 322 that of films for electrochemical cells), U.S. Pat. No. 5,364,562 can heat the Substrate (by means such as a conduction heater (aerosol plasma deposition of insulating oxide powder), U.S. or an infrared heater) and/or cool the substrate (by means Pat. No. 5.366,770 (aerosol plasma deposition of films for Such as liquid nitrogen or water). electronic cells), and the like. The entire disclosure of each 0283 The sputtering operation increases the pressure of these United States patents is hereby incorporated by within the region of the sputtered particles 320. In general, reference into this specification. the pressure within the area of the sputtered particles 320 is 0292. The reactor 402 may be sputtering reactor 300 at least 100 times, and preferably 1000 times, greater than depicted in FIG. 6. the base pressure. 0293 Referring again to FIG. 7, it will be seen that an 0284. Referring again to FIG. 6 a cryo pump 324 is energy source 4045 is preferably used in order to cause preferably used to maintain the base pressure within vacuum reaction between moieties A, B, and C. The energy source chamber 318. In the embodiment depicted, a mechanical 404 may be an electromagnetic energy source that Supplies pump (dry pump) 326 is operatively connected to the cryo energy to the reactor 400. In one embodiment, there are at pump 324. Atmosphere from chamber 318 is removed by least two species of moiety A present, and at least two dry pump 326 at the beginning of the evacuation. At some species of moiety C present. The two preferred moiety C point, shutter 328 is removed and allows cryo pump 324 to species are oxygen and nitrogen. continue the evacuation. A valve 330 controls the flow of 0294 Within reactor 402 moieties A, B, and C are atmosphere to dry pump 326 so that it is only open at the preferably combined into a metastable state. This metastable beginning of the evacuation. state is then caused to travel towards collector 406. Prior to 0285) It is preferred to utilize a substantially constant the time it reaches the collector 406, the ABC moiety is pumping speed for cryo pump 324, i.e., to maintain a formed, either in the reactor 3 and/or between the reactor constant outflow of gases through the cryo pump 324. This 402 and the collector 406. US 2006/01 02871 A1 May 18, 2006 22

0295). In one embodiment, collector 406 is preferably example, in U.S. Pat. Nos. 5,001,014, 5,000,909, 4,966,625, cooled with a chiller 408 so that its surface 410 is at a 4,960,582, 4,957,812, 4,880,599, 4,862,117, 4,855,205, temperature below the temperature at which the ABC moiety 4,680,130, 4,490,268, 3,822,210, 3,635,898, 3,542,685, interacts with surface 410; the goal is to prevent bonding 3,421,933, and the like. The disclosure of each of these between the ABC moiety and the surface 410. In one patents is hereby incorporated by reference into this speci embodiment, the surface 410 is at a temperature of less than fication. Reference may also be had to pages 269-406 of the about 30 degrees Celsius. In another embodiment, the tem Von Aulock book for a discussion of spinel ferrites. As will perature of Surface 410 is at the liquid nitrogen temperature, be apparent, the corresponding nitrides also may be made. i.e., about 77 degrees Kelvin. 0303. In yet another embodiment, the ferromagnetic 0296. After the ABC moieties have been collected by material contains a lithium ferrite. Lithium ferrites are often collector 406, they are removed from surface 410. described by the formula (Lios Feos)+(Fe)3+O. Some illustrative lithium ferrites are described on pages 407-434 0297 FIG. 8 is a schematic illustration of one process of of the aforementioned Von Aulock book and in U.S. Pat. the invention that may be used to make nanomagnetic Nos. 4,277,356, 4,238,342, 4,177,438, 4,155,963, 4,093, material. This FIG. 8 is similar in many respects to the FIG. 781, 4,067,922, 3,998,757, 3,767,581, 3,640,867, and the 1 of U.S. Pat. No. 5,213,851, the entire disclosure of which like. The disclosure of each of these patents is hereby is hereby incorporated by reference into this specification. incorporated by reference into this specification. As will be 0298 Referring to FIG. 8, and in the preferred embodi apparent, the corresponding nitrides also may be made. ment depicted therein, it is preferred that the reagents charged into misting chamber 511 will be sufficient, in one 0304. In yet another embodiment, the ferromagnetic embodiment, to form a nano-sized ferrite in the process. The material contains a hexagonal ferrite. These ferrites are well term ferrite, as used in this specification, refers to a material known and are disclosed on pages 451-518 of the Von that exhibits ferromagnetism. Ferromagnetism is a property, Aulock book and also in U.S. Pat. Nos. 4,816,292, 4,189, exhibited by certain metals, alloys, and compounds of the 521, 5,061,586, 5,055,322, 5,051201, 5,047,290, 5,036,629, transition (iron group) rare earth and actinide elements, in 5,034,243, 5,032,931, and the like. The disclosure of each of which the internal magnetic moments spontaneously orga these patents is hereby incorporated by reference into this nize in a common direction; ferromagnetism gives rise to a specification. As will be apparent, the corresponding nitrides permeability considerably greater than that of vacuum and to also may be made. magnetic hysteresis. See, e.g., page 706 of Sybil B. Parkers 0305. In yet another embodiment, the ferromagnetic “McGraw-Hill Dictionary of Scientific and Technical material contains one or more of the moieties A, B, and C Terms. Fourth Edition (McGraw-Hill Book Company, New disclosed in the phase diagram disclosed elsewhere in this York, N.Y., 1989). specification and discussed elsewhere in this specification. 0299. As will be apparent to those skilled in the art, in 0306 Referring again to FIG. 8, and in the preferred addition to making nano-sized ferrites by the process embodiment depicted therein, it will be appreciated that the depicted in FIG. 8, one may also make other nano-sized solution 509 will preferably comprise reagents necessary to materials such as, e.g., nano-sized nitrides and/or nano-sized form the required magnetic material. For example, in one oxides containing moieties A, B, and C, as is described embodiment, in order to form the spinel nickel ferrite of the elsewhere in this specification. For the sake of simplicity of formula NiFe O, the solution should contain nickel and description, and with regard to FIG. 8, a discussion will be iron, which may be present in the form of nickel nitrate and had regarding the preparation of ferrites, it being understood iron nitrate. By way of further example, one may use nickel that, e.g., other materials may also be made by Such process. chloride and iron chloride to form the same spinel. By way 0300 Referring again to FIG. 8, and to the production of of further example, one may use nickel Sulfate and iron ferrites by Such process, in one embodiment, the ferromag sulfate. netic material contains FeO. See, for example, U.S. Pat. 0307. It will be apparent to skilled chemists that many No. 3,576,672 of Harris et al., the entire disclosure of which other combinations of reagents, both Stoichiometric and is hereby incorporated by reference into this specification. nonstoichiometric, may be used in applicants’ process to As will be apparent, the corresponding nitrides also may be make many different magnetic materials. made. 0308). In one preferred embodiment, the solution 509 0301 In one embodiment, the ferromagnetic material contains the reagent needed to produce a desired ferrite in contains garnet. Pure iron garnet has the formula MFesO2: stoichiometric ratio. Thus, to make the NiFe O ferrite in see, e.g., pages 65-256 of Wilhelm H. Von Aulock’s “Hand this embodiment, one mole of nickel nitrate may be charged book of Microwave Ferrite Materials” (Academic Press, with every two moles of iron nitrate. New York, 1965). Garnet ferrites are also described, e.g., in U.S. Pat. No. 4,721,547, the disclosure of which is hereby 0309. In one embodiment, the starting materials are pow incorporated by reference into this specification. As will be ders with purities exceeding 99 percent. apparent, the corresponding nitrides also may be made. 0310. In one embodiment, compounds of iron and the 0302) In another embodiment, the ferromagnetic material other desired ions are present in the solution in the stoichio contains a spinel ferrite. Spinel ferrites usually have the metric ratio. formula MFeO, wherein M is a divalent metal ion and Fe 0311. In one preferred embodiment, ions of nickel, zinc, is a trivalent iron ion. M is typically selected from the group and iron are present in a stoichiometric ratio of 0.5/0.5/2.0, consisting of nickel, Zinc, magnesium, manganese, and like. respectively. In another preferred embodiment, ions of These spinel ferrites are well known and are described, for lithium and iron are present in the ratio of 0.5/2.5. In yet US 2006/01 02871 A1 May 18, 2006 another preferred embodiment, ions of magnesium and iron 0321) The ions present in the solution may contain are present in the ratio of 1.0/2.0. In another embodiment, barium, iron, iridium, and zinc in the ratio of 1.0/12-2d/d/d, ions of manganese and iron are present in the ratio 1.0/2.0. wherein d is from 0.0 to 0.6. In yet another embodiment, ions of yttrium and iron are present in the ratio of 3.0/5.0. In yet another embodiment, 0322 The ions present in the solution may contain ions of lanthanum, yttrium, and iron are present in the ratio barium, nickel, gallium, and iron in the ratio of 1.0/2.0/7.0/ of 0.5/2.5/5.0. In yet another embodiment, ions of neody 9.0, or 1.0/2.0/5.0/11.0. Alternatively, the ions may contain mium, yttrium, gadolinium, and iron are present in the ratio barium, Zinc, gallium or aluminum, and iron in the ratio of of 1.0/1.07/0.93/5.0, or 1.0/1.1/0.9/5.0, or 1/1.12/0.88/5.0. 1.0/2.0/3...Of 13.O. In yet another embodiment, ions of Samarium and iron are 0323 Each of these ferrites is well known to those in the present in the ratio of 3.0/5.0. In yet another embodiment, ferrite art and is described, e.g., in the aforementioned Von ions of neodymium, Samarium, and iron are present in the Aulock book. ratio of 0.1/2.9/5.0, or 0.25/2.75/5.0, or 0.375/2.625/5.0. In yet another embodiment, ions of neodymium, erbium, and 0324. The ions described above are preferably available iron are present in the ratio of 1.5/1.5/5.0. In yet another in solution 509 in water-soluble form, such as, e.g., in the embodiment, Samarium, yttrium, and iron ions are present in form of water-soluble salts. Thus, e.g., one may use the the ratio of 0.51/2.49/5.0, or 0.84/2.16/5.0, or 1.5/1.5/5.0. In nitrates or the chlorides or the sulfates or the phosphates of yet another embodiment, ions of yttrium, gadolinium, and the cations. Other anions which form soluble salts with the iron are present in the ratio of 2.25/0.75/5.0, or 1.5/1.5/5.0, cation(s) also may be used. or 0.75/2.25/5.0. In yet another embodiment, ions of ter bium, yttrium, and iron are present in the ratio of 0.8/2.2/5.0, 0325 Alternatively, one may use salts soluble in solvents or 1.0/2.0/5.0. In yet another embodiment, ions of dyspro other than water. Some of these other solvents which may be sium, aluminum, and iron are present in the ratio of 3/x/5-X, used to prepare the material include nitric acid, hydrochloric when X is from 0 to 1.0. In yet another embodiment, ions of acid, phosphoric acid, Sulfuric acid, and the like. As is well dysprosium, gallium, and iron are also present in the ratio of known to those skilled in the art, many other suitable 3/x/5-X. In yet another embodiment, ions of dysprosium, Solvents may be used; see, e.g., J. A. Riddicket al., “Organic chromium, and iron are also present in the ratio of 3/x/5-X. Solvents, Techniques of Chemistry. Volume II, 3rd edition (Wiley-Interscience, New York, N.Y., 1970). 0312 The ions present in the solution, in one embodi ment, may be holmium, yttrium, and iron, present in the ratio 0326 In one preferred embodiment, where a solvent of Z/3-Z/5.0, where Z is from about 0 to 1.5. other than water is used, each of the cations is present in the 0313 The ions present in the solution may be erbium, form of one or more of its oxides. For example, one may gadolinium, and iron in the ratio of 1.5/1.5/5.0. The ions may dissolve iron oxide in nitric acid, thereby forming a nitrate. be erbium, yttrium, and iron in the ratio of 1.5/1.5/1.5, or For example, one may dissolve Zinc oxide in Sulfuric acid, 0.5/2.5/5.0. thereby forming a sulfate. One may dissolve nickel oxide in hydrochloric acid, thereby forming a chloride. Other means 0314. The ions present in the solution may be thulium, of providing the desired cation(s) will be readily apparent to yttrium, and iron, in the ratio of 0.06/2.94/5.0. those skilled in the art. 0315. The ions present in the solution may be ytterbium, 0327 In general, as long as the desired cation(s) are yttrium, and iron, in the ratio of 0.06/2.94/5.0. present in the solution, it is not significant how the Solution 0316 The ions present in the solution may be lutetium, was prepared. yttrium, and iron in the ratio of y/3-y/5.0, whereiny is from O to 3.O. 0328. In general, one may use commercially available reagent grade materials. Thus, by way of illustration and not 0317. The ions present in the solution may be iron, which limitation, one may use the following reagents available in can be used to form FeOs (two formula units of FeO). The the 1988-1989 Aldrich catalog (Aldrich Chemical Company, ions present may be barium and iron in the ratio of 1.0/6.0, Inc., Milwaukee, Wis.): barium chloride, catalog number or 2.0/8.0. The ions present may be strontium and iron, in the 31,866-3; barium nitrate, catalog number 32.806-5; barium ratio of 1.0/12.0. The ions present may be strontium, chro sulfate, catalog number 20,276-2: strontium chloride hex mium, and iron in the ratio of 1.0/1.0/10.0, or 1.0/6.0/6.0. hydrate, catalog number 20,466-3; strontium nitrate, catalog The ions present may be suitable for producing a ferrite of number 20,449-8; yttrium chloride, catalog number 29,826 the formula (Me.)+Ba-Fe2O, wherein Me is a rare 3; yttrium nitrate tetrahydrate, catalog number 21,723-9: earth selected from the group consisting of lanthanum, yttrium sulfate octahydrate, catalog number 20,493-5. This promethium, neodymium, Samarium, europium, and mix list is merely illustrative, and other compounds that can be tures thereof. used will be readily apparent to those skilled in the art. Thus, 0318. The ions present in the solution may contain any of the desired reagents also may be obtained from the barium, either lanthanum or promethium, iron, and cobalt in 1989-1990 AESAR catalog (Johnson Matthey/AESAR the ratio of 1-a/a/12-a/a, wherein a is from 0.0 to 0.8. Group, Seabrook, N.H.), the 1990/1991 Alfa catalog 0319. The ions present in the solution may contain (Johnson Matthey/Alfa Products, Ward Hill, Ma.), the Fisher barium, cobalt, titanium, and iron in the ratio of 1.0/b/b/12 88 catalog (Fisher Scientific, Pittsburgh, Pa.), and the like. 2b, wherein b is from 0.0 to 1.6. 0329. As long as the metals present in the desired ferrite 0320 The ions present in the solution may contain material are present in solution 509 in the desired stoichi barium, nickel or cobalt or Zinc, titanium, and iron in the ometry, it does not matter whether they are present in the ratio of 1.0/cfc/12-2c, wherein c is from 0.0 to 1.5. form of a salt, an oxide, or in another form. In one embodi US 2006/01 02871 A1 May 18, 2006 24 ment, however, it is preferred to have the solution contain Interior, Bureau of Mines, 1968), the disclosure of which is either the salts of such metals, or their oxides. hereby incorporated by reference into this specification. 0330. The solution 509 of the compounds of such metals 0341. As used in this specification, the term mist refers to preferably will be at a concentration of from about 0.01 to gas-Suspended liquid particles which have diameters less about 1,000 grams of said reagent compounds per liter of the than 10 microns. resultant solution. As used in this specification, the term liter 0342. The aerosol/mist consisting of gas-Suspended liq refers to 1,000 cubic centimeters. uid particles with diameters less than 10 microns may be 0331. In one embodiment, it is preferred that solution 509 produced from solution 509 by any conventional means that have a concentration of from about 1 to about 300 grams per causes sufficient mechanical disturbance of said solution. liter and, preferably, from about 25 to about 170 grams per Thus, one may use mechanical vibration. In one preferred liter. It is even more preferred that the concentration of said embodiment, ultrasonic means are used to mist Solution 9. solution 9 be from about 100 to about 160 grams per liter. As is known to those skilled in the art, by varying the means In an even more preferred embodiment, the concentration of used to cause Such mechanical disturbance, one can also said solution 509 is from about 140 to about 160 grams per vary the size of the mist particles produced. liter. 0343 As is known to those skilled in the art, ultrasonic 0332. In one preferred embodiment, aqueous solutions of sound waves (those having frequencies above 20,000 hertz) nickel nitrate, and iron nitrate with purities of at least 99.9 may be used to mechanically disturb solutions and cause percent are mixed in the molar ratio of 1:2 and then them to mist. Thus, by way of illustration, one may use the dissolved in distilled water to form a solution with a con ultrasonic nebulizer sold by the DeVilbiss Health Care, Inc. centration of 150 grams per liter. of Somerset, Pa.; see, e.g., the “Instruction Manual for the “Ultra-Neb 99 Ultrasonic Nebulizer, publication A-850-C 0333. In one preferred embodiment, aqueous solutions of (published by DeVilbiss. Somerset, Pa., 1989). nickel nitrate, Zinc nitrate, and iron nitrate with purities of at least 99.9 percent are mixed in the molar ratio of 0.5:0.5:2 0344) In the embodiment shown in FIG. 8, the oscillators and then dissolved in distilled water to form a solution with of ultrasonic nebulizer 513 are shown contacting an exterior surface of misting chamber 511. In this embodiment, the a concentration of 150 grams per liter. ultrasonic waves produced by the oscillators are transmitted 0334. In one preferred embodiment, aqueous solutions of via the walls of the misting chamber 511 and effect the Zinc nitrate, and iron nitrate with purities of at least 99.9 misting of solution 509. percent are mixed in the molar ratio of 1:2 and then dissolved in distilled water to form a solution with a con 0345. In another embodiment, not shown, the oscillators of ultrasonic nebulizer 513 are in direct contact with solution centration of 150 grams per liter. 509. 0335) In one preferred embodiment, aqueous solutions of 0346. In one embodiment, it is preferred that the ultra nickel chloride, and iron chloride with purities of at least Sonic power used with Such machine is in excess of one watt 99.9 percent are mixed in the molar ratio of 1:2 and then and, more preferably, in excess of 10 watts. In one embodi dissolved in distilled water to form a solution with a con ment, the power used with such machine exceeds about 50 centration of 150 grams per liter. WattS. 0336. In one preferred embodiment, aqueous solutions of 0347 During the time solution 509 is being caused to nickel chloride, zinc chloride, and iron chloride with purities mist, it is preferably contacted with carrier gas to apply of at least 99.9 percent are mixed in the molar ratio of pressure to the solution and mist. It is preferred that a 0.5:0.5:2 and then dissolved in distilled water to form a Sufficient amount of carrier gas beintroduced into the system solution with a concentration of 150 grams per liter. at a sufficiently high flow rate so that pressure on the system 0337. In one preferred embodiment, aqueous solutions of is in excess of atmospheric pressure. Thus, for example, in Zinc chloride, and iron chloride with purities of at least 99.9 one embodiment wherein chamber 511 has a volume of percent are mixed in the molar ratio of 1:2 and then about 200 cubic centimeters, the flow rate of the carrier gas dissolved in distilled water to form a solution with a con was from about 100 to about 150 milliliters per minute. centration of 150 grams per liter. 0348. In one embodiment, the carrier gas 515 is intro 0338. In one embodiment, mixtures of chlorides and duced via feeding line 517 at a rate sufficient to cause nitrides may be used. Thus, for example, in one preferred solution 509 to mist at a rate of from about 0.5 to about 20 embodiment, the solution is comprised of both iron chloride milliliters per minute. In one embodiment, the misting rate and nickel nitrate in the molar ratio of 2.0/1.0. of solution 9 is from about 1.0 to about 3.0 milliliters per minute. 0339) Referring again to FIG. 8, and to the preferred embodiment depicted therein, the solution 509 in misting 0349 Substantially any gas that facilitates the formation chamber 511 is preferably caused to form into an aerosol, of plasma may be used as carrier gas 515. Thus, by way of Such as a mist. illustration, one may use oxygen, air, argon, nitrogen, mix tures thereof and the like; in one embodiment, a mixture of 0340. The term aerosol, as used in this specification, oxygen and nitrogen is used. It is preferred that the carrier refers to a suspension of ultramicroscopic Solid or liquid gas used be a compressed gas under a pressure in excess 760 particles in air orgas, such as Smoke, fog, or mist. See, e.g., millimeters of mercury. In this embodiment, the use of the page 15 of “A dictionary of mining, mineral, and related compressed gas facilitates the movement of the mist from terms,” edited by Paul W. Thrush (U.S. Department of the the misting chamber 511 to the plasma region 521. US 2006/01 02871 A1 May 18, 2006

0350. The misting container 511 may be any reaction 0360. In general, the energy is applied at a frequency of chamber conventionally used by those skilled in the art and from about 100 to about 30,000 kilohertz. In one embodi preferably is constructed out of such acid-resistant materials ment, the radio frequency used is from about 1 to 20 Such as glass, plastic, and the like. megahertz. In another embodiment, the radio frequency used 0351) The mist from misting chamber 511 is fed via is from about 3 to about 5 megahertz. misting outlet line 519 into the plasma region 521 of plasma 0361. As is known to those skilled in the art, such radio reactor 525. In plasma reactor 525, the mist is mixed with frequency alternating currents may be produced by conven plasma generated by plasma gas 527 and Subjected to radio tional radio frequency generators. Thus, by way of illustra frequency radiation provided by a radio-frequency coil 529. tion, said TAPA Inc. “model 56 torch” may be attached to a radio frequency generator rated for operation at 35 kilowatts 0352. The plasma reactor 525 provides energy to form which manufactured by Lepel Company (a division of TAFA plasma and to cause the plasma to react with the mist. Any Inc.) and which generates an alternating current with a of the plasmas reactors well known to those skilled in the art frequency of 4 megaherZ at a power input of 30 kilowatts. may be used as plasma reactor 525. Some of these plasma Thus, e.g., one may use an induction coil driven at 2.5-5.0 reactors are described in J. Mort et al.’s “Plasma Deposited megahertz that is sold as the “PLASMOC 2 by ENI Power Thin Films” (CRC Press Inc., Boca Raton, Fla., 1986); in Systems, Inc. of Rochester, N.Y. “Methods of Experimental Physics.” Volume 9 Parts A and B, Plasma Physics (Academic Press, New York, 1970/1971): 0362. The use of these type of radio-frequency generators and in N. H. Burlingame’s “Glow Discharge Nitriding of is described in the Ph.D. theses entitled (1) “Heat Transfer Oxides.” Ph.D. thesis (Alfred University, Alfred, N.Y., Mechanisms in High-Temperature Plasma Processing of 1985), available from University Microfilm International, Glasses.” Donald M. McPherson (Alfred University, Alfred, Ann Arbor, Mich. N.Y., January, 1988) and (2) the aforementioried Nicholas H. Burlingame's “Glow Discharge Nitriding of Oxides.” 0353. In one preferred embodiment, the plasma reactor 525 is a “model 56 torch available from the TAFA Inc. of 0363 The plasma vapor 523 formed in plasma reactor Concord, N.H. It is preferably operated at a frequency of 525 is allowed to exit via the aperture 542 and can be about 4 megahertz and an input power of 30 kilowatts. visualized in the flame region 540. In this region, the plasma contacts air that is at a lower temperature than the plasma 0354) Referring again to FIG. 8, and to the preferred region 521, and a flame is visible. A theoretical model of the embodiment depicted therein, it will be seen that into plasma/flame is presented on pages 88 et seq. of said feeding lines 529 and 531 is fed plasma gas 527. As is McPherson thesis. known to those skilled in the art, a plasma can be produced by passing gas into a plasma reactor. A discussion of the 0364 The vapor 544 present in flame region 540 is formation of plasma is contained in B. Chapman’s “Glow propelled upward towards substrate 546. Any material onto Discharge Processes” (John Wiley & Sons, New York, 1980) which vapor 544 will condense may be used as a substrate. Thus, by way of illustration, one may use nonmagnetic 0355. In one preferred embodiment, the plasma gas used materials such alumina, glass, gold-plated ceramic materi is a mixture of argon and oxygen. In another embodiment, als, and the like. In one embodiment, Substrate 46 consists the plasma gas is a mixture of nitrogen and oxygen. In yet essentially of a magnesium oxide material Such as single another embodiment, the plasma gas is pure argon or pure crystal magnesium oxide, polycrystalline magnesium oxide, nitrogen. and the like. 0356. When the plasma gas is pure argon or pure nitro 0365. In another embodiment, the substrate 546 consists gen, it is preferred to introduce into the plasma reactor at a essentially of Zirconia Such as, e.g., yttrium stabilized cubic flow rate of from about 5 to about 30 liters per minute. Zirconia. 0357 When a mixture of oxygen and either argon or 0366. In another embodiment, the substrate 546 consists nitrogen is used, the concentration of oxygen in the mixture essentially of a material selected from the group consisting preferably is from about 1 to about 40 volume percent and, of strontium titanate, stainless Steel, alumina, Sapphire, and more preferably, from about 15 to about 25 volume percent. the like. When such a mixture is used, the flow rates of each gas in the mixture should be adjusted to obtain the desired gas 0367 The aforementioned listing of substrates is merely concentrations. Thus, by way of illustration, in one embodi meant to be illustrative, and it will be apparent that many ment that uses a mixture of argon and oxygen, the argon flow other substrates may be used. Thus, by way of illustration, rate is 15 liters per minute, and the oxygen flow rate is 40 one may use any of the substrates mentioned in M. Sayers liters per minute. “Ceramic Thin Films ...” article, supra. Thus, for example, in one embodiment it is preferred to use one or more of the 0358 In one embodiment, auxiliary oxygen 533 is fed substrates described on page 286 of “Superconducting into the top of reactor 25, between the plasma region 521 and Devices, edited by S. T. Ruggiero et al. (Academic Press, the flame region 540, via lines 536 and 538. In this embodi Inc., Boston, 1990). ment, the auxiliary oxygen is not involved in the formation of plasma but is involved in the enhancement of the oxida 0368 One advantage of this embodiment of applicants tion of the ferrite material. process is that the Substrate may be of Substantially any size or shape, and it may be stationary or movable. Because of 0359 Radio frequency energy is applied to the reagents the speed of the coating process, the substrate 546 may be in the plasma reactor 525, and it causes vaporization of the moved across the aperture 542 and have any or all of its mist. surface be coated. US 2006/01 02871 A1 May 18, 2006 26

0369. As will be apparent to those skilled in the art, in the micron. It is preferred that at least about 90 percent of such embodiment depicted in FIG. 8, the substrate 546 and the particles are smaller than 1 micron. Because of this fine coating 548 are not drawn to scale but have been enlarged grain size, the surface of the film is relatively smooth. to the sake of ease of representation. 0380. In one preferred embodiment, the as-deposited film 0370 Referring again to FIG. 8, the substrate 546 may be is post-annealed. at ambient temperature. Alternatively, one may use addi tional heating means to heat the Substrate prior to, during, or 0381. It is preferred that the generation of the vapor in after deposition of the coating. plasma rector 525 be conducted under substantially atmo spheric pressure conditions. As used in this specification, the 0371 Referring again to FIG. 8, and in one preferred term “substantially atmospheric' refers to a pressure of at embodiment, a heater (not shown) is used to heat the least about 600 millimeters of mercury and, preferably, from substrate to a temperature of from about 100 to about 800 about 600 to about 1,000 millimeters of mercury. It is degrees centigrade. preferred that the vapor generation occur at about atmo 0372. In one aspect of this embodiment, temperature spheric pressure. As is well known to those skilled in the art, sensing means (not shown) may be used to sense the atmospheric pressure at sea level is 760 millimeters of temperature of the substrate and, by feedback means (not mercury. shown), adjust the output of the heater (not shown). In one 0382. The process of this invention may be used to embodiment, not shown, when the substrate 46 is relatively produce coatings on a flexible Substrate Such as, e.g., stain near flame region 40, optical pyrometry measurement means less steel strips, silver strips, gold strips, copper strips, (not shown) may be used to measure the temperature near aluminum strips, and the like. One may deposit the coating the substrate. directly onto Such a strip. Alternatively, one may first deposit 0373) In one embodiment, a shutter (not shown) is used one or more buffer layers onto the strip(s). In other embodi to selectively interrupt the flow of vapor 544 to substrate ments, the process of this invention may be used to produce 546. This shutter, when used, should be used prior to the coatings on a rigid or flexible cylindrical Substrate. Such as time the flame region has become stable; and the vapor a tube, a rod, or a sleeve. should preferably not be allowed to impinge upon the 0383 Referring again to FIG. 8, and in the embodiment Substrate prior to such time. depicted therein, as the coating 548 is being deposited onto 0374. The substrate 546 may be moved in a plane that is the substrate 546, and as it is undergoing solidification substantially parallel to the top of plasma chamber 525. thereon, it is preferably subjected to a magnetic field pro Alternatively, or additionally, it may be moved in a plane duced by magnetic field generator 550. that is Substantially perpendicular to the top of plasma chamber 525. In one embodiment, the substrate 46 is moved 0384. In this embodiment, it is preferred that the mag stepwise along a predetermined path to coat the Substrate netic field produced by the magnetic field generator 550 only at certain predetermined areas. have a field strength of from about 2 Gauss to about 40 Tesla. 0375. In one embodiment, rotary substrate motion is 0385) It is preferred to expose the deposited material for utilized to expose as much of the Surface of a complex at least 10 seconds and, more preferably, for at least 30 shaped article to the coating. This rotary Substrate motion seconds, to the magnetic field, until the magnetic moments may be effectuated by conventional means. See, e.g., “Physi of the nano-sized particles being deposited have been Sub cal Vapor Deposition.” edited by Russell J. Hill (Temescal stantially aligned. Division of The BOC Group, Inc., Berkeley, Calif., 1986). 0386 As used herein, the term “substantially aligned 0376 The process of this embodiment of the invention means that the inductance of the device being formed by the allows one to coat an article at a deposition rate of from deposited nano-sized particles is at least 90 percent of its about 0.01 to about 10 microns per minute and, preferably, maximum inductance. One may determine when Such par from about 0.1 to about 1.0 microns per minute, with a ticles have been aligned by, e.g., measuring the inductance, Substrate with an exposed Surface of 35 square centimeters. the permeability, and/or the hysteresis loop of the deposited One may determine the thickness of the film coated upon material. said reference substrate material (with an exposed surface of 35 square centimeters) by means well known to those skilled 0387 Thus, e.g., one may measure the degree of align in the art. ment of the deposited particles with an impedance meter, a inductance meter, or a SQUID. 0377 The film thickness can be monitored in situ, while the vapor is being deposited onto the substrate. Thus, by way 0388. In one embodiment, the degree of alignment of the of illustration, one may use an IC-6000 thin film thickness deposited particles is measured with an inductance meter. monitor (also referred to as “deposition controller) manu One may use, e.g., a conventional conductance meter Such factured by Leybold Inficon Inc. of East Syracuse, N.Y. as, e.g., the conductance meters disclosed in U.S. Pat. Nos. 4,779,462, 4,937,995, 5,728,814 (apparatus for determining 0378. The deposit formed on the substrate may be mea and recording injection does in Syringes using electrical sured after the deposition by standard profilometry tech inductance), U.S. Pat. Nos. 6,318,176, 5,014,012, 4,869, niques. Thus, e.g., one may use a DEKTAKSurface Profiler, 598, 4.258,315 (inductance meter), U.S. Pat. No. 4,045,728 model number 900051 (available from Sloan Technology (direct reading inductance meter), U.S. Pat. Nos. 6.252,923, Corporation, Santa Barbara, Calif.). 6,194,898, 6,006,023 (molecular sensing apparatus), U.S. 0379. In general, at least about 80 volume percent of the Pat. No. 6,048,692 (sensors for electrically sensing binding particles in the as-deposited film are smaller than about 1 events for supported molecular receptors), and the like. The US 2006/01 02871 A1 May 18, 2006 27 entire disclosure of each of these United States patents is Superconducting magnets for magnetic resonance imaging), hereby incorporated by reference into this specification. U.S. Pat. No. 6,476,700 (superconducting magnet system), U.S. Pat. No. 4,763.404 (low current superconducting mag 0389. When measuring the inductance of the coated net), U.S. Pat. No. 6,172.587 (superconducting high field sample, the inductance is preferably measured using an magnet), U.S. Pat. No. 5,406.204, and the like. The entire applied wave with a specified frequency. As the magnetic disclosure of each of these United States patents is hereby moments of the coated Samples align, the inductance incorporated by reference into this specification. increases until a specified value; and it rises in accordance with a specified time constant in the measurement circuitry. 0395. In one embodiment, no magnetic field is applied to the deposited coating while it is being solidified. In this 0390. In one embodiment, the deposited material is con embodiment, as will be apparent to those skilled in the art, tacted with the magnetic field until the inductance of the there still may be some alignment of the magnetic domains deposited material is at least about 90 percent of its maxi in a plane parallel to the surface of substrate as the deposited mum value under the measurement circuitry. At this time, particles are locked into place in a matrix (binder) deposited the magnetic particles in the deposited material have been onto the Surface. aligned to at least about 90 percent of the maximum extent possible for maximizing the inductance of the sample. 0396. In one embodiment, depicted in FIG. 8, the mag netic field 552 is preferably delivered to the coating 548 in 0391 By way of illustration and not limitation, a metal a direction that is substantially parallel to the surface 556 of rod with a diameter of 1 micron and a length of 1 millimeter, the substrate 546. In another embodiment, not shown, the when uncoated with magnetic nano-sized particles, might magnetic field 558 is delivered in a direction that is sub have an inductance of about 1 nanohenry. When this metal stantially perpendicular to the surface 556. In yet another rod is coated with, e.g., nano-sized ferrites, then the induc embodiment, the magnetic field 560 is delivered in a direc tance of the coated rod might be 5 nanohenries or more. tion that is angularly disposed vis-a-vis surface 556 and may When the magnetic moments of the coating are aligned, then form, e.g., an obtuse angle (as in the case of field 62). As will the inductance might increase to 50 nanohenries, or more. be apparent, combinations of these magnetic fields may be As will be apparent to those skilled in the art, the inductance used. of the coated article will vary, e.g., with the shape of the article and also with the frequency of the applied electro 0397 FIG. 9 is a flow diagram of another process that magnetic field. may be used to make the nanomagnetic compositions of this invention. Referring to FIG.9, and to the preferred process 0392 One may use any of the conventional magnetic depicted therein, it will be seen that nano-sized ferromag field generators known to those skilled in the art to produce netic material(s), with a particle size less than about 100 Such as magnetic field. Thus, e.g., one may use one or more nanometers, is preferably charged via line 660 to mixer 63. of the magnetic field generators disclosed in U.S. Pat. Nos. It is preferred to charge a sufficient amount of Such nano 6.503,364, 6,377,149 (magnetic field generator for magne sized material(s) so that at least about 10 weight percent of tron plasma generation), U.S. Pat. No. 6,353.375 (magne the mixture formed in mixer 663 is comprised of such tostatic wave device), U.S. Pat. No. 6,340,888 (magnetic nano-sized material. In one embodiment, at least about 40 field generator for MRI), U.S. Pat. Nos. 6,336,989, 6.335, weight percent of such mixture in mixer 663 is comprised of 617 (device for calibrating a magnetic field generator), U.S. Such nano-sized material. In another embodiment, at least Pat. Nos. 6,313,632, 6,297.634, 6,275,128, 6.246,066 (mag about 50 weight percent of such mixture in mixer 663 is netic field generator and charged particle beam irradiator), comprised of Such nano-sized material. U.S. Pat. No. 6,114,929 (magnetostatic wave device), U.S. Pat. No. 6,099.459 (magnetic field generating device and 0398. In one embodiment, one or more binder materials method of generating and applying a magnetic field), U.S. are charged via line 664 to mixer 662. In one embodiment, Pat. Nos. 5,795.212, 6,106,380 (deterministic magnetorheo the binder used is a ceramic binder. These ceramic binders logical finishing), U.S. Pat. No. 5,839,944 (apparatus for are well known. Reference may be had, e.g., to pages deterministic magnetorheological finishing), U.S. Pat. No. 172-197 of James S. Reed’s “Principles of Ceramic Pro 5.971,835 (system for abrasive jet shaping and polishing of cessing.” Second Edition (John Wiley & Sons, Inc., New a Surface using a magnetorheological fluid), U.S. Pat. Nos. York, N.Y., 1995). As is disclosed in the Reed book, the 5,951.369, 6,506,102 (system for magnetorheological fin binder may be a clay binder (such as fine kaolin, ball clay, ishing of substrates), U.S. Pat. Nos. 6,267,651, 6,309.285 and bentonite), an organic colloidal particle binder (Such as (magnetic wiper), and the like. The entire disclosure of each microcrystalline cellulose), a molecular organic binder (Such of these United States patents is hereby incorporated by as natural gums, polyScaccharides, lignin extracts, refined alginate, cellulose ethers, polyvinyl alcohol, polyvinylbu reference into this specification. tyral, polymethyl methacrylate, polyethylene glycol, paraf 0393. In one embodiment, the magnetic field is 1.8 Tesla fin, and the like.). etc. or less. In this embodiment, the magnetic field can be applied with, e.g., electromagnets disposed around a coated 0399. In one embodiment, the binder is a synthetic poly substrate. meric or inorganic composition. Thus, and referring to George S. Brady et al.’s “Materials Handbook.” (McGraw 0394 For fields greater than about 2 Tesla, one may use Hill, Inc., New York, N.Y. 1991), the binder may be acry Superconducting magnets that produce fields as high as 40 lonitrile-butadiene-styrene (see pages 5-6), an acetal resin Tesla. Reference may be had, e.g., to U.S. Pat. No. 5,319.333 (see pages 6-7), an acrylic resin (see pages 10-12), an (Superconducting homogeneous high field magnetic coil), adhesive composition (see pages 14-18), an alkyd resin (see U.S. Pat. Nos. 4,689,563, 6,496.091 (superconducting mag page 27-28), an allyl plastic (see pages 31-32), an amor net arrangement), U.S. Pat. No. 6,140,900 (asymmetric phous metal (see pages 53-54), a biocompatible material US 2006/01 02871 A1 May 18, 2006 28

(see pages 95-98), boron carbide (see page 106), boron comprises a polymer binder, thereby forming a nanomag nitride (see page 107), camphor (see page 135), one or more netic paint. In one embodiment, the nanomagnetic paint is carbohydrates (see pages 138-140), carbon steel (see pages formulated without abrasive particles of cerium dioxide. In 146-151), casein plastic (see page 157), cast iron (see pages another embodiment, the nanomagnetic fluid further com 159-164), cast steel (see pages 166-168), cellulose (see prises a polymer binder, and aluminum nitride is substituted pages 172-175), cellulose acetate (see pages 175-177), cel for cerium dioxide. lulose nitrate (see pages 177), cement (see page 178-180), ceramics (see pages 180-182), cermets (see pages 182-184), 04.04 There are many suitable mixing processes and chlorinated polyethers (see pages 191-191), chlorinated rub apparatus for the milling, particle size reduction, and mixing ber (see pages 191-193), cold-molded plastics (see pages of fluids comprising Solid particles. For example, e.g., iron 220-221), concrete (see pages 225-227), conductive poly carbonyl particles or other ferromagnetic particles of the mers and elastomers (see pages 227-228), degradable plas paint may be further reduced to a size on the order of 100 tics (see pages 261-262), dispersion-strengthened metals nanometers or less, and/or thoroughly mixed with a binder (see pages 273-274), elastomers (see pages 284-290), polymer and/or a liquid solvent by the use of a ball mill, a enamel (see pages 299-301), epoxy resins (see pages 301 sand mill, a paint shaker holding a vessel containing the 302), expansive metal (see page 313), ferrosilicon (see page paint components and hard steel or ceramic beads; a homog 327), fiber-reinforced plastics (see pages 334-335), fluoro enizer (such as the Model Ytron Z made by the Ytron plastics (see pages 345-347), foam materials (see pages Quadro Corporation of Chesham, United Kingdom, or the 349-351), fusible alloys (see pages 362-364), glass (see Microfluidics M700 made by the MFIC Corporation of pages 376-383), glass-ceramic materials (see pages 383 Newton, Ma.), a powder dispersing mixer (such as the Ytron 384), gypsum (see pages 406-407), impregnated wood (see Zyclon mixer, or the Ytron Xyclon mixer, or the Ytron PID pages 422-423), latex (see pages 456-457), liquid crystals mixer by the Ytron Quadro Corporation); a grinding mill (see page 479). lubricating grease (see pages 488-492), (such as the Model F10 Mill by the Ytron Quadro Corpo magnetic materials (see pages 505-509), melamine resin ration); high shear mixers (such as the Ytron Y mixer by the (see pages 5210-521), metallic materials (see pages 522 Ytron Quadro Corporation), the Silverson Laboratory Mixer 524), nylon (see pages 567-569), olefin copolymers (see sold by the Silverson Corporation of East Longmeadow, pages 574-576), phenol-formaldehyde resin (see pages 615 Ma. and the like. The use of one or more of these apparatus 617), plastics (see pages 637-639), polyarylates (see pages in series or in parallel may produce a suitably formulated 647-648), polycarbonate resins (see pages 648), polyester nanomagnetic paint. thermoplastic resins (see pages 648-650), polyester thermo 04.05 Referring again to FIG. 9, the former 666 is setting resins (see pages 650-651), polyethylenes (see pages preferably equipped with an input line 68 and an exhaust line 651-654), polyphenylene oxide (see pages 644-655), 670 so that the atmosphere within the former can be con polypropylene plastics (see pages 655-656), polystyrenes trolled. One may utilize an ambient atmosphere, an inert (see pages 656-658), proteins (see pages 666-670), refrac atmosphere, pure nitrogen, pure oxygen, mixtures of various tories (see pages 691-697), resins (see pages 697-698), gases, and the like. Alternatively, or additionally, one may rubber (see pages 706-708), silicones (see pages 747-749), use lines 668 and 670 to afford subatmospheric pressure, starch (see pages 797-802), superalloys (see pages 819-822), atmospheric pressure, or Superatomspheric pressure within Superpolymers (see pages 823-825), thermoplastic elas former 666. tomers (see pages 837-839), urethanes (see pages 874-875), 0406. In the embodiment depicted, former 666 is also vinyl resins (see pages 885-888), wood (see pages 912-916), preferably comprised of an electromagnetic coil 672 that, in mixtures thereof, and the like. response from signals from controller 674, can control the 0400 Referring again to FIG. 9, one may charge to line extent to which, if any, a magnetic field is applied to the 664 either one or more of these “binder material(s)' and/or mixture within the former 666 (and also within the mold 667 the precursor(s) of these materials that, when subjected to and/or the spinnerette 669). the appropriate conditions in former 666, will form the 0407. The controller 674 is also adapted to control the desired mixture of nanomagnetic material and binder. temperature within the former 666 by means of heating/ 04.01 Referring again to FIG. 9, and in the preferred cooling assembly. process depicted therein, the mixture within mixer 63 is preferably stirred until a Substantially homogeneous mixture 0408 Referring again to FIG. 8, and in one preferred is formed. Thereafter, it may be discharged via line 665 to embodiment, a heater (not shown) is used to heat the former 66. substrate 546 to a temperature of from about 100 to about 800 degrees centigrade. 0402 One process for making a fluid composition com prising nanomagnetic particles is disclosed in U.S. Pat. No. 04.09. In one aspect of this embodiment, temperature 5,804.095, “Magnetorheological Fluid Composition,”, of sensing means (not shown) may be used to sense the Jacobs et al; the disclosure of this patent is incorporated temperature of the substrate 546 and, by feedback means herein by reference. In this patent, there is disclosed a (not shown), adjust the output of the heater (not shown). In process comprising numerous material handling steps used one embodiment, not shown, when the substrate 546 is to prepare a nanomagnetic fluid comprising iron carbonyl relatively near flame region 540, optical pyrometry mea particles. One suitable source of iron carbonyl particles Surement means (not shown) may be used to measure the having a median particle size of 3.1 microns is the GAF temperature near the Substrate. Corporation. 0410. In one embodiment, a shutter (not shown) is used 0403. The process of Jacobs et al., is applicable to the to selectively interrupt the flow of vapor 544 to substrate present invention, wherein such nanomagnetic fluid further 546. This shutter, when used, should be used prior to the US 2006/01 02871 A1 May 18, 2006 29 time the flame region has become stable; and the vapor 0420 Referring again to FIG. 8, and in the embodiment should preferably not be allowed to impinge upon the depicted therein, as the coating 548 is being deposited onto Substrate prior to such time. the Substrate 546, and as it is undergoing Solidification 0411 The substrate 546 may be moved in a plane that is thereon, it is preferably subjected to a magnetic field pro substantially parallel to the top of plasma chamber 525. duced by magnetic field generator 550. Alternatively, or additionally, it may be moved in a plane 0421. In this embodiment, it is preferred that the mag that is Substantially perpendicular to the top of plasma netic field produced by the magnetic field generator 550 chamber 525. In one embodiment, the substrate 546 is have a field strength of from about 2 Gauss to about 40 Tesla. moved stepwise along a predetermined path to coat the Substrates with Composite Coatings Disposed Thereon Substrate only at certain predetermined areas. 0422 FIGS. 10-14 are sectional views of coated sub 0412. In one embodiment, rotary substrate motion is strates wherein the coatings comprise two more discrete utilized to expose as much of the Surface of a complex layers of different materials. shaped article to the coating. This rotary Substrate motion 0423 FIG. 10 is a sectional view one preferred coated may be effectuated by conventional means. See, e.g., “Physi assembly 731 that is comprised of a conductor 733 and, cal Vapor Deposition.” edited by Russell J. Hill (Temescal disposed around Such conductor 733, a layer of nanomag Division of The BOC Group, Inc., Berkeley, Calif., 1986). netic material 735. 0413. The process of this embodiment of the invention allows one to coat an article at a deposition rate of from 0424. In the embodiment depicted in FIG. 10, the layer about 0.01 to about 10 microns per minute and, preferably, 735 of nanomagnetic material preferably has a thickness of from about 0.1 to about 1.0 microns per minute, with a at least 150 nanometers and, more preferably, at least about Substrate with an exposed Surface of 35 square centimeters. 200 nanometers. In one embodiment, the thickness of layer One may determine the thickness of the film coated upon 735 is from about 500 to about 1,000 nanometers. said reference substrate material (with an exposed surface of 0425 FIG. 11 is a schematic sectional view of a mag 35 square centimeters) by means well known to those skilled netically shielded assembly 739 that is similar to assembly in the art. 731 but differs therefrom in that a layer 741 of nanoelectrical 0414. The film thickness can be monitored in situ, while material is disposed around layer 735. the vapor is being deposited onto the substrate. Thus, by way 0426. The layer of nanoelectrical material 741 preferably of illustration, one may use an IC-6000 thin film thickness has a thickness of from about 0.5 to about 2 microns. In this monitor (also referred to as “deposition controller) manu embodiment, the nanoelectrical material comprising layer factured by Leybold Inficon Inc. of East Syracuse, N.Y. 741 has a resistivity of from about 1 to about 100 microohm centimeters. As is known to those skilled in the art, when 0415. The deposit formed on the substrate may be mea nanoelectrical material is exposed to electromagnetic radia sured after the deposition by standard profilometry tech tion, and in particular to an electric field, it will shield the niques. Thus, e.g., one may use a DEKTAKSurface Profiler, substrate over which it is disposed from such electrical field. model number 900051 (available from Sloan Technology Reference may be had, e.g., to International patent publica Corporation, Santa Barbara, Calif.). tion WO982O719 in which reference is made to U.S. Pat. 0416) In general, at least about 80 volume percent of the No. 4.963,291; each of these patents and patent applications particles in the as-deposited film are smaller than about 1 is hereby incorporated by reference into this specification. micron. It is preferred that at least about 90 percent of such 0427 As is disclosed in U.S. Pat. No. 4,963,291, one may particles are smaller than 1 micron. Because of this fine produce electromagnetic shielding resins comprised of elec grain size, the surface of the film is relatively smooth. troconductive particles. Such as iron, aluminum, copper, 0417. In one preferred embodiment, the as-deposited film silver and steel in sizes ranging from 0.5 to 0.50 microns. is post-annealed. The entire disclosure of this United States patent is hereby 0418. It is preferred that the generation of the vapor in incorporated by reference into this specification. plasma rector 525 be conducted under substantially atmo 0428 The nanoelectrical particles used in this aspect of spheric pressure conditions. As used in this specification, the the invention preferably have a particle size within the range term “substantially atmospheric' refers to a pressure of at of from about 1 to about 100 microns, and a resistivity of least about 600 millimeters of mercury and, preferably, from from about 1.6 to about 100 microohm-centimeters. In one about 600 to about 1,000 millimeters of mercury. It is embodiment, such nanoelectrical particles comprise a mix preferred that the vapor generation occur at about atmo ture of iron and aluminum. In another embodiment, Such spheric pressure. As is well known to those skilled in the art, nanoelectrical particles consist essentially of a mixture of atmospheric pressure at sea level is 760 millimeters of iron and aluminum. mercury. 0429. It is preferred that, in such nanoelectrical particles, 0419. The process of this invention may be used to and in one embodiment, at least 9 moles of aluminum are produce coatings on a flexible Substrate such as, e.g., stain present for each mole of iron. In another embodiment, at less steel strips, silver strips, gold strips, copper strips, least about 9.5 moles of aluminum are present for each mole aluminum strips, and the like. One may deposit the coating of iron. In yet another embodiment, at least 9.9 moles of directly onto Such a strip. Alternatively, one may first deposit aluminum are present for each mole of iron. one or more buffer layers onto the strip(s). In other embodi 0430. In one embodiment, and referring again to FIG. 13, ments, the process of this invention may be used to produce the layer 741 of nanoelectrical material has a thermal coatings on a rigid or flexible cylindrical Substrate, such as conductivity of from about 1 to about 4 watts/centimeter a tube, a rod, or a sleeve. degree Kelvin. US 2006/01 02871 A1 May 18, 2006 30

0431. In one embodiment, not shown, in either or both of another embodiment, Such particles have an average particle layers 735 and 741 there is present both the nanoelectrical size of less than about 10 nanometers. material and the nanomagnetic material One may produce such a layer 735 and/or 741 by simultaneously depositing 0439. The nanoelectrical particles of this invention have the nanoelectrical particles and the nanomagnetic particles surface area to volume ratio of from about 0.1 to about 0.05 with, e.g., Sputtering technology Such as, e.g., the Sputtering l/nanometer. technology described elsewhere in this specification. 0440 When the nanoelectrical particles of this invention are agglomerated into a cluster, or when they are deposited 0432 FIG. 12 is a sectional schematic view of a mag onto a substrate, the collection of particles preferably has a netically shielded assembly 743 that differs from assembly relative dielectric constant of less than about 1.5. In one 731 in that it contains a layer 745 of nanothermal material embodiment, such relative dielectric constant is less than disposed around the layer 735 of nanomagnetic material. about 1.2. The layer 745 of nanothermal material preferably has a thickness of less than 2 microns and a thermal conductivity 0441. In one embodiment, the nanoelectrical particles of of at least about 150 watts/meter-degree Kelvin and, more this invention are preferably comprised of aluminum, mag preferably, at least about 200 watts/meter-degree Kelvin. It nesium, and nitrogen atoms. This embodiment is illustrated is preferred that the resistivity of layer 745 be at least about in FIG. 15. 10" microohm-centimeters and, more preferably, at least 0442 FIG. 15 illustrates a phase diagram 800 comprised about 10' microohm-centimeters. In one embodiment, the of moieties E, F, and G. Moiety E is preferably selected from resistivity of layer 745 is at least about 10' microohm the group consisting of aluminum, copper, gold, silver, and centimeters. In one embodiment, the nanothermal layer is mixtures thereof. It is preferred that the moiety E have a comprised of AlN. resistivity of from about 2 to about 100 microohm-centime 0433. In one embodiment, depicted in FIG. 12, the ters. In one preferred embodiment, moiety E is aluminum thickness 747 of all of the layers of material coated onto the with a resistivity of about 2.824 microohm-centimeters. As conductor 733 is preferably less than about 20 microns. will apparent, other materials with resistivities within the desired range also may be used. 0434) In FIG. 13, a sectional view of an assembly 749 is depicted that contains, disposed around conductor 733, 0443 Referring again to FIG. 15, moiety G is selected layers of nanomagnetic material 735, nanoelectrical material from the group consisting of nitrogen, oxygen, and mixtures 741, nanomagnetic material 735, and nanoelectrical material thereof. In one embodiment, C is nitrogen, A is aluminum, 741. and aluminum nitride is present as a phase in the system. 0435. In FIG. 14, a sectional view of an assembly 751 is 0444 Referring again to FIG. 15, and in one embodi depicted that contains, disposed around conductor 733, a ment, moiety F is preferably a dopant that is present in a layer 735 of nanomagnetic material, a layer 741 of nano minor amount in the preferred aluminum nitride. In general, electrical material, a layer 735 of nanomagnetic material, a less than about 50 percent (by weight) of the F moiety is layer 745 of nanothermal material, and a layer 735 of present, by total weight of the doped aluminum nitride. In nanomagnetic material. Optionally disposed in layer 753 is one aspect of this embodiment, less than about 10 weight antithrombogenic material that is biocompatible with the percent of the F moiety is present, by total weight of the living organism in which the assembly 751 is preferably doped aluminum nitride. disposed. 0445. The F moiety may be, e.g., magnesium, zinc, tin, indium, gallium, niobium, Zirconium, strontium, lanthanum, 0436. In the embodiments depicted in FIGS. 10 through tungsten, mixtures thereof, and the like. In one embodiment, 14, the coatings 735, and/or 741, and/or 745, and/or 753, are F is selected from the group consisting of magnesium, Zinc, disposed around a conductor 733. In one embodiment, the tin, and indium. In another especially preferred embodiment, conductor so coated is preferably part of medical device, the F moiety is magnesium. preferably an implanted medical device (such as, e.g., a pacemaker). In another embodiment, in addition to coating 0446. Referring again to FIG. 15, and when E is alumi the conductor 733, or instead of coating the conductor 733, num, F is magnesium, and G is nitrogen, it will be seen that the actual medical device itself is coated. regions 802 and 804 correspond to materials which have a low relative dielectric constant (less than about 1.5), and a Preparation of Coatings Comprised of Nanoelectrical Mate high relative dielectric constant (greater than about 1.5), rial respectively. 0437. In this portion of the specification, coatings com A Preferred Drug Delivery Assembly prised of nanoelectrical material will be described. In accor dance with one aspect of this invention, there is provided a 0447. In this section of the specification, applicants will nanoelectrical material with an average particle size of less describe a medical device with improved drug delivery than 100 nanometers, a surface area to volume ratio of from capabilities. This medical device is similar to the medical about 0.1 to about 0.05 l/nanometer, and a relative dielectric device disclosed in published United States patent applica constant of less than about 1.5. tion 2004/0030379, the entire disclosure of which is hereby incorporated by reference into this specification. However, 0438. The nanoelectrical particles of this aspect of the because applicants use an improved form of magnetic par invention have an average particle size of less than about ticles in the device, applicants device provides Superior 100 nanometers. In one embodiment, such particles have an magnetic performance and, additionally, Superior MRI average particle size of less than about 50 nanometers. In yet imageability. US 2006/01 02871 A1 May 18, 2006

0448. The medical system described in this section of the patent application 2004/0030379. Referring to FIG. 19, and specification is preferably a stent 1010 (see FIG. 16) com in the preferred embodiment depicted therein, it will be seen prised of wire like struts 1020 (also see FIG. 16). As is that, in this embodiment, the coated strut 1021 contains a disclosed in paragraph 22 of published United States patent coating comprised of a first coating layer 1040 comprising application 2004/0030379, “The system of the present a biologically active material 1045 and preferably a poly invention comprises (1) a medical device having a coating meric material disposed over the surface 1030 of the strut containing a biologically active material, and (2) a Source of 1025. A second coating layer or sealing layer 1070 com electromagnetic energy or a source for generating an elec prising magnetic particles 1055 and a polymeric material is tromagnetic field. The present invention can facilitate and/or disposed on top of the first coating layer 1040. modulate the delivery of the biologically active material from the medical device. The release of the biologically 0456 FIG. 20 illustrates the effect of exposing a patient active material from the medical device is facilitated or (not shown) who is implanted with a stent having struts 1021 modulated by the electromagnetic energy source or field. To shown in FIG. 19 to an electromagnetic field 1090; this utilize the system of the present invention, the practitioner Figure is similar to FIG. 3B of United States published may implant the coated medical device using regular pro patent application 2004/0030379. Referring to FIG. 20 cedures. After implantation, the patient is exposed to an when such a field 1090 is applied, the magnetic particles extracorporal or external electromagnetic energy source or 1055 move through the sealing layer 1070 as shown by the field to facilitate the release of the biologically active upward arrow 1110, and they create channels 1100 in the material from the medical device. The delivery of the sealing layer 1070. The biologically active material 1045 in biologically active material is on-demand, i.e., the material the underlying first coating layer 1040 is allowed to travel is not delivered or released from the medical device until a through the channels 1100 in the sealing layer 1070 and be practitioner determines that the patient is in need of the released to the surrounding tissue 1120. Since the biologi biologically active material. The coating of the medical cally active material 1045 is in a separate first coating layer device of the present invention further comprises particles 1040 and must migrate through the second coating layer or comprising a magnetic material, i.e., magnetic particles. . . the sealing layer 1070, the release of the biologically active 99 material 1045 is controlled after formation of the channels 11OO. 0449 One embodiment of the medical device 1001 (see FIG. 16) is illustrated in FIG. 17, which shows a cross 0457 FIG. 21 is similar to FIG. 4A of published United sectional view of a coated Strut 1020 of the stent. States patent application 2004/0030379, and it shows 0450. In the embodiment depicted in FIG. 17, the coated another embodiment of a coated stent strut 1023. In this strut 1020 comprises a strut 1025 having a surface 1030. The embodiment, the coating comprises a coating layer 1080 coated Strut 1020 has a composite coating that comprises a comprising a biologically active material 1045, magnetic first coating layer 1040 that contains a biologically active particles 1055, and a polymeric material. material 1045; in one embodiment, this first coating layer 0458 FIG. 22, which is similar to FIG. 4B of published 1040 also contains polymeric material. United States patent application 2004/0030379, illustrates 0451 Referring again to FIG. 17, a second coating layer the effect of exposing a patient (not shown) who is implanted 1050 comprising nanomagnetic particles 1055 is disposed with a stent having struts 1023 to an electromagnetic field over the first coating layer 1040. This second coating layer 1090. The field 1090 is applied, the magnetic particles 1055 1055, in one embodiment, also includes polymeric material. move through the layer 1080 as shown by the arrow 1110 0452 Referring again to FIG. 17, and in the preferred and create channels in the coating layer 1080. The biologi embodiment depicted, a third coating layer or sealing layer cally active material 1045 can then be released to the 1060 is disposed on top of the second coating layer 1050. surrounding tissue 1120. 0453 FIG. 18 is similar to FIG. 2B of United States 0459. In another embodiment, and referring to FIGS. 16 published patent application 2004/0030379; and it illustrates and 23, the medical device 1001 of the present invention the effect of exposing a patient (not shown), who is may be a stent having struts coated with a coating compris implanted with a stent having struts 1020 shown in FIG. 17. ing more than one coating layer containing a magnetic to an electromagnetic energy source or field 1090. When material. FIG. 23 illustrates such a coated strut 1027. The such a field 1090 is applied, the magnetic particles 1055 coating comprises a first coating layer 1040 containing a move out of the second coating layer 1050 in the direction polymeric material and a biologically active material 1045 of upward arrow 1110. This movement disrupts the sealing which is disposed on the surface 1030 of a strut 1025. A layer 1160 and forms channels 1100 in such sealing layer second coating layer 1050 comprising a polymeric material 1060. and magnetic particles 1055 is disposed over the first coating layer 1040. A third coating layer 1044 comprising a poly 0454 Referring again to FIG. 18, it will be seen that the meric material and a biologically active material 1045 is size of the channels 1100 formed generally depends on the disposed over the second coating layer 1050. A fourth size of the magnetic particles 1055 used. The biologically coating layer 1054 comprising a polymeric material and active material 1045 can then be released from the coating magnetic particles 1055 is disposed over this third layer through the disrupted sealing layer 1060 into the surround 1044. Finally a sealing layer 1060 of a polymeric material is ing tissue 1120. The duration of exposure to the field and the disposed over the fourth coating layer 1054. The permeabil strength of the electromagnetic field 1090 determine the rate ity of the coating layers may be different from layer to layer of delivery of the biologically active material 1045. so that the release of the biologically active material from 0455 FIG. 19 illustrates another coated stent 1003; this each layer can differ. Also, the magnetic susceptibility of the Figure is similar to FIG. 3A of United States published magnetic particles may differ from layer to layer. The US 2006/01 02871 A1 May 18, 2006 32 magnetic Susceptibility may be varied using different con device in a patient. Such as restenosis and damaged blood centrations or percentages of magnetic particles in the vessel surface. The nitric oxide is attached to a carrier coating layers. The magnetic Susceptibility of the magnetic molecule and Suspended in the polymer of the coating, but particles may also be varied by changing the size and type it is only biologically active after a bond breaks, thereby of material used for the magnetic particles. When the releasing the Smaller nitric oxide molecule in the polymer magnetic Susceptibility of the magnetic particles differs from and eluting into the Surrounding tissue. Typical nitric oxide layer to layer, different excitation intensity and/or frequency adducts include, e.g., nitroglycerin, Sodium nitroprusside, are required to activate the magnetic particles in each layer. S-nitroso-proteins, S-nitroso-thiols, long carbon-chain lipo philic S-nitrosothiols, S-nitrosodithiols, iron-nitrosyl com 0460 Referring again to FIG. 23, (and also to paragraph pounds, thionitrates, thionitrites, Sydnonimines, furoxans, 27 at page 3 of published United States patent application organic nitrates, and nitrosated amino acids, preferably 2004/0030379), the nanomagnetic particles preferably used mono- or poly-nitrosylated proteins, particularly polynitro in the embodiment depicted in FIG. 23 may be coated with a biologically active material and then incorporated into a sated albumin or polymers or aggregates thereof. The albu coating for the medical device. In one embodiment, the min is preferably human or bovine, including humanized biologically active material is a nucleic acid molecule. The bovine serum albumin. Such nitric oxide adducts are dis nucleic acid coated nanomagnetic magnetic particles may be closed in U.S. Pat. No. 6,087,479 to Stamler et al., the entire formed by painting, dipping, or spraying the magnetic disclosure of which is incorporated herein by reference into particles with a solution comprising the nucleic acid. The this specification. nucleic acid molecules may adhere to the nanomagnetic 0465. In one embodiment, the application of the electro particles via adsorption. Also the nucleic acid molecules magnetic field 1090 effects a chemical change in the poly may be linked to the magnetic particles chemically, via mer coating, thereby allowing for faster release of the linking agents, covalent bonds, or chemical groups that have biologically active material from the coating. affinity for charged molecules. Application of an external 0466 Paragraphs 32-35 of published United States patent electromagnetic field can cause the adhesion between the application 2004/0030379 are applicable to the devices of biologically active material and the magnetic particle to the instant invention. They are presented herein in their break, thereby allowing for release of the biologically active entireties. “B. Drug Release Modulation Employing a material. Mechanical Vibrational Energy Source' 0461 In another embodiment, and referring to such 0467 “Another embodiment of the present invention is a FIGS. 16-23, the magnetic particles may be molded into or system for delivering a biologically active material to a body coated onto a non-metallic medical device, including a of a patient that comprises a mechanical vibrational energy bio-absorb able medical device. The magnetic properties of Source and an insertable medical device comprising a coat the preferred nanomagnetic particles allow the non-metallic ing containing the biologically active material. The coating implant to be extracorporally imaged, vibrated, or moved. In can optionally contain magnetic particles. After the device is specific embodiments, the nanomagnetic particles are implanted in a patient, the biologically active material can be painted, dipped or sprayed onto the outer Surface of the delivered to the patient on-demand or when the material is device. The naomagnetic particles may also be suspended in needed by the patient. To deliver the biologically active a curable coating, such as a UV curable epoxy, or they may material, the patient is exposed to an extracorporal or be electrostatically sprayed onto the medical device and external mechanical vibrational energy source. The subsequently coated with a UV or heat curable polymeric mechanical vibrational energy source includes various material. Sources which cause vibration Such as Sonic or ultrasonic 0462. Additionally, and in some embodiments, the move energy. Exposure to such energy source causes disruption in ment of the magnetic particles that occurs when the patient the coating that allows for the biologically active material to implanted with the coated device is exposed to an external be released from the coating and delivered to body tissue.” electromagnetic field, releases mechanical energy into the 0468 “Moreover, in certain embodiments, the biologi Surrounding tissue in which the medical device is implanted cally active material contained in the coating of the medical and triggers histamine production by the Surrounding tis device is in a modified form. The modified biologically Sues. The histamine has a protective effect in preventing the active material has a chemical moiety bound to the biologi formation of scar tissues in the vicinity at which the medical cally active material. The chemical bond between the moiety device is implanted. and the biologically active material is broken by the 0463. In one embodiment, the movement of the preferred mechanical vibrational energy. Since the biologically active nanomagnetic particles creates a Sufficient amount of heat to material is generally Smaller than the modified biologically kill cells by hyperthermia. This embodiment is described active material, it is more easily released from the coating. elsewhere in this specification, wherein nanomagnetic par Examples of such modified biologically active materials ticles with specified Curie temperatures that preferentially include the nitric oxide adducts described above.” kill cancer cells when heated are described. 0469) “In another embodiment, the coating comprises at 0464) In one preferred embodiment, the application of the least a coating layer containing a polymeric material whose external electromagnetic field 9090 activates the biologi structural properties are changed by mechanical vibrational cally active material in the coating of the medical device. A energy. Such change facilitates release of the biologically biologically active material that may be used in this embodi active material which is contained in the same coating layer ment may be a thermally sensitive substance that is coupled or another coating layer.’ to nitric oxide, e.g., nitric oxide adducts, which prevent 0470 Paragraphs 36, 37, 38, 39, 40, and 41 of published and/or treat adverse effects associated with use of a medical United States patent application 2004/0030379 are also US 2006/01 02871 A1 May 18, 2006

applicable to the medical devices of this invention. They are ferred device, the magnetic particles of Such device are presented below in their entireties. replaced with certain nanomagnetic particles described else where in this specification These nanomangetic particles “C. Materials Suitable for the Invention 1. Suitable Medical Devices preferably have the properties described below. 0476. The nanomagnetic particles are usually in to form 0471) “The medical devices of the present invention are of a coating a nanomagnetic material comprised of Such insertable into the body of a patient. Namely, at least a particles. An assembly comprised of a device, wherein said portion of such medical devices may be temporarily inserted device comprises a Substrate and, disposed over Such Sub into or semi-permanently or permanently implanted in the strate, nanomagnetic material and magetoresistive material, body of a patient. Preferably, the medical devices of the wherein the nanomagnetic material has a Saturation magen present invention comprise a tubular portion which is insert tization of from about 2 to about 3000 electromagnetic units able into the body of a patient. The tubular portion of the per cubic centimeter. The nanomagnetic particles generally medical device need not to be completely cylindrical. For have an average particle size of less than about 100 nanom instance, the cross-section of the tubular portion can be any eters, wherein the average coherence length between adja shape. Such as rectangle, a triangle, etc., not just a circle.” cent nanomagnetic particles is less than 100 nanometers. 0472 “The medical devices suitable for the present 0477. In one embodiment, the nanomagnetic material has invention include, but are not limited to, Stents, Surgical an average particle size of less than about 20 nanometers and Staples, catheters, such as central venous catheters and a phase transition temperature of less than about 200 degrees arterial catheters, guidewires, balloons, filters (e.g., Vena Celsius. cava filters), cannulas, cardiac pacemaker leads or lead tips, cardiac defibrillator leads or lead tips, implantable vascular 0478. In one embodiment, the average particle size of access ports, stent grafts, vascular grafts or other grafts, Such nanomagnetic particles is less than about 15 nanom interluminal paving system, intra-aortic balloon pumps, eters. In another embodiment, the nanomagentic material heart valves, cardiovascular Sutures, total artificial hearts has a Saturation magnetization of at least 2,000 electromag and Ventricular assist pumps.” netic units per cubic centimeter. 0473 "Medical devices which are particularly suitable 0479. In yet another embodiment, the nanomagnetic for the present invention include any kind of stent for material has a saturation magnetization of at least 2,500 medical purposes, which are known to the skilled artisan. electromagnetic units per cubic centimeter. Suitable stents include, for example, vascular stents such as self-expanding stents and balloon expandable stents. 0480. In yet another embodiment, the particles of nano Examples of self-expanding stents useful in the present magnetic material have a squareness of from about 0.05 to invention are illustrated in U.S. Pat. Nos. 4,655,771 and about 1.0. 4,954,126 issued to Wallsten and U.S. Pat. No. 5,061,275 0481. In yet another embodiment, the particles of nano issued to Wallsten et al. Examples of appropriate balloon magnetic material are at least triatomic, being comprised of expandable stents are shown in U.S. Pat. No. 4,733,665 a first distinct atom, a second distinct atom, and a third issued to Palmaz, U.S. Pat. No. 4,800,882 issued to Giant distinct atom. In one aspect of this embodiment, the first urco, U.S. Pat. No. 4,886,062 issued to Wiktor and U.S. Pat. distinct atom is an atom selected from the group consisting No. 5,449,373 issued to Pinchasik et al. A bifurcated stent is of atoms of actinium, americium, berkelium, californium, also included among the medical devices suitable for the cerium, chromium, cobalt, curium, dysprosium, einsteinium, present invention.” erbium, europium, fermium, gadolinium, holmium, iron, 0474 “The medical devices suitable for the present lanthanum, lawrencium, lutetium, manganese, men invention may be fabricated from polymeric and/or metallic delevium, nickel, neodymium, neptunium, nobelium, pluto materials. Examples of Such polymeric materials include nium, praseodymium, promethium, protactinium, Samarium, polyurethane and its copolymers, silicone and its copoly terbium, thorium, thulium, uranium, and ytterbium. In mers, ethylene vinyl-acetate, poly(ethylene terephthalate), another aspect of this embodiment, the distinct atom is a thermoplastic elastomer, polyvinyl chloride, polyolephines, cobalt atom. cellulosics, polyamides, polyesters, polysulfones, polytet 0482 In yet another embodiment, the particles of nano rafluoroethylenes, acrylonitrile butadiene styrene copoly magnetic material are comprised of atoms of cobalt and mers, acrylics, polyactic acid, polyclycolic acid, polycapro atoms of iron. lactone, polyacetal, poly(lactic acid), polylactic acid polyethylene oxide copolymers, polycarbonate cellulose, 0483. In yet another embodiment, such first distinct atom collagen and chitins. Examples of suitable metallic materials is a radioactive cobalt atom. In yet another embodiment, the include metals and alloys based on titanium (e.g., nitinol, particles of nanomagnetic material are comprised of a said nickel titanium alloys, thermo-memory alloy materials), first distinct atom, said second distinct atom, said third stainless Steel, platinum, tantalum, nickel-chrome, certain distinct atom, and a fourth distinct atom. In one aspect of this cobalt alloys including cobalt-chromium-nickel alloys (e.g., embodiment, the particles of nanomagnetic material are Elgiloy(R) and PhynoXR) and gold/platinum alloy. Metallic comprised of a fifth distinct atom. materials also include clad composite filaments, such as those disclosed in WO 94/16646. 0484. In yet another embodiment, such particles of nano magnetic material have a sqareness of from about 0.1 to 0475 Paragraphs 42-47 of published United States patent about 0.9. In one aspect of this embodiment, such particles application 2004/0030379 describes the magnetic particles of nanomagnetic material have a squarenessS is from about used in the device of Such application. In applicants pre 0.2 to about 0.8. US 2006/01 02871 A1 May 18, 2006 34

0485. In yet another embodiment, the nanomagnetic par krypton, oxygen, neon, nitrogen, phosphorus, Sulfur, and ticles have an average size of less of less than about 3 xenon. In one aspect of this embodiment, the third distinct nanometers. In yet another embodiment, the nanomagnetic atom is nitrogen. particles have an average size of less than about 15 nanom 0495. In yet another embodiment, the nanomagnetic par eters. In yet another embodiment, the nanomagnetic par ticles are represented by the formula AxByCZ, wherein A is ticles have an average size is less than about 11 nanometers. said first distinct atom, B is said second distinct atom, C is 0486 In yet another embodiment, the nanomagnetic par said third distinct atom, and X-y+Z is equal to 1. In one ticles have a phase transition temperature of less than 46 aspect of this embodiment, such nanomagnetic particles are degrees Celsius. In yet another embodiment, the nanomag comprised of atoms of oxygen. In another aspect of this netic particles have a a phase transition temperature of less embodiment, the nanomagnetic particles are comprised of than about 50 degrees Celsius. atoms of iro which optionally me be radioactive. In another aspect of this embodiment, such nanomagnetic particles are 0487. In yet another embodiment, the nanomagnetic comprised of atoms of cobalt which, optinally, may be material has a coercive force of from about 0.1 to about 10 radioactive. Oersteds. 0496. In yet another embodiment, the particles of nano 0488. In yet another embodiment, the nanomagnetic par magnetic material are present in the form of a coating with ticles have a relative magnetic permeability of from about a thickness of from about 400 to about 2000 nanometers. In 1.5 to about 2,000. one aspect of this embodiment, the coating has a thickness 0489. In yet another embodiment, the nanomagnetic par of from about 600 to about 1200 nanometers. In another ticles have a saturation magnetization of at least 100 elec aspect of this embodiment, the coating has a morphological tromagnetic units per cubic centimeter. In one aspect of this density of at least about 98 percent, preferably at least about embodiment, the particles of nanomagnetic material have a 99 percent, and more preferably at least about 99.5 percent. saturation magnetization of at least about 200 electromag In another aspect of this embodiment, Such coating has an netic units (emu) per cubic centimeter. In yet another aspect average Surface roughness of less than about 100 nanom of this embodiment, the particles of nanomagnetic material eters, and preferably of less than about 10 nanometers. In another aspect of this embodiment, such coating is biocom have a saturation magnetization of at least about 1,000 patiable. In another aspect of this embodiment, such coating electromagnetic units per cubic centimeter. is is hydrophobic. In yet another aspect of this embodiment, 0490. In yet another embodiment, the nanomagnetic par Such coating is hydrophilic. ticles have a coercive force of from about 0.01 to about 0497 Paragraphs 48, through 72 of published United 5,000 Oersteds. In one aspect of this embodiment, such States patent application 2004/0030379 describe biologi particles of nanomagnetic material have a coercive force of cally active material that may be used in the device of this from about 0.01 to about 3,000 Oersteds. invention. This paragraphs are presented below in their 0491 In yet another embodiment, the nanomagnetic par entireties. ticles have a relative magnetic permeability of from about 1 “3. Biologically Active Material” to about 500,000. In one aspect of this embodiment, such particles have a relative magnetic permeability of from 0498 “The term biologically active material encom about 1.5 to about 260,000. passes therapeutic agents, such as drugs, and also genetic materials and biological materials. The genetic materials 0492. In yet another embodiment, the nanomagnetic par mean DNA or RNA, including, without limitation, of DNA/ ticles have a mass density of at least about 0.001 grams per RNA encoding a useful protein stated below, anti-sense cubic centimeter. In one aspect of this embodiment, Such DNA/RNA, intended to be inserted into a human body particles of nanomagnetic material have a mass density of at including viral vectors and non-viral vectors. Examples of least about 1 gram per cubic centimeter. In another aspect of DNA suitable for the present invention include DNA encod this embodiment, such particles of nanomagnetic material ing . . . anti-sense RNA . . . thNA or rRNA to replace have a mass density of at least about 3 grams per cubic defective or deficient endogenous molecules . . . angiogenic centimeter. In yet another aspect of this embodiment, Such factors including growth factors, such as acidic and basic particles of nanomagnetic material have a mass density of at fibroblast growth factors, vascular endothelial growth factor, least about 4 grams per cubic centimeter. epidermal growth factor, transforming growth factor C. and 0493. In yet another embodiment, the second distinct B, platelet-derived endothelial growth factor, plateletderived atom of Such nanomagnetic particles has a relative magnetic growth factor, tumor necrosis factor C. hepatocyte growth permeability of about 1.0. In one aspect of this embodiment, factor and insulin like growth factor . . . cell cycle inhibitors Such second distinct atom is an atom selected from the group including CD inhibitors . . . thymidine kinase (“TK) and consisting of aluminum, antimony, barium, beryllium, other agents useful for interfering with cell proliferation, and boron, bismuth, calcium, gallium, germanium, gold, indium, ... the family of bone morphogenic proteins (“BMPs') as lead, magnesium, palladium, platinum, silicon, silver, stron explained below. Viral vectors include adenoviruses, gutted tium, tantalum, tin, titanium, tungsten, yttrium, Zirconium, adenoviruses, adeno-associated virus, retroviruses, alpha magnesium, and Zinc. virus (Semliki Forest, Sindbis, etc.), lentiviruses, herpes simplex virus, ex vivo modified cells (e.g., stem cells, 0494. In yet another embodiment, the nanomagnetic par fibroblasts, myoblasts, satellite cells, pericytes, cardiomyo ticles are comprised of a third distinct atom that is an atom cytes, sketetal myocytes, macrophage), replication compe selected from the group consisting of argon, bromine, car tent viruses (e.g., ONYX-015), and hybrid vectors. Non bon, chlorine, fluorine, helium, helium, hydrogen, iodine, viral vectors include artificial chromosomes and mini US 2006/01 02871 A1 May 18, 2006

chromosomes, plasmid DNA vectors (e.g., pCOR), cationic Vascular Endothelial Growth Factors (FEGF, all types polymers (e.g., polyethyleneimine, polyethyleneimine including VEGF-2), growth factor receptors, transcriptional (PEI) graft copolymers (e.g., polyether-PEI and polyethyl activators, and translational promotors; vascular cell growth ene oxide-PEI), neutral polymers PVP, SP1017 inhibitors such as antiproliferative agents, growth factor (SUPRATEK), lipids or lipoplexes, nanoparticles and inhibitors, growth factor receptor antagonists, transcrip microparticles with and without targeting sequences such as tional repressors, translational repressors, replication inhibi the protein transduction domain (PTD).” tors, inhibitory antibodies, antibodies directed against growth factors, bifunctional molecules consisting of a 0499. “The biological materials include cells, yeasts, growth factor and a cytotoxin, bifunctional molecules con bacteria, proteins, peptides, cytokines and hormones. sisting of an antibody and a cytotoxin; . . . cholesterol Examples for peptides and proteins include growth factors lowering agents; vasodilating agents; and agents which (FGF, FGF-1, FGF-2, VEGF, Endotherial Mitogenic Growth interfere with endogenous vasoactive mechanisms; . . . Factors, and epidermal growth factors, transforming growth anti-oxidants, such as probucol; . . . antibiotic agents, such factor C. and B, platelet derived endothelial growth factor, as penicillin, cefoxitin, oxacillin, tobranycin . . . angiogenic platelet derived growth factor, tumor necrosis factor C. Substances, such as acidic and basic fibrobrast growth fac hepatocyte growth factor and insulin like growth factor), tors, estrogen including estradiol (E2), estriol (E3) and transcription factors, proteinkinases, CD inhibitors, thymi 17-Beta Estradiol; and . . . drugs for heart failure, such as dine kinase, and bone morphogenic proteins (BMPs). Such digoxin, beta-blockers, angiotensin-converting enzyme as BMP-2, BMP-3, BMP-4, BMP-5, BMP-6 (Vgr-1), (ACE) inhibitors including captopril and enalopril.” BMP-7 (OP-1), BMP-8. BMP-9, BMP-10, BMP-11, BMP 12, BMP-13, BMP-14, BMP-15, and BMP-16. Currently 0500 “Also, the biologically active materials of the preferred BMP's are BMP-2, BMP-3, BMP-4, BMP-5, present invention include trans-retinoic acid and nitric oxide BMP-6, BMP-7. Alternatively or in addition, molecules adducts. A biologically active material may be encapsulated capable of inducing an upstream or downstream effect of a in micro-capsules by the known methods.” BMP can be provided. Such molecules include any of the "hedgehog proteins, or the DNA’s encoding them. These 0501 Paragraphs 73 through 82 of published United dimeric proteins can be provided as homodimers, het States patent application 1004/0030379 describe coating erodimers, or combinations thereof, alone or together with compositions that may be used in the device of the instant other molecules. Cells can be of human origin (autologous invention; and they are reproduced in their entireties below. or allogeneic) or from an animal source (Xenogeneic), 0502 “4. Coating Compositions . . . The coating com genetically engineered, if desired, to deliver proteins of positions suitable for the present invention can be applied by interest at the transplant site. The delivery media can be any method to a surface of a medical device to form a formulated as needed to maintain cell function and viability. coating. Examples of Such methods are painting, spraying, Cells include whole bone marrow, bone marrow derived dipping, rolling, electrostatic deposition and all modern mono-nuclear cells, progenitor cells (e.g., endothelial pro chemical ways of immobilization of bio-molecules to sur gentitor cells) stem cells (e.g., mesenchymal, hematopoietic, faces.” neuronal), pluripotent stem cells, fibroblasts, macrophage, and satellite cells.’"Biologically active material also 0503 “The coating composition used in the present includes non-genetic therapeutic agents, such as: . . . anti invention may be a solution or a Suspension of a polymeric thrombogenic agents such as heparin, heparin derivatives, material and/or a biologically active material and/or mag urokinase, and PPack (dextrophenylalanine proline arginine netic particles in an aqueous or organic solvent Suitable for chloromethylketone); . . . anti-proliferative agents such as the medical device which is known to the skilled artisan. A enoxaprin, angiopeptin, or monoclonal antibodies capable of slurry, wherein the solid portion of the Suspension is com blocking Smooth muscle cell proliferation, hirudin, and paratively large, can also be used as a coating composition acetylsalicylic acid, amlodipine and doxazosin; . . . anti for the present invention. Such coating composition may be inflammatory agents such as glucocorticoids, betametha applied to a Surface, and the solvent may be evaporated, and Sone, dexamethasone, prednisolone, corticosterone, budes optionally heat or ultraviolet (UV) cured.” onide, estrogen, SulfaSalazine, and mesalamine; . . . 0504 “The solvents used to prepare coating composi immunosuppressants such as sirolimus (RAPAMYCIN), tions include ones which can dissolve the polymeric material tacrolimus, everolimus and examethasone, . . . antineoplas into Solution and do not alter or adversely impact the tic/antiproliferative/anti-miotic agents such as paclitaxel, therapeutic properties of the biologically active material 5-fluorouracil, cisplatin, vinblastine, Vincristine, employed. For example, useful solvents for silicone include epothilones, methotrexate, azathioprine, halofluginone, tetrahydrofuran (THF), chloroform, toluene, acetone, isooc adriamycin, actinomycin and mutamycin; cladribine; tane, 1,1,1-trichloroethane, dichloromethane, and mixture endostatin, angiostatin and thymidine kinase inhibitors, and thereof.” its analogs or derivatives; . . . anesthetic agents such as lidocaine, bupivacaine, and ropivacaine; . . . anti-coagulants 0505) “A coating of a medical device of the present such as D-Phe-Pro-Arg chloromethyl keton, an RGD pep invention may consist of various combinations of coating tide-containing compound, heparin, antithrombin com layers. For example, the first layer disposed over the surface pounds, platelet receptor antagonists, anti-thrombin antibod of the medical device can contain a polymeric material and ies, anti-platelet receptor antibodies, aspirin (aspirin is also a first biologically active material. The second coating layer, classified as an analgesic, antipyretic and anti-inflammatory that is disposed over the first coating layer, contains mag drug), dipyridamole, protamine, hirudin, prostaglandin netic particles and optionally a polymeric material. The inhibitors, platelet inhibitors and tick antiplatelet peptides; . second coating layer protects the biologically active material . . Vascular cell growth promoters such as growth factors, in the first coating layer from exposure during implantation US 2006/01 02871 A1 May 18, 2006 36 and prior to delivery. Preferably, the second coating layer is medical device or polymers having relatively low melting substantially free of a biologically active material.” points that can be blended with biologically active materials. Additional Suitable polymers include, thermoplastic elas 0506 “Another layer, i.e. sealing layer, which is free of tomers in general, polyolefins, polyisobutylene, ethylene magnetic particles, can be provided over the second coating alphaolefin copolymers, acrylic polymers and copolymers, layer. Further, there may be another coating layer containing vinyl halide polymers and copolymers such as polyvinyl a second biologically active material disposed over the chloride, polyvinyl ethers such as polyvinyl methyl ether, second coating layer. The first and second biologically active polyvinylidene halides such as polyvinylidene fluoride and materials may be identical or different. When the first and polyvinylidene chloride, polyacrylonitrile, polyvinyl second biologically active material are identical, the con ketones, polyvinyl aromatics Such as polystyrene, polyvinyl centration in each layer may be different. The layer contain esters such as polyvinyl acetate, copolymers of vinyl mono ing the second biologically active material may be covered mers, copolymers of vinyl monomers and olefins such as with yet another coating layer containing magnetic particles. ethylene-methyl methacrylate copolymers, acrylonitrile-sty The magnetic particles in two different layers may have an rene copolymers, ABS (acrylonitrile-butadiene-styrene) res identical or a different average particle size and/or an ins, ethylene-vinyl acetate copolymers, polyamides Such as identical or a different concentrations. The average particle Nylon 66 and polycaprolactone, alkyd resins, polycarbon size and concentration can be varied to obtain a desired ates, polyoxymethylenes, polyimides, epoxy resins, rayon release profile of the biologically active material. In addi triacetate, cellulose, cellulose acetate, cellulose butyrate, tion, the skilled artisan can choose other combinations of cellulose acetate butyrate, cellophane, cellulose nitrate, cel those coating layers.” lulose propionate, cellulose ethers, carboxymethyl cellulose, 0507 “Alternatively, the coating of a medical device of collagens, chitins, polylactic acid, polyglycolic acid, poly the present invention may comprise a layer containing both lactic acid-polyethylene oxide copolymers, EPDM (etylene a biologically active material and magnetic particles. For propylene-diene) rubbers, fluorosilicones, polyethylene gly example, the first coating layer may contain the biologically col, polysaccharides, phospholipids, and combinations of active material and magnetic particles, and the second the foregoing. Preferred is polyacrylic acid, available as coating layer may contain magnetic particles and be Sub HYDROPLUSR) (Boston Scientific Corporation, Natick, stantially free of a biologically active material. In such Mass.), and described in U.S. Pat. No. 5,091,205, the embodiment, the average particle size of the magnetic disclosure of which is hereby incorporated herein by refer particles in the first coating layer may be different than the ence. In a most preferred embodiment of the invention, the average particle size of the magnetic particles in the second polymer is a copolymer of polylactic acid and polycapro coating layer. In addition, the concentration of the magnetic lactone.” particles in the first coating layer may be different than the concentration of the magnetic particles in the second coating 0509) “More preferably for medical devices which layer. Also, the magnetic Susceptibility of the magnetic undergo mechanical challenges, e.g. expansion and contrac tion, the polymeric materials should be selected from elas particles in the first coating layer may be different than the tomeric polymers such as silicones (e.g. polysiloxanes and magnetic susceptibility of the magnetic particles in the Substituted polysiloxanes), polyurethanes, thermoplastic second coating layer.’ elastomers, ethylene vinyl acetate copolymers, polyolefin 0508 “The polymeric material should be a material that elastomers, and EPDM rubbers. Because of the elastic is biocompatible and avoids irritation to body tissue. nature of these polymers, the coating composition adheres Examples of the polymeric materials used in the coating better to the surface of the medical device when the device composition of the present invention include, but not limited is subjected to forces, stress or mechanical challenge.” to, polycarboxylic acids, cellulosic polymers, including cel lulose acetate and cellulose nitrate, gelatin, polyvinylpyr 0510) “The amount of the polymeric material present in rolidone, cross-linked polyvinylpyrrolidone, polyanhydrides the coatings can vary based on the application for the including maleic anhydride polymers, polyamides, polyvi medical device. One skilled in the art is aware of how to nyl alcohols, copolymers of vinyl monomers such as EVA, determine the desired amount and type of polymeric mate polyvinyl ethers, polyvinyl aromatics, polyethylene oxides, rial used in the coating. For example, the polymeric material glycosaminoglycans, polysaccharides, polyesters including in the first coating layer may be the same as or different than polyethylene terephthalate, polyacrylamides, polyethers, the polymeric material in the second coating layer. The polyether Sulfone, polycarbonate, polyalkylenes including thickness of the coating is not limited, but generally ranges polypropylene, polyethylene and high molecular weight from about 25 um to about 0.5 mm. Preferably, the thickness polyethylene, halogenated polyalkylenes including polytet is about 30 um to 100 um.” rafluoroethylene, polyurethanes, polyorthoesters, proteins, 0511 Paragraphs 84 thrugh 92 of published United States polypeptides, silicones, siloxane polymers, polylactic acid, patent application 2004/0030379 describes certain energy polyglycolic acid, polycaprolactone, polyhydroxybutyrate Sources which may be used in conjunction with the medical Valerate, styrene-isobutylene copolymers and blends and devices of this invention. These paragraphs are presented copolymers thereof. Also, other examples of Such polymers below in their entireties. include polyurethane (BAYHDROL(R), etc.) fibrin, collagen and derivatives thereof, polysaccharides Such as celluloses, 0512 “5. Electromagnetic Sources . . . An external elec starches, dextrans, alginates and derivatives, hyaluronic tromagnetic source or field may be applied to the patient acid, and squalene. Further examples of the polymeric having an implanted coated medical device using any materials used in the coating composition of the present method known to skilled artisan. In the method of the invention include other polymers which can be used include present invention, the electromagnetic field is oscillated. ones that can be dissolved and cured or polymerized on the Examples of devices which can be used for applying an US 2006/01 02871 A1 May 18, 2006 37 electromagnetic field include a magnetic resonance imaging mal and thermotherapeutic effect in diseased tissue. U.S. (“MRI) apparatus. Generally, the magnetic field strength Pat. No. 5,873,828 discloses a device having an ultrasonic suitable is within the range of about 0.50 to about 5 Tesla vibrator with either a microwave or radio frequency probe. (Webber per square meter). The duration of the application U.S. Pat. No. 6,056,735 discloses an ultrasonic treating may be determined based on various factors including the device having a probe connected to a ultrasonic transducer strength of the magnetic field, the magnetic Substance con and a holding means to clamp a tissue. Any of those methods tained in the magnetic particles, the size of the particles, the and devices can be adapted for use in the method of the material and thickness of the coating, the location of the present invention.” particles within the coating, and desired releasing rate of the 0517 “Ultrasound energy application can be conducted biologically active material.” percutaneously through Small skin incisions. An ultrasonic 0513. “In an MRI system, an electromagnetic field is vibrator or probe can be inserted into a subject’s body uniformly applied to an object under inspection. At the same through a body lumen, such as blood vessels, bronchus, time, a gradient magnetic field, Superposing the electromag urethral tract, digestive tract, and vagina. However, an netic field, is applied to the same. With the application of ultrasound probe can be appropriately modified, as known in these electromagnetic fields, the object is applied with a the art, for Subcutaneous application. The probe can be selective excitation pulse of an electromagnetic wave with a positioned closely to an outer Surface of the patient body resonance frequency which corresponds to the electromag proximal to the inserted medical device.” netic field of a specific atomic nucleus. As a result, a 0518 “The duration of the procedure depends on many magnetic resonance (MR) is selectively excited. A signal factors, including the desired releasing rate and the location generated is detected as an MR signal. See U.S. Pat. No. of the inserted medical device. The procedure may be 4,115,730 to Mansfield, U.S. Pat. No. 4,297,637 to Crooks performed in a Surgical Suite where the patient can be et al., and U.S. Pat. No. 4,845,430 to Nakagayashi. For the monitored by imaging equipment. Also, a plurality of probes present invention, among the functions of the MRI appara can be used simultaneously. One skilled in the art can tus, the function to create an electromagnetic field is useful determine the proper cycle of the ultrasound, proper inten for the present invention. The implanted medical device of sity of the ultrasound, and time to be applied in each specific the present can be located as usually done for MRI imaging, case based on experiments using an animal as a model.” and then an electromagnetic field is created by the MRI 0519) “In addition, one skilled in the art can determine apparatus to facilitate release of the biologically active the excitation source frequency of the mechanical vibra material. The duration of the procedure depends on many tional energy source. For example, the mechanical vibra factors, including the desired releasing rate and the location tional energy source can have an excitation source frequency of the inserted medical device. One skilled in the art can in the range of about 1 Hertz to about 300 kiloHertz. Also, determine the proper cycle of the electromagnetic field, the shape of the frequency can be of different types. For proper intensity of the electromagnetic field, and time to be example, the frequency can be in the form of a square pulse, applied in each specific case based on experiments using an ramp, Sawtooth, sine, triangle, or complex. Also, each form animal as a model. can have a varying duty cycle.” 0514) “In addition, one skilled in the art can determine 0520 Paragraphs 93 through 97 of published United the excitation source frequency of the elecromagnetic States patent application 2004/0030379 describe processes energy source. For example, the electromagnetic field can for treating body tissue that may be used in conjunction with have an excitation Source frequency in the range of about 1 the medical device of this invention. These paragraphs are Hertz to about 300 kiloHertz. Also, the shape of the fre presented below in their entireties.” quency can be of different types. For example, the frequency 0521 “D. Treatment of Body Tissue With the Invention can be in the form of a square pulse, ramp, Sawtooth, sine, ... The present invention provides a method of treatment to triangle, or complex. Also, each form can have a varying reduce or prevent the degree of restenosis or hyperplasia duty cycle.” after vascular intervention Such as angioplasty, stenting, 0515 “6. Mechanical Vibrational Energy Source ... The atherectomy and grafting. All forms of vascular intervention mechanical vibrational energy source includes various are contemplated by the invention, including, those for Sources which cause vibration Such as ultrasound energy. treating diseases of the cardiovascular and renal system. Examples of suitable ultrasound energy are disclosed in U.S. Such vascular intervention include, renal angioplasty, per Pat. No. 6,001,069 to Tachibana et al. and U.S. Pat. No. cutaneous coronary intervention (PCI), percutaneous trans 5,725,494 to Brisken, PCT publications WO00/16704, luminal coronary angioplasty (PTCA); carotid percutaneous WO00/18468, WO00/00095, WO00/07508 and WO99/ transluminal angioplasty (PTA); coronary by-pass grafting, 33391, which are all incorporated herein by reference. angioplasty with stent implantation, peripheral percutaneous Strength and duration of the mechanical vibrational energy transluminal intervention of the iliac, femoral or popliteal of the application may be determined based on various arteries, carotid and cranial vessels, Surgical intervention factors including the biologically active material contained using impregnated artificial grafts and the like. Furthermore, in the coating, the thickness of the coating, structure of the the system described in the present invention can be used for coating and desired releasing rate of the biologically active treating vessel walls, portal and hepatic veins, esophagus, material.” intestine, ureters, urethra, intracerebrally, lumen, conduits, channels, canals, vessels, cavities, bile ducts, or any other 0516 “Various methods and devices may be used in duct or passageway in the human body, either in-born, built connection with the present invention. For example, U.S. in or artificially made. It is understood that the present Pat. No. 5,895.356 discloses a probe for transurethrally invention has application for both human and veterinary applying focused ultrasound energy to produce hyperther SC. 99 US 2006/01 02871 A1 May 18, 2006

0522 “The present invention also provides a method of cation, discloses and claims “1. A medical preparation treatment of diseases and disorders involving cell overpro including nanoscalar particles that generate heat when an liferation, cell migration, and enlargement. Diseases and alternating electromagnetic field is applied, said nanoscalar disorders involving cell overproliferation that can be treated particles comprising: a core containing iron oxide and an or prevented include but are not limited to malignancies, inner shell with groups that are capable of forming cationic premalignant conditions (e.g., hyperplasia, metaplasia, dys groups, wherein the iron oxide concentration is in the range plasia), benign tumors, hyperproliferative disorders, benign from 0.01 to 50 mg/ml of synovial fluid at a power absorp dysproliferative disorders, etc. that may or may not result tion in the range from 50 to 500 mW/mg of iron and heating from medical intervention. For a review of such disorders, to a temperature in the range from 42 to 50° C.; and see Fishman et al., 1985, Medicine, 2d Ed., J. B. Lippincott pharmacologically active species bound to said inner shell Co., Philadelphia.” selected from the group consisting of thermosensitizers and 0523 “Whether a particular treatment of the invention is thermosensitive chemotherapeutics or isotopes thereof. effective to treat restenosis or hyperplasia of a body lumen wherein said preparation is used for treating arthrosis, arthri can be determined by any method known in the art, for tis and rheumatic joint diseases by directly injecting said example but not limited to, those methods described in this nanoscalar particles into the synovial fluid, said nanoscalar section. The safety and efficiency of the proposed method of particles being absorbed by said fluid and transported to the treatment of a body lumen may be tested in the course of inflamed synovial membrane where they are activated after systematic medical and biological assays on animals, toxi a predefined period of time by applying said alternating cological analyses for acute and systemic toxicity, histologi electromagnetic field.” cal studies and functional examinations, and clinical evalu 0528 Applicants’ medical preparation is similar to the ation of patients having a variety of indications for preparation of U.S. Pat. No. 6,669,623 but differs therefrom restenosis or hyperplasia in a body lumen.” in that, instead of an iron oxide core, applicants preparation 0524 “The efficacy of the method of the present inven is comprised of the nanomagnetic material described else tion may be tested in appropriate animal models, and in where in this specification. human clinical trials, by any method known in the art. For 0529) As is disclosed in column 2 of U.S. Pat. No. example, the animal or human Subject may be evaluated for 6,669,623. “The invention is based on the concept of using any indicator of restenosis or hyperplasia in a body lumen a Suspension of nanoscalar particles designed based on the that the method of the present invention is intended to treat. description given in DE 19726 282 for treating rheumatic The efficacy of the method of the present invention for joint diseases, said particles comprising, in a first embodi treatment of restenosis or hyperplasia can be assessed by ment, a core containing iron oxide, an inner shell that measuring the size of a body lumen in the animal model or encompasses said core and comprises groups capable of human Subject at Suitable time intervals before, during, or forming cationic groups, and an outer shell made of species after treatment. Any change or absence of change in the size comprising neutral and/or anionic groups, and radionuclides of the body lumen can be identified and correlated with the and cytotoxic Substances bound to said inner shell. These effect of the treatment on the subject. The size of the body nanoscalar particles may also be one-shelled, i.e. consist just lumen can be determined by any method known in the art, of the core and the inner shell, designed as described above. for example, but not limited to, angiography, ultrasound, . . . It has been found that despite the fact that phagocytic fluoroscopy, magnetic resonance imaging, optical coherence activity in the synovial fluid decreases as the patients age tumography and histology.” increases, intracellular adsorption of the particles according 0525) In one preferred embodiment, also described in to the invention in macrophages is increased even in patho more detail in another portion of this specification, inorganic logically changed macrophage titers in the joint cavity, and tubules of halloysite are coated with nanomagnetic material that the inflammatory process is controlled as said particles (see, e.g., FIG. 33 and its accompanying description) and adhere to actively proliferating cells of the synovia. Due to thereafter filled with one or more biologically active mate these effects and the heat generated when applying an rials; the nanomagnetic material is preferably chosen so that alternating electromagnetic field, the radionuclides show it has a ferrogmagnetic resonance frequency of from about increased efficacy as compared to radiosynoviorthesis. Last 9 to about 10 gigahertz. The filled, coated halloysite tubules but not least, Success of treatment is increased beyond the thus produced may be, e.g., incorporated into a binder additive effect of each component due to binding Substances (which may be polymeric, resinous, elastomeric, and/or that have a cytotoxic effect when exposed to heat to the ceramic, as is described elsewhere in this specification); and particles, as this efficiently combines radiotherapy, thermo thus composite material may then be irradiated with a source therapy, and chemotherapy.” of electromagnetic energy that will cause the nanomagenetic material to absorb Such energy and convert Some of it to 0530. As is disclosed at columns 2-3 of U.S. Pat. No. heat. The heating of the filled tubules will cause some or all 6,669,623. “According to an embodiment that utilizes the of the biologically active material to elute. invention, a suspension of nanoscalar particles formed by an iron oxide core and two shells, with doxorubicin as a A Medical Preparation for Treating Arthrosis, Arthritis, and heat-sensitive cytotoxic material and beta emitting radionu Other Diseases clides bound to said particles, is directly injected into the 0526 In one embodiment of this invention, a novel joint cavity to be treated. Depending on phagocytic activity medical preparation comprised of applicants nanomagnetic in the synovia, the Suspension will stay there without gen particles is provided. This preparation is similar to the erating heat for a period of time that is determined before the preparation described in U.S. Pat. No. 6,669,623. therapy begins. This period can be from 1 hour to 72 hours. 0527 U.S. Pat. No. 6,669,623, the entire disclosure of In this period, the two-shelled nanoparticles according to the which is hereby incorporated by reference into this specifi invention are absorbed by the synovial fluid and flow into US 2006/01 02871 A1 May 18, 2006 39 the inflamed synovial membrane. The therapist then ascer tively is possible, and the outer shell(s) being constituted by tains using magnetic resonance tomography whether the species having neutral and/or anionic groups which, from nanoparticles are really deposited in the synovial membrane, without, make the nanoscale particles appear neutral or the adjacent lymph nodes, and in the healthy tissue. If negatively charged and which is (are) degraded by the required, an extravasation to adjacent areas may be per human or animal body tissue to expose the underlying formed but this should not be necessary due to the high rate shell(s) at a rate which is higher than that for the innermost of phagocytosis. . . . Subsequently, the area is exposed to an shell but still low enough to ensure a sufficient distribution alternating electromagnetic field with an excitation fre of said nanoscale particles within a body tissue which has quency in the range from 1 kHz and 100 MHz. Its actual been punctually infiltrated therewith.” The particles of this value depends on the location of the diseased joint. While published application comprise an iron-oxide-contianing hands and arms are treated at higher frequencies, 500 kHz core with at least two shells (coats). will be sufficient for back pain, the lower joints and the thigh joints. The alternating electromagnetic field brings out the 0533. As is disclosed in paragraphs 0005 and 0006 of localized heat; at the same time, the radionuclide and the published United States patent application 2003/018370, “. cytotoxic Substances (here: doxorubicin) are activated, and ... Such particles can be obtained by providing a (preferably success of treatment beyond the added effects of its com Superparamagnetic) iron oxide-containing core with at least ponents is achieved due to the trimodal combinatorial effect two shells (coats), the shell adjacent to the core having many of therapies and the differential endocytosis and high rate of positively charged functional groups which permits an easy phagocytosis of the nano-particles. This means that the incorporation of the thus encased iron oxide-containing synovial membrane shows increased and Sustained Scleros cores into the inside of the tumor cells, said inner shell ing with this treatment as compared to other medical prepa additionally being degraded by the (tumor) tissue at Such a rations and methods of treating rheumatic diseases. . . . The low rate that the cores encased by said shell have sufficient heat that can be generated by the alternating electromagnetic time to adhere to the cell Surface (e.g. through electrostatic field applied to the nanoparticles, or, in other words, the interactions between said positively charged groups and duration of applying the alternating electromagnetic field to negatively charged groups on the cell Surface) and to Sub obtain a specific equilibrium temperature is calculated in sequently be incorporated into the inside of the cell. In advance based on the iron oxide concentration that is contrast thereto, the outer shell(s) is (are) constituted by typically in the range from 0.01 to 50 mg/ml of synovial species which shield (mask) or compensate, respectively, or fluid and power absorption that is typically in the range from even overcompensate the underlying positively charged 50 to 500 mW/mg of iron. Then the field strength is reduced groups of the inner shell (e.g. by negatively charged func to keep the temperature on a predefined level of, for tional groups) so that, from without, the nanoscale particle example, 45° C. However, there is a considerable tempera having said outer shell(s) appears to have an overall neutral ture drop from the synovial layer treated to adjacent carti or negative charge. Furthermore the outer shell(s) is (are) lage and bone tissue so that the cartilage layer and the bone degraded by the body tissue at a (Substantially) higher rate will not be damaged by this heat treatment. The temperature than the innermost shell, said rate being however still low in the cartilage layer is slightly increased as compared to enough to give the particles Sufficient time to distribute normal physiological conditions (38° C. to 40° C.). The themselves within the tissue if they are injected punctually resulting stimulation of osteoblasts improves the reconsti into the tissue (e.g. in the form of a magnetic fluid). In the tution of degeneratively modified bone borders and carti course of the degradation of said outer shell(s) the shell lage. Repeated applications of the alternating electromag adjacent to the core is exposed gradually. As a result thereof, netic field not only counteract recurring inflammation after due the outer shell(s) (and their electroneutrality or negative the decline of radioactivity but—at an equilibrium tempera charge as seen from the exterior) the coated cores initially ture in the range from 38 to 40° C.—are also used to become well distributed within the tissue and upon their stimulate osteoblast division. When applying static magnetic distribution they also will be readily imported into the inside field gradients, the particles can be concentrated in the of the tumor cells (and first bound to the surfaces thereof, treated joint (magnetic targeting). “The iron-oxide core of respectively), due to the innermost shell that has been the particles of this U.S. Pat. No. 6,669.223 may advanta exposed by the biological degradation of the outer shell(s). geously be replaced with the nanomagnetic material core of ... Thus the present invention relates to nanoscale particles having an iron oxide-containing core (which is ferro-, ferri the present invention. or, preferably, Superparamagnetic) and at least two shells 0531. By way of further illustration, one may replace the Surrounding said core, the (innermost) shell adjacent to the iron-oxide containing core of the nanoparticles of published core being a coat that features groups capable of forming United States patent application US2003/0180370 with the cationic groups and that is degraded by the human or animal nanomagnetic material of this invention. The entire disclo body tissue at Such a low rate that an association of the core sure of this published United States patent application is surrounded by said coat with the surfaces of cells and the hereby incorporated by reference into this specification. incorporation of said core into the inside of cells, respec 0532 Claim 1 of published United States patent applica tively is possible, and the outer shell(s) being constituted by tion 2003/0180370 describes “1. Nanoscale particles having species having neutral and/or anionic groups which, from an iron oxide-containing core and at least two shells Sur without, make the nanoscale particles appear neutral or rounding said core, the (innermost) shell adjacent to the core negatively charged and which is (are) degraded by the being a coat that features groups capable of forming cationic human or animal body tissue to expose the underlying groups and that is degraded by the human or animal body shell(s) at a rate which is higher than that for the innermost tissue at Such a low rate that an association of the core shell but still low enough to ensure a sufficient distribution surrounded by said coat with the surfaces of cells and the of said nanoscale particles within a body tissue which has incorporation of said core into the inside of cells, respec been punctually infiltrated therewith.” US 2006/01 02871 A1 May 18, 2006 40

0534) Paragraph 0007 of published United States patent shell(s) may then be effected by (e.g., enzymatic) cleavage application US2003/0180370 indicates that the core of the of said bonds, whereby at the same time said amino groups particles of this patent application "... consists of pure iron are regenerated.” oxide. . . . . Applicants advantageously Substitute their 0537) The particles of published United States patent nanomagnetic material of this invention for Such “ . . . pure application 2003/0180370 (and the related particles of the iron oxide. . . . ' instant invention) may be used to deliver therapeutic agents 0535 The shells of published United States patent appli to the inside of cells in the manner disclosed in paragraphs cation US2003/0180370 are discussed in paragraphs 0013 0017 et seq. of published United States patent application through 0016 of such patent application. As is disclosed in 2003/0180370. As is disclosed in such published patent these paragraphs, “According to the present invention one or application, "Although the essential elements of the nanos more (preferably one) outer shells are provided on the cale particles according to the present invention are (i) the described innermost shell . . . the outer shell serves to iron oxide-containing core, (ii) the inner shell which in its achieve a good distribution within the tumor tissue of the exposed state is positively charged and which is degradable iron oxide-containing cores having said inner shell, said at a lower rate, and (iii) the outer shell which is biologically outer shell being required to be biologically degradable (i.e., degradable at a higher rate and which, from without, makes by the tissue) after having served its purpose to expose the the nanoscale particles appear to have an overall neutral or underlying innermost shell, which permits a smooth incor negative charge, the particles according to the invention still poration into the inside of the cells and an association with may comprise other, additional components. In this context the surfaces of the cells, respectively. The outer shell is there may particularly be cited Substances which by means constituted by species having no positively charged func of the particles of the present invention are to be imported tional groups, but on the contrary having preferably nega into the inside of cells (preferably tumor cells) to enhance tively charged functional groups so that, from without, said the effect of the cores excited by an alternating magnetic nanoscale particles appear to have an overall neutral charge field therein or to fulfill a function independent thereof. Such (either by virtue of a shielding (masking) of the positive substances are coupled to the -inner shell preferably via charges inside thereof and/or neutralization thereof by nega covalent bonds or electrostatic interactions (preferably prior tive charges as may, for example, be provided by carboxylic to the synthesis of the outer shell(s)). This can be effected groups) or even a negative charge (for example due to an according to the same mechanisms as in the case of attaching excess of negatively charged groups). According to the the outer shell to the inner shell. Thus, for example in the present invention for said purpose there may be employed, case of using aminosilanes as the compounds constituting for example, readily (rapidly) biologically degradable poly the inner shell, part of the amino groups present could be mers featuring groups suitable for coupling to the underlying employed for attaching Such compounds. However, in that shell (particularly innermost shell), e.g., (co)polymers based case there still must remain a Sufficient number of amino on C-hydroxycarboxylic acids (such as, e.g., polylactic acid, groups (after the degradation of the outer shell) to ensure the polyglycolic acid and copolymers of said acids) or polyacids Smooth importation of the iron oxide-containing cores into (e.g., sebacic acid). The use of optionally modified, naturally the inside of the cells. Not more than 10% of the amino occurring Substances, particularly biopolymers, is particu groups present should in general be consumed for the larly preferred for said purpose. Among the biopolymers the importation of other substances into the inside of the cells. carbohydrates (Sugars) and particularly the dextrans may, for However, alternatively or cumulatively it is also possible to example, be cited. In order to generate negatively charged employ silanes different from aminosilanes and having groups in said neutral molecules one may employ, for different functional groups for the synthesis of the inner example, weak oxidants that convert part of the hydroxyl or shell, to Subsequently utilize said different functional groups aldehyde functionalities into (negatively charged) carboxy for the attachment of other substances and/or the outer shell lic groups).” to the inner shell. Examples of other functional groups are, 0536 Published United States patent application 2003/ e.g., unsaturated bonds or epoxy groups as they are provided 0180370 also discloses that: “ . . . in the synthesis of the by, for example, silanes having (meth)acrylic groups or outer coat one is not limited to carbohydrates or the other epoxy groups.” species recited above but that on the contrary any other 0538 Published United States patent application 2003/ naturally occurring or synthetic Substances may be 0180370 also discloses that “According to the present inven employed as well as long as they satisfy the requirements as tion it is particularly preferred to link to the inner shell to biological degradability (e.g. enzymatically) and charge substances which become completely effective only at or masking of charge, respectively. . . . The outer layer may slightly elevated temperatures as generated by the excitation be coupled to the inner layer (or an underlying layer, of the iron oxide-containing cores of the particles according respectively) in a manner known to the person skilled in the to the invention by an alternating magnetic field, Such as, art. The coupling may, for example, be of the electrostatic, e.g., thermosensitive chemotherapeutic agents (cytostatic covalent or coordination type. In the case of covalent agents, thermosensitizers such as doxorubicin, proteins, interactions there may, for example, be employed the con etc.). If for example a thermosensitizer is coupled to the ventional bond-forming reactions of organic chemistry. Such innermost shell (e.g. via amino groups) the corresponding as, e.g., ester formation, amide formation and imine forma tion. It is, for example, possible to react a part of or all of the thermosensitizer molecules become reactive only after the amino groups of the innermost shell with carboxylic groups degradation of the outer coat (e.g. of dextran) upon genera or aldehyde groups of corresponding species employed for tion of heat (by the alternating magnetic field).” the synthesis of the outer shell(s), whereby said amino 0539. Such “thermosensitive chemotherapeutic agents' groups are consumed (masked) with formation of (poly are also referred to in claim 18 of U.S. Pat. No. 6,541,039 )amides or imines. The biological degradation of the outer (“ . . . at least one pharmacologically active species is US 2006/01 02871 A1 May 18, 2006

selected from the group consisting of thermosensitizers and tissue already due to diffusion and tumor pressure or become thermosensitive chemotherapeutic agents), and in claim 6 of deactivated by biodegradation. Said processes cannot take U.S. Pat. No. 6,669,623 (“thermosensitive cytotxic agents place with the nanoscale particles of the present invention bound to said inner shell); the entire disclosure of each of since on the one hand they are already Small enough to be these United States patent applications is hereby incorpo able to penetrate interstices of the tissue (which is not rated by reference into this specification. possible with particles in the um range, for example, lipo Somes) and on the other hand are larger than molecules and, 0540. These “thermosensitive cytotoxic agents' are also therefore cannot leave the tissue through diffusion and referred to in paragraph 18 of published United States patent capillary pressure. Moreover, in the absence of an alternat application US 2003/0180370, wherein it is disclosed that: ing magnetic field, the nanoscale particles lack osmotic “According to the present invention it is particularly pre activity and hardly influence the tumor growth, which is ferred to link to the inner shell substances which become absolutely necessary for an optimum distribution of the completely effective only at slightly elevated temperatures particles within the tumor tissue. . . . If an early loading of as generated by the excitation of the iron oxide-containing the primary tumor is effected the particles will be incorpo cores of the particles according to the invention by an rated to a high extent by the tumor cells and will later also alternating magnetic field, such as, e.g., thermosensitive be transferred to the daughter cells at a probability of 50% chemotherapeutic agents (cytostatic agents, thermosensitiz via the parental cytoplasm. Thus, if also the more remote erS Such as doxorubicin, proteins, etc.). If for example a Surroundings of the tumor and known sites of metastatic thermosensitizer is coupled to the innermost shell (e.g. via spread, respectively are subjected to an alternating magnetic amino groups) the corresponding thermosensitizer mol field individual tumor cells far remote from the primary ecules become reactive only after the degradation of the tumor will be affected by the treatment as well. Particularly outer coat (e.g. of dextran) upon generation of heat (by the the therapy of affected lymphatic nodes can thus be con alternating magnetic field).” ducted more selectively than in the case of chemotherapy. 0541. The activity of the compositions of published Additional actions by gradients of a static magnetic field at United States patent application US2003/0180370 (and of sites of risk of a Subsequent application of an alternating applicants derivative compositions) is described in paragar field may even increase the number of hits of loaded tumor phs 0019-0020 of published United States patent application cells. 2003/0180370. As is disclosed in these paragraphs, “For achieving optimum results, e.g. in tumor therapy, the exci 0543. The composition of published United States patent tation frequency of the alternating magnetic field applicator application US 2003/0180370, and also of applicants’ must be tuned to the size of the nanoscale particles according related composition, also effect an anti-mitotic activity to the present invention in order to achieve a maximum because of “selective embolization.” Thus, as is disclosed in energy yield. Due to the good distribution of the particle paragraphs 24-25 of Such United States patent application, Suspension within the tumor tissue, spaces of only a few “Due to the two-stage interlesional application a selective micrometers in length can be bridged in a so-called accumulation is not necessary. Instead the exact localization “bystander effect known from gene therapy, on the one of the lesion determined in the course of routine examination hand by the generation of heat and on the other hand through and the Subsequently conducted infiltration, in stereotactic the effect of the thermosensitizer, especially if excited sev manner or by means of navigation systems (robotics), of the eral times by the alternating field, with the result that magnetic fluid into a target region of any Small (or bigger) eventually the entire tumor tissue becomes destroyed. . . . size are sufficient. . . . The combination with a gradient of a Particles leaving the tumor tissue are transported by capil static magnetic field permits a regioselective chemoembo laries and the lymphatic system into the blood stream, and lization since not only the cyctostatic agent preferably from there into liver and spleen. In said organs the biogenous present on the particles of the invention is activated by heat degradation of the particles down to the cores (usually iron but also a reversible aggregation of the particles and, thus a oxide and iron ions, respectively) then takes place, which selective embolization may be caused by the static field.” cores on the one hand become excreted and on the other 0544. It is known that, when cancer cells are treated with hand also become resorbed and introduced into the body's hyperthermia, the survival levels of cells treated in the iron pool. Thus, if there is a time interval of at least 0.5 to absence of nutrients is greatly reduced over those heat 2 hours between the intralesional application of magnetic treated with nutrients; see, e.g., an article by G. M. Hahn, fluid and the excitation by the alternating field the surround "Metabolic aspects of the role of hyperthermia in mamma ing environment of the tumor itself has “purged itself of the lian cell inactivation and their possible relevance to cancer magnetic particles so that during excitation by the alternat treatment, Cancer Res. 34:3117-3123, November, 1974. In ing field indeed only the lesion, but not the Surrounding this Hahn article, it was disclosed that “The sensitivity of neighborhood will be heated.” cells to hyperthermia (as well as their ability to repair heat-induced damage after 43 degrees) is strongly related to 0542. When, however, the particles in question are nano their nutritional history. Chinese hamster cells chronically sized (as is the case with applicants nanomagnetic par deprived of serum (and probably other medium components) ticles), they do not leave the tissue in which they have been applied. Thus, as is disclosed in paragraph 0021 of published become extremely heat sensitive. United States patent application 2003/0180370, “ . . . 0545. In one embodiment of the instant invention, appli nanoparticles do not leave the tissue into which they have cants’ “two-shell nanomagnetic compositions' are incorpo been applied, but get caught within the interstices of the rated into tumor cells and, with the use of an external tissue. They will get transported away only via vessels that electromagnetic field, used to cause a regioselective embo have been perforated in the course of the application. High lization. Thereafter, when the tumor cells have been molecular weight Substances, on the other hand, leave the deprived of serum, the nanomagnetic materials permanently US 2006/01 02871 A1 May 18, 2006 42 disposed within the cells are caused to heat up and kill the 6,541,039, the entire disclosure of which is hereby incor cells, which are now more sensitive to hyperthermia. porated by reference into this specification. 0546). Other applications for applicants’ compositions 0549) Claim 1 of U.S. Pat. No. 6,541,039 describes: “1. (and the related compositions of published United States A method of hyperthermic treatment of a region of the body patent application 2003/0180370) are discussed in para selected from the group consisting of hyperthermic tumor graphs 0026 and 0027 of such patent application, wherein it therapy, heat-induced lysis of a thrombus, and thermoabla is disclosed that: “In addition to tumor therapy, further tion of a target region, comprising: (a) accumulating in the applications of the nanoscale particles according to the region of the body a magnetic fluid comprising nanoscale present invention (optionally without the outer shell(s)) are particles Suspended in a fluid medium, each particle having the heat-induced lysis of clotted microcapillaries (thrombi) an iron oxide-containing core and at least two shells Sur of any localization in areas which are not accessible by rounding said core, (1) the innermost shell adjacent to the Surgery and the Successive dissolution of thrombi in coro core being a shell that: (a) is formed from polycondensable nary blood vessels. For example thrombolytic enzymes silanes comprising at least one aminosilane and comprises which show an up to ten-fold increase in activity under the groups that are positively charged or positively chargeable, action of heat or even become reactive only on heating, and (b) is degraded by human or animal body tissue at Such respectively may for said purpose be coupled to the inner a low rate that adhesion of the core surrounded by the shell of the particles according to the invention. Following innermost shell with the surface of a cell through said intraarterial puncture of the vessel in the immediate vicinity positively charged or positively chargeable groups of the of the clogging the particles will automatically be trans innermost shell and incorporation of the core into the ported to the “point of congestion” (e.g., under MRT con interior of the cell are possible, and (2) the outer shell or trol). A fiberoptical temperature probe having a diameter of shells comprising at least one species that: (a) is a biologi e.g., 0.5 mm is introduced angiographically and the tem cally degradable polymer selected from (co)polymers based perature is measured in the vicinity of the point of conges on alpha.-hydroxycarboxylic acids, polyols, polyacids, and tion while, again by external application of an alternating carbohydrates optionally modified by carboxylic groups and magnetic field, a microregional heating and activation of comprises neutral and/or negatively charged groups so that said proteolytic enzymes is caused. In the case of precise the nanoscale particle has an overall neutral or negative application of the magnetic fluid and of MRT control a charge from the outside of the particle, and (b) is degraded determination of the temperature can even be dispensed with by human or animal body tissue to expose the underlying on principle since the energy absorption to be expected can shell or shells at a rate which is higher than that for the already be estimated with relatively high accuracy on the innermost shell but is still low enough to ensure a sufficient basis of the amount of magnetic fluid applied and the known distribution of a plurality of the nanoscale particles within a field strength and frequency. The field is reapplied in inter body tissue which has been infiltrated therewith; and (b) vals of about 6 to 8 hours. In the intervals of no excitation applying an alternating magnetic field to generate heat in the the body has the opportunity to partly transport away cell region by excitation of the iron oxide-containing cores of the debris until eventually, supported by the body itself, the particles, thereby causing the hyperthermic treatment clogging is removed. Due to the Small size of the particles 0550 Claims 2-15 of U.S. Pat. No. 6,541,039 are depen of the invention the migration of said particles through the dent upon claim 1. Claim 3 describes “3. The method of ventricles of the heart and the blood vessels is uncritical. claim 1 that is a method of heat-induced lysis of a thrombus, Eventually the particles again reach liver and spleen via comprising accumulating in the thrombus the magnetic RES. fluid, and applying an alternating magnetic field to generate 0547) Published United States patent application US heat by excitation of the iron oxide-containing cores of the 2003/0180370 also discloses that: “Apart from classical particles to cause heat-induced lysis of the thrombus.” Claim hyperthermia at temperatures of up to 46/47 C. also a 4 describes “4. The method of claim 1 that is a method of thermoablation can be conducted with the nanoscale par thermoablation of a target region, comprising accumulating ticles of the present invention. According to the state of the in the target region the magnetic fluid, and applying an art mainly interstitial laser systems that are in part also used alternating magnetic field to generate heat by excitation of in Surgery are employed for thermoablative purposes. A big the iron oxide-containing cores of the particles to cause disadvantage of said method is the high invasivity of the thermoablation of the target region.” Claim 10 describes microcatheter-guided fiberoptical laser provision and the “10. The method of claim 1 where the innermost shell is hard to control expansion of the target Volume. The nano derived from aminosilanes.” Claim 11 describes “11. The particles according to the present invention can be used for method of claim 1 where the at least one species comprising Such purposes in a less traumatic way: following MRT-aided the outer shell or shells is selected from carbohydrates accumulation of the particle Suspension in the target region, optionally modified by carboxylic groups.’ claim 12 at higher amplitudes of the alternating field also tempera describes “12. The method of claim 11 where the at least one tures above 50° C. can homogeneously be generated. Tem species comprising the outer shell or shells is selected from perature control may, for example, also be effected through dextrans optionally modified by carboxylic groups.’ claim an extremely thin fiberoptical probe having a diameter of 13 describes “13. The method of claim 12 where the at least less than 0.5 mm. The energy absorption as such is non one species comprising the outer shell or shells is selected invasive.” from dextrans modified by carboxylic groups.’ claim 14 describes “4. The method of claim 1 where at least one 0548. The compositions described in published United pharmacologically active species is linked to the innermost States patent application US 2003/0180370 may be used in shell.’ claim 15 describes “15. The method of claim 14 the processes described by the claims of U.S. Pat. No. where the at least one pharmacologically active species is US 2006/01 02871 A1 May 18, 2006

selected from the group consisting of thermosensitizers and treating the resulting Suspension with ultrasound until at thermosensitive chemotherapeutic agents least 70% of the particles present have a size within the range from 20% below to 20% above the mean particle 0551) The other independent claim in U.S. Pat. No. diameter; (4) removing the water by distillation under the 6,541,039 is claim 16, which describes “16. A method of tumor therapy by hyperthermia, comprising: (a) accumulat action of ultrasound; and (5) removing the agglomerates ing in the tumor a magnetic fluid comprising nanoscale which have not been broken up.” particles Suspended in a fluid medium, each particle having An Anticancer Agent Releasing Microcapsule a Superparamagnetic iron oxide-containing core having an 0555. In one embodiment of the invention, a microcap average particle size of 3 to 30 nm comprising magnetite, Sule for hyperthermia treatment is made by coating nano maghemite, or stoichiometric intermediate forms thereof magnetic particles with cis-platinum diamine dichloride and at least two shells Surrounding said core, (1) the inner (CDDP), and then covering the layer of anticancer agent most shell adjacent to the core being a shell that: (a) is with a mixture of hydroxylpropyl cellulse and mannitol. formed from polycondensable aminosilanes and comprises This microcapsule is similar to the microcapsule described groups that are positively charged or positively chargeable, in an article by Tomoya Sato et al., “The Development of and (b) is degraded by human or animal body tissue at Such Anticancer Agent Releasing Microcapusle Made of Ferro a low rate that adhesion of the core surrounded by the magnetic Amorphous Flakes for Intratissue Hyperthermia,” innermost shell with the surface of a cell through said IEEE Transactions on Magnetics, Volume 29, Noumber 6, positively charged or positively chargeable groups of the November, 1993. innermost shell and incorporation of the core into the interior of the cell are possible, and (2) the outer shell or 0556. The “core” of the Sato et al. microcapsule was shells being a shell or shells comprising at least one species ferromagnetic amorphous flakes with an average size of that: (a) is a biologically degradable polymer selected from about 50 microns and a Curie temperature of about 45 dextrans optionally modified by carboxylic groups and com degrees Centigrade. In one embodiment of the instant inven prises neutral and/or negatively charged groups so that the tion, the Sato et al. ferromagnetic material is replaced with nanoscale particle has an overall neutral or negative charge the nanomagnetic material of this invention. from the outside of the particle, and (b) is degraded by 0557. The core of the Sato et al. microcapsule was then human or animal body tissue to expose the underlying shell coated with an anticancer agent, Such as Cis-platinum diam or shells at a rate which is higher than that for the innermost mine dichloride (CDDP). Thereafter, the coated cores were shell but is still low enough to ensure a sufficient distribution then coated with a material that did not react with the of a plurality of the nanoscale particles within a body tissue anticancer agent. As is disclosed on page 3329 of the article, which has been infiltrated therewith; and (b) applying an “A wide variety of anticancer agents and macromolecular alternating magnetic field to generate heat in the tumor by compounds can be used for coating of amorphous flakes, but excitation of the iron oxide-contain cores of the particles, the absence of reaction between the anticancer agent and the thereby causing hyperthermia of the tumor.” macromolecular compound as the base is the primary con 0552) Claims 17 and 18 of U.S. Pat. No. 6,541,039 are dition for their selection. In this study, CDDP was used as dependent upon claim 16. Claim 17 describes “17. The the anticancer agent, and a mixture of hydroxypropyl cel method of claim 16 where at least one pharmacologically lulse (HPC H) and mannitol, which do not ract with active species is linked to the innermost shell.’ claim 18 CDDP was used as the macromolecular coating material.” describes “18. The method of claim 17 where the at least one 0558. The coating used in the Sato et al. microcapsule pharmacologically active species is selected from the group was designed to dissolve in bodily fluid when it was heated consisting of thermosensitizers and thermosensitive chemo to a temperature greater than about 40 degrees Centigrade. therapeutic agents.” Thus, as is disclosed at page 3329 of the Sato et al. article, “We noted the characteristics of HPC H that it becomes a 0553 As will be apparent to those skilled in the art, all of viscous gel in water at 38 degrees C. or below but loses its the processes described in U.S. Pat. No. 6,541,039 may be viscosity above 40 degrees C. Because of this property, we conducted with a composition that contains applicants expected that it would remain a viscous gel and slowly nanomagnetic material rather than the iron oxide material of release CDDP at body temperatures of 36 to 37 degrees C. the Lesniak et al. patent. but would lose its viscosity and release more CDDP when it 0554. The nanosize iron-containing oxide particles used is heated to 40 degrees C. or above, and we attempted to in the process of U.S. Pat. No. 6,541,039 may be prepared regulate the release of CDDP by hyperthermia.” by conventional means such as, e.g., the process desircribed in U.S. Pat. No. 6,183,658. This latter patent claims “1. A Mixtures of Nanomagnetic Material and a Clay Mineral process for producing an-agglomerate-free Suspension of 0559). In one embodiment of this invention, a mixture is stably coated nanosize iron-containing oxide particles, com provided of the nanomagnetic material of this invention prising the following steps in the order indicated: (1) pre (described elsewhere in this specification) and a second paring an aqueous Suspension of nanosize iron-containing material selected from the group consisting of a clay mineral oxide particles which are partly or completely present in the material and an organic materal. The nanomagnetic material form of agglomerates; (2) adding (i) a trialkoxysilane which is present in this composition at aconcentration of from has a hydrocarbon group which is directly bound to Si and about 1 to about 99 percent, by weight of the nanomagnetic to which is bound at least one group selected from amino, material and the second material. In one embodiment, nano carboxyl, epoxy, mercapto, cyano, hydroxy, acrylic, and magnetic material is present at a concentration of from about methacrylic, and (ii) a water-miscible polar organic solvent 5 to about 95 weight percent, by total weight of the two whose boiling point is at least 10°C. above that of water; (3) materials. In anotherembodiment, the nanomagnetic mate US 2006/01 02871 A1 May 18, 2006 44 rial is present at a concentration of from about 10 to about agitated in a fluid Such as water to disperse the rods, the 90 percent. In yet another embodiment, at least 50 weight dispersion can be shaped, dried and calcined to provide a percent of the mixture of the two materials is nanomagentic porous body having a large pore volume present as 200-700 material. Angstroms diameter pores. When the shaping is by extru sion, however, it has been found that mixtures of dispersed 0560. In one aspect of this embodiment, the second clay rods of the halloysite type, do not extrude well. The material is a mineral. As is known to those skilled in the art, rods on the surface of the extruded bodies tend to realign, a mineral is a native, nonorganic or fossilized organic destroying the desirable pore structure at the surface of the Substance having a definite chemical composition and catalyst. This is defined herein as a “skin effect”. It has been formed by inorganic reactions. See, e.g., page 431 of Julius discovered, however, that if a second fibrous clay with Grant’s “Hackh's Chemical Dictionary.” Fourth Edition longer, narrower and presumably more flexible, fibers is (McGraw-Hill Book Company, New York, N.Y., 1972). codispersed with the halloysite-type clay, the resulting com 0561. In one embodiment, the mineral used is a clay position is easily extrudible, and there is no significant skin mineral, i.e., a mineral found in clay. These materials are effect. "Codispersed' is defined herein as having rod- or well known in the patent literature. Reference may be had, tube-like clay particles of at least two distinct types sub e.g., to U.S. Pat. Nos. 3,873,585; 3,915,731: 4,405,371 (clay stantially randomly oriented to one another.” mineral color developer); U.S. Pat. Nos. 4,600,437; 4,798, 0565 U.S. Pat. No. 4.364,857 also discloses that “The 630; 4.810,737; 4,839,221 (gasket containing PTFE and clay second fibrous clay should have long slender fibers typically mineral): U.S. Pat. No. 4,929,580(process for treating clay about 1-5 microns in length with a diameter range of about minerals); U.S. Pat. Nos. 4,990,544; 5,908,500(activated 50-100 Angstroms. Clays for use as the second component clay composition); U.S. Pat. Nos. 5,322,879; 5,936,023(clay include attapulgite, crysotile, immogolite, palygorskite, mineral/rubber composition); U.S. Pat. No. 5,973,053 (com posite clay material); U.S. Pat. Nos. 6,103,817; 6,121, sepiolite and the like.’ 361(clay rubber); U.S. Pat. No. 6,416,573 (pigment); U.S. 0566 U.S. Pat. No. 4.364,857 also discloses that “The Pat. No. 6,562,891 (modified clay mineral): U.S. Pat. No. composition of the present invention is prepared by vigor 6,737,166; and the like. The entire disclosure of each of ously agitating a mix comprising the first fibrous clay and a these United States patents is hereby incorporated by refer second fibrous clay in a liquid dispersing medium. Water is ence into this specification. a satisfactory dispersing agent. It is preferred that the slurry contain no more than 25 weight percent of total solids. The 0562. In one embodiment, the clay mineral used is a vigorous agitation can be accomplished in any Suitable fibrous clay mineral, as that term is described in U.S. Pat. No. 4.364,857, the entire disclosure of which is hereby manner. In the laboratory, excellent codispersions are incorporated by reference into this specification. This patent achieved with a Waring blender. It is observed that the slurry claims (in claim 1) “1. A porous composition of matter thickens with agitation, apparently due to the rods dispers comprising codispersed rods of a first fibrous clay and a ing. Agitation is continued until the slurry maintains a second fibrous clay, said first fibrous clay having predomi constant thickness. Excess water is removed by slow evapo nantly rods with the length range of 0.5-2 microns and a ration at 110°C. until a workable plastic mass is formed. The diameter range of 0.04-0.2 microns and said second fibrous mass can be shaped, using well known techniques such as clay having predominantly rods with a length range of 1-5 extrusion, pelletizing, or spheredizing to form catalyst bod microns and a diameter range of 50-100 Angstroms.” These ies. The shaped particles are then calcined at 500° C. "fibrous clays.” and their preparation and processing, are 0567 U.S. Pat. No. 4,364,857 also discloses that “To described at columns 2-4 of U.S. Pat. No. 4,365,857, increase the crush strength of the catalyst Support, a refrac wherein it is disclosed that “The clay halloysite is readily tory inorganic binder oxide Such as alumina, Silica, boria, available from natural deposits. It can also be synthesized, if titania, magnesia, or the like can be added to the composi desired. In its natural state, halloysite often comprises tion. Preferably, the finished catalyst support contains less bundles of tubular rods or needles consolidated or bound than about 15 weight percent binder oxide, based on the total together in weakly parallel orientation. These rods have a weight of clay plus binder oxide. An especially preferable length range of about 0.5-2 microns and a diameter range of inorganic oxide range is about 3-7 percent by weight of the about 0.04-0.2 microns. Halloysite rods have a central Support.” co-axial hole approximately 100-300 Angstroms in diameter 0568 U.S. Pat. No. 4.364,857 also discloses that “If an forming a scroll-like structure.” inorganic oxide component is to be present into the com 0563 U.S. Pat. No. 4,364,857 also discloses that “It has position of the present invention, codispersal of the rods of been found that halloysite can make a suitable catalyst for the fibrous clay is preferably carried out in the presence of use in demetalizing and hydroprocessing asphaltenes. The an aqueous hydrogel or the Sol precursor of the inorganic halloysite is processed to break up the bundles of rods so that oxide gel component. The preferred inorganic oxide is each rod is freely movable with respect to the other rod. alumina. Mixture of two or more inorganic oxides are When substantially all the rods are freely movable with Suitable for the present invention for example, silica and respect to all the other rods, the rods are defined herein as alumina.” “dispersed”. When the dispersed rod clay is dried and calcined, the random orientation of the rods provides pores 0569 U.S. Pat. No. 4,364,857 also discloses that “A of an appropriate size for hydroprocessing and hydrodemet function of the inorganic oxide gel component is to act as a alizing asphaltene fractions.” bonding agent for holding or bonding the clay rods in a rigid, three-dimensional matrix. The resulting rigid skeletal frame 0564 U.S. Pat. No. 4.364,857 also discloses that “When work provides a catalyst body with high crush strength and halloysite rods or other rods of similar dimensions are attrition resistance.” US 2006/01 02871 A1 May 18, 2006

0570 U.S. Pat. No. 4.364,857 also discloses that “The morillonite is formed by 2:1 bonding of a tetrahedron layer catalyst may also include one or more catalytically active of silicic acid and an octahedron layer of alumina, and a pair metals, such as transition metals. A first preferred group of of tetrahedron layers of silicic acid are placed from both catalytically active metals for use in catalysts of this inven sides of the octahedron layer of alumina. The crystalline clay tion, is the group of chromium, molybdenum, tungsten and mineral of 2-1 type is higher in the content of silicic acid and Vanadium. A second preferred group of catalytically active lower in the content of alumina, as compared with the metals is the group of iron, nickel, and cobalt. Preferably, crystalline clay mineral of 1-1 type.” one or more of the metals of the first group is present in the catalyst at a total amount as metal of about 0.1-10 weight 0575 U.S. Pat. No. 5,624,544 also discloses that percent and one or more of the metals of the second group “Among overlapped unit layers of crystalline clay mineral of is present at a total amount as metal of from about 0.1-10 2-1 type such as montmorillonite, water molecules, Na ions, weight percent, based on the total catalyst weight. Especially Ca ions and other cations are invading, and generally preferred combinations include between 0.1 and 10 weight bonding between layers is weak, and a large amount of water percent of at least one metal from both the first and second molecules can be aspirated between the layers.” preferred groups, for example, molybdenum and cobalt, 0576 U.S. Pat. No. 5,624,544 also discloses that “The molybdenum and nickel, tungsten and nickel, and Vanadium crystalline clay mineral of 1-1 type is formed by 1:1 bonding and nickel.” of tetrahedron layer of silicic acid and octahedron layer of alumina, and kaolinite and halloysite belong to the crystal 0571 U.S. Pat. No. 4.364,857 also discloses that “The line clay mineral of 1-1 type. In kaolinite, the alumina plane metal component can be added to the catalyst composition of basic unit layer is bonded with silicic acid plane of other at any stage of the catalyst preparation by any conventional basic unit layer by hydrogen bond, and groups of 0.03 to metal addition step. For example, metals or metal com 0.05 um are formed. In halloysite, on the other hand, one pounds can be added to the slurry as Solids or in solution, water molecule layer is present between basic unit layers, preferably before dispersion of the clay rods. Alternatively, and this unit is grouped into a proper size, and the shape is an aqueous solution of metal can impregnate the dried or varied including hollow tube, sphere, and cabbage form.” calcined bodies. The metals can be present in reduced form or as one or more metal compounds Such as oxides or 0577 U.S. Pat. No. 5,624,544 also discloses that “In the Sulfides. One preferred method is impregnating the calcined tetrahedron layer of silicic acid of lamellar clay mineral catalyst bodies with a solution of phosphomolybdic acid and generally recognized, usually, one silicon ion is Surrounded nickel nitrate.” by four oxygenatoms, and the coordination is stable, but in the process of formation of clay mineral, its silicon ion 0572 In one embodiment, the clay mineral used is a (valence of plus 4) may be sometimes replaced by an crystalline clay mineral, as that term is used in the claims of aluminum ion (valence of plus 3). At this time, the tetrahe U.S. Pat. No. 5,624,544, the entire disclosure of which is dron layer of silicic acid comes to have one unit of negative hereby incorporated by reference into this specification. charge (1.6x10' coulombs). Similarly, the aluminum ion Claim 1 of this patent describes “1. A method for manufac in the octahedron of alumina may be replaced by Mg ion or turing ionized water comprising: a first step of dissolving Fe ion, and this octahedron of alumina also possesses one crystalline clay minerals selected from the group consisting unit of negative charge. The permanent electric charge of montmorillonite and halloysite in water for electrolysis generated in Such clay mineral continues to exist regardless treatment, and a second step of further dissolving crystal of the ambient conditions. In particular, the montmorillonite clay minerals in alkaline ionized water and acidic ionized has this property very obviously, and its charging density is water obtained at the first step, and Supplying respectively to a negative charge of 10 units per 1 cm, and in spite of its the cathode side and anode side, and performing electrolysis very large charge density, its structure is stably chemically.” treatment so as to produce strong alkaline and strong acidic ionized water maintaining a stable pH, respectively at the 0578 U.S. Pat. No. 5,624,544 also discloses that “A pair cathode side and anode side.” of tetrahedrons of silicic acid or a pair of octahedrons of alumina share an oxygen atom, but at the terminal end (end 0573 The crystalline clay minerals of U.S. Pat. No. face), silicon or aluminum is present only at one side, and 5,624,544 are described in columns 3-4 of this patent, the negative charge of oxygen is not satisfied. The clay wherein it is disclosed that “By repeating dissolution of mineral is very fine and large in specific Surface area (for crystalline clay minerals and electrolysis plural times on the example, montmorillonite has a thickness of about 0.002 to alkaline ionized water and acidic ionized water, the alkaline 0.02 um in the expanse of 0.1 um class, and kaolinite has a ionized water comes to have a further higher pH value and length of 0.07 to 3.5 um, width of 0.5 to 2.1 um, and the acidic ionized water, a further lower pH value. As a thickness of 0.03 to 0.05 um), and even a trace diffuses result, finally, an alkaline ionized water at pH 12 or more, sufficiently in water, and electric (electronic) effects are very and an acidic ionized water at pH 3 or less are produced. large.” Moreover, the obtained alkaline ionized water and acidic ionized water are hardly changed in the time course, and the 0579 U.S. Pat. No. 5,624,544 also discloses that “On the initial pH value is maintained stably for a long period. The end face of the tetrahedron of silicic acid, a negative charge crystalline clay minerals are formed in a thin layer state by is exposed on the Surface, and H+ ions are weakly taken in, secondary growth by bonding of tetrahedron of silicic acid and an electric neutrality is maintained. This bond is, how and octahedron of alumina. Structurally, crystalline clay ever, very weak, and although it is stable when many H+ minerals are classified into 2-1 type and 1-1 type.” ions are present in the material water (ionized water) to be electrolyzed (acid and low in pH value), but when the pH 0574 U.S. Pat. No. 5,624,544 also discloses that “The value of the material water (ionized water) becomes large crystalline clay mineral of 2-1 type represented by mont and the concentration of OH- ions is high, H+ ions pop out US 2006/01 02871 A1 May 18, 2006 46 from the tetrahedron of silicic acid accordingly, and silicic hydrated halloysite, etc., by the manner described hereinaf acid is charged negatively. That is, when the pH of the ter contains free water, bound water, and water of crystal material water (ionized water) is larger, it tends to charge lization. . . . ' negatively, and as the pH value is Smaller, it approaches the neutrality.” 0586. As is also disclosed in U.S. Pat. No. 6,401,816(see lines 58-65 of column 3), “The nomenclature for this hal 0580 U.S. Pat. No. 5,624,544 also discloses that “By loysite mineral is not uniform. In the United States, the contrast, the octahedron of alumina is firmly bonded with hydrated tubule form of the mineral is called endellite, and OH- ions in the state of the positive charge of aluminum the dehydrated form is called halloysite. In Europe, the exposed on the Surface, and as a result, electrically, it is hydrated tubule form of the mineral is called halloysite, and minus and further attracts H+ ions to be charged positively. the dehydrated form is called is called meta-halloysite. To That is, through the intervening OH- ions, H+ is attracted. avoid confusion, mineralogists will frequently refer to the This reaction is progressed when the H+ concentration of hydrated mineral as halloysite 10.A., and the dehydrated material water becomes large (the pH value becomes lower), mineral as halloysite 7.A.” and it is likely to be charged positively when the pH value 0587. As is also disclosed in U.S. Pat. No. 6,401,816 (see of the material water (ionized water) becomes lower.” the paragraph commencing on line 66 of column 3), it was 0581 U.S. Pat. No. 5,624,544 also discloses that reported by Bates et al. that the tube diameter of halloysite “Accordingly, on the end face of clay mineral, when the pH ranges from 400 to 1900 angstroms with a median value of value of the water to be electrolyzed becomes higher, the 700 angsgtroms, the hole diameter of halloyite ranges from negative charge (OH) increases relatively, and when the pH 200 to 1000 angstroms with a median value of 400 ang becomes lower, the positive charge (H) becomes domi stroms, and the wall thickness of halloysite ranges from 100 nant. to 700 agnstroms with a median value of 200 angstroms. 0582. In one preferred embodiment, the clay mineral is 0588. As is also disclosed in U.S. Pat. No. 6,401,816(see selected from the group consisting of Smectite clay minerals the paragraph starting at line 9 of column 4). “Tube lengths (e.g., montmorillonite, Saponite, hectolite, beidellite, Steven range from 0.1 to about 0.75 um. Morphologically, both site, nontronite), Vermiculite, halloysite or fluorine mica. hydrated and dehydrated halloysite comprise layers of single Reference may be had, e.g., to U.S. Pat. No. 5,936,023, the silica tetrahedral and alumina octahedral units. They differ in entire disclosure of which is hereby incorporated by refer the presence or absence of a layer of water molecules ence into this specification. between the silicate and alumina layers. The basal spacing of the dehydrated form is about 7.2 angstroms, and the basal 0583. In one preferred embodiment, the clay mineral is spacing of the hydrated form is about 10.1 angstroms (hence halloysite, a hydrated aluminosilicate that contains alumina the names halloysite 7.A. and halloysite 10.A). The differ (Al2O), silica (SiO2), and water (H2O). In one embodiment, ence, about 2.9.A., is about the thickness of a monolayer of the halloysite contains abut 3 moles of silica and 2 moles of water molecules.” water for each mole ofalumina, it has a molecular weight of 318.1, and it has a melting point above 1,500 degrees 0589 As is also disclosed in U.S. Pat. No. 6,401,816 (see Celsius. the paragraph beginning at line 19 of column 4). “A theory for the formation of hollow tubular microcrystals is pre 0584) As is disclosed in U.S. Pat. No. 6,401,816, the sented in Bates et al. There is a lattice mismatch between the entire disclosure of which is hereby incorporated by refer gibbsite (AlO) and silicate (SiO) layers. Water molecules ence into this specification, “Several naturally occurring interposed between the layers prevents “tetrahedral rotation' minerals will, under appropriate hydration conditions, form in the silicate layer. Halloysite 10.angstroms dehydrates to tubules and other microstructures suitable for use in the halloysite 7...angstroms at about 110°C. All structural water present invention. The most common of these is halloysite, is lost at about 575° C. The interlayer water in halloysite an inorganic aluminosilicate belonging to the kaolinite 10.angstroms may be replaced by organic liquids such as group of clay minerals. See generally, Bates et al., “Mor ethylene glycol, di- and triethylene glycol, and glycerine.” phology and structure of endellite and halloysite'. American Minerologists 35 463-85 (1950), which remains the defini 0590. In one embodiment, the clay mineral used in appli tive paper on halloysite. The mineral has the chemical cants’ composition is endellite. As is disclosed in U.S. Pat. formula Al-O.2SiOnH2O. In hydrated form the mineral No. 6,401,816, endellite is the hydrated form of halloysite: forms good tubules. In dehydrated form the mineral forms see, e.g., column 3 of Such patent. Reference may also be had to U.S. Pat. No. 3,956,140 (drilling fluids), U.S. Pat. No. broken, collapsed, split, or partially unrolled tubules.” (See 4,375,406 (fibrous clay composition), U.S. Pat. No. 4,150, lines 46-57 of column 3) 099 (synthetic halloysites), U.S. Pat. No. 4,158,521 (method 0585. The term “hydrated halloysite' is used in the of stabilizing clay formations), U.S. Pat. No. 4,421,699 claims of U.S. Pat. No. 4,019,934, the entire disclosure of (method for producing a cordierite body), U.S. Pat. No. which is hereby incorporated by reference into this specifi 4.505,833 (stabilizing clayey formations), U.S. Pat. No. cation. Claim 1 of this patent refers to an “inorganic gel.” 4.509,985 (early high-strength mineral polymers), U.S. Pat. Claim 4 of the patent recites that “4. The inorganic gel Nos. 4,828 5,561,976(release of active agents using in, 726 ammonium nitrate composite material as claimed in claim 1 (stabilizing clayey formations), organic tubules), U.S. Pat. wherein said inorganic gel is prepared from a material No. 5,820,302 microstructures is imogolite.” Reference also selected from the group consisting of hydrated halloysite may be had, e.g., to United States patents (aggregate mix and montmorillonite.” As is disclosed in column 1 of such tures and structures), and the like. The entire disclosure of patent, "The purified and Swollen inorganic gel prepared each of these United States patents is hereby incorporated by from a clay Such as montmorillonite group, Vermiculite, reference into this specification. US 2006/01 02871 A1 May 18, 2006 47

0591. In another embodiment, the clay mineral used in agents of interest to the present invention, can enter or exit applicants composition is cylindrite. As is disclosed in U.S. from the internal volume (lumen) of a cylindrical tubule by Pat. No. 6,401,816 (see column 4). “Another mineral that several mechanisms. For example, active agents can enter or will, under appropriate conditions, form tubules and other exit tubules by capillary action, if the tubules are sufficiently microstructures is cylindrite. Cylindrite belongs to the class wide. Capillary attraction and release occurs in tubules of minerals known as sulfosalts.” Reference may also be having inner diameters of at least about 0.2 Lum. Capillary had, e.g., to U.S. Pat. Nos. 4415,711, 5,561,976 (controlled attraction is relatively weak: agents in tubules having inner release of active agents with inorganic tubules), U.S. Pat. diameters of at least about 10 um. typically will be released No. 5,701,191 (sustained delivery of active compounds from in a matter of hours, without the use of other barriers to tubules), U.S. Pat. No. 5,753,736 (dimensionally stable release.” fibers), and the like. The entire disclosure of each of these 0597 U.S. Pat. No. 5,651,976 also discloses that “In United States patents is hereby incorporated by reference contrast to capillary action, adsorption/desorption processes into this specification. occur over much smaller distance scales, typically on the 0592. In another embodiment, the clay mineral used a order of about 1000. Angstroms. Thus, for tubules in this size sulfosalt known as “Boulangerite. Reference may be had, range, adsorption/desorption is the controlling process for e.g., to column 4 of U.S. Pat. No. 6,401,816. Reference may the release of an active agent inside the interior volume of also be had to U.S. Pat. Nos. 4,515,688; 4,626,279; 4,650, a microtubule. For a molecule of an active agent contained 569; 5,182,014: 5,615,976 (inorganic tubules); U.S. Pat. No. within the interior volume of a microtubule to reach the end 5,705,191 (sustained active delivery of compounds from of the tubule, so that the molecule can be released into the tubules); U.S. Pat. No. 6,669,882 (process for making fiber environment, the molecule must diffuse through the interior having functional mineral powder), and the like. The entire of the tubule while repeatedly being adsorbed and then disclosure of each of these United States patents is hereby desorbed by the inner surface of the tubule. This process, incorporated by reference into this specification. which may be conceptualized as a chromatography type of 0593. In another embodiment, the clay mineral used is process, is much slower than capillary action, by several imogolite. Reference may be had,e.g., to U.S. Pat. No. orders of magnitude.” 6,401,816 (see column 4). Reference also may be had, e.g., 0598 U.S. Pat. No. 5,651,976 also discloses that “Sev to U.S. Pat. No. 4,152.404 (synthetic imogolite), U.S. Pat. eral naturally occurring minerals will, under appropriate No. 4,241,035 (synthetic imogolite), U.S. Pat. No. 4,252, hydration conditions, form tubules and other microstructures 799 (synthetic imogolite), U.S. Pat. No. 4.394,253 (imog Suitable for use in the present invention. The most common olite catalyst), U.S. Pat. No. 4,446,244 (imogolite catalyst), of these is halloysite, an inorganic aluminosilicate belonging and the like. The entire disclosure of each of these United to the kaolinite group of clay minerals. See generally, Bates States patents is hereby incorporated by reference into this et al., “Morphology and structure of endellite and hal specification. loysite', American Minerologists 35 463-85 (1950), which 0594. In one preferred embodiment, and as is described remains the definitive paper on halloysite. The mineral has in the claims of U.S. Pat. No. 5,651,976 (the entire disclo the chemical formula A12 O3.2SiO2.nH2O. In hydrated sure of which is hereby incorporated by reference into this form the mineral forms good tubules. In dehydrated form the specification), the clay mineral is comprised of hollow mineral forms broken, collapsed, split, or partially unrolled mineral microtubules with an inner diameter of from about tubules. 200 angstroms to about 2000 angstroms and having lengths ranging from about 0.1 microns to about 2.0 microns. This 0599) U.S. Pat. No. 5,651,976 also discloses that “The patent claims (in claim 1) “1. A composition for use in the nomenclature for this mineral is not uniform. In the United delivery of an active agent at an effective rate for a selected States, the hydrated tubule form of the mineral is called time, comprising: hollow mineral microtubules selected endellite, and the dehydrated form is called halloysite. In from the group consisting of halloysite. cylindrite, bou Europe, the hydrated tubule form of the mineral is called langerite, and imogolite, wherein said microtubules have halloysite, and the dehydrated form is called is called inner diameters ranging from about 200 Angstroms to about meta-halloysite. To avoid confusion, mineralogists will fre 2000 Angstroms, and have lengths ranging from about 0.1 quently refer to the hydrated mineral as halloysite 10.Ang um to about 2.0 um, wherein said active agent is selected stroms, and the dehydrated mineral as halloysite 7. Angt from the group consisting of pesticides, antibiotics, antihel stroms. metics, antifouling compounds, dyes, enzymes, peptides, 0600 U.S. Pat. No. 5,651,976 also discloses that “Bates bacterial spores, fungi, hormones, and drugs and is con et al. present data on the tubes, which is summarized below. tained within the lumen of said microtubules, and wherein . . . Tube lengths range from 0.1 to about 0.75 um. Mor outer and end Surfaces of said microtubules are essentially phologically, both hydrated and dehydrated halloysite com free of said adsorbed active agent.” prise layers of single silica tetrahedral and alumina octahe 0595. The incorporation of “active agents’ into microtu dral units. They differ in the presence or absence of a layer bules is descrigbed at columns 3-8 of U.S. Pat. No. 5,651, of water molecules between the silicate and alumina layers. 976. The process described in this patent may also be used The basal spacing of the dehydrated form is about 7.2. Angt to incorporate the nanomagnetic material of this invention stroms, and the basal spacing of the hydrated form is about into such microtubules. The entire disclosure of such United 10.1. AngtrSoms (hence the names halloysite 7.A. and hal States patent is hereby incorporated by reference into this loysite 10). The difference, about 2.9. Angtroms, is about the specification. thickness of a monolayer of water molecules.” 0596) As is disclosed is U.S. Pat. No. 5,651,976 (see 0601 U.S. Pat. No. 5,651,976 also discloses that “A columns 3 et seq.), “Chemical agents, including the active theory for the formation of hollow tubular microcrystals is US 2006/01 02871 A1 May 18, 2006 48 presented in Bates et al. Water molecules interposed microstructure contains both an active agent and a carrier. between the gibbsite (Al2O3) and silicate (SiO2) layers This carrier further modulates the release of the active agent results in a mismatch between the layers, which is compen from the lumen of the microstructure. The active agent may sated by curvature of the layers. Halloysite 10.A. dehydrates be soluble or mobile in the carrier. In this case, the release to halloysite 7.A. at about 110°C. All structural water is lost rate of the active agent will depend on the solubility and at about 575°C. The interlayer water in halloysite 10. A. may diffusion rate of the active agent through the carrier and any be replaced by organic liquids such as ethylene glycol, di coating or matrix. The active agent may be insoluble or and triethylene glycol, and glycerine.” immobile in the carrier. In this case, the release rate of the 0602 U.S. Pat. No. 5,651,976 also discloses that active agent will depend on the release rate of the carrier “Another mineral that will, under appropriate hydration from the tubule, and any coating or matrix.’ conditions, form tubules and other microstructures is imo 0610 U.S. Pat. No. 5,651,976 also discloses that “In golite.” another embodiment of the invention, the microstructure is 0603 U.S. Pat. No. 5,651,976 also discloses that coated with a coating material. This coating further modu “Another mineral that will, under appropriate conditions, lates the release of the active agent from the lumen of the form tubules and other microstructures is cylindrite. Cylin microstructure. By carefully selecting a coating for its drite belongs to the class of minerals known as Sulfosalts.” chemical and physical properties, very precise control of the release of the active agent from the lumen of the micro 0604 U.S. Pat. No. 5,651,976 also discloses that “Yet structure can be achieved.” another mineral that will, under appropriate conditions, form tubules and other microstructures is boulangerite. Bou 0611 U.S. Pat. No. 5,651,976 also discloses that “For langerite also belongs to the class of minerals known as example, a thermoset polymer may be used as a coating in sulfosalts.” a preferred embodiment of the invention. By carefully selecting the degree of crosslinking in a thermoset polymer 0605 U.S. Pat. No. 5,651,976 also discloses that “In coating, and thus the porosity of the thermoset polymer preferred embodiments of the invention, an active agent is adsorbed onto the inner surface of the lumen of a mineral coating, one can obtain a precise degree of control over the microstructure. Skilled practitioners will be able to employ release of the active agent from the lumen of the micro known techniques for introducing a wide range of active structure. Highly crosslinked thermoset coatings will retard agents into the lumen of a mineral microstructure according the release of the active agent from the lumen more effec to the invention, thereby making a structure for the modu tively than less crosslinked thermoset coatings.” lated release of the active agent. Such structures according 0612 U.S. Pat. No. 5,651,976 also discloses that “Like to the invention may be used as-is, i.e., as free structures wise, the chemical properties of a coating may be used to which may be dispensed as desired. Dispensing techniques modulate the release of an active agent from the lumen of a include scattering, spreading, injecting, etc.” microstructure. For example, it may be desired to use a 0606 U.S. Pat. No. 5,651,976 also discloses that “An hydrophobic active agent in an aqueous use environment. important aspect of the microstructures is the size of the However, if one were to load a highly hydrophobic active lumen. Preferred inner diameters range from about 200. Ang agent into the lumen of a microstructure according to the stromsto about 2000. Angtstroms. Preferred lengths range invention, and then place this loaded microstructure in an from about 0.1 um. to about 2.0 Lum. Lumen size selection is aqueous use environment, the active agent typically would governed in part by the availability of ceramic or inorganic release into the use environment unacceptably slowly, if at microstructures within the Suitable size range. Lumen size all. selection is also governed by the choice of active agent, and 0613 U.S. Pat. No. 5,651,976 also discloses that “This the choice of any carrier, coating, or matrix (see infra). The problem of active agents that are highly insoluble in an physical and chemical properties (e.g., viscosity, Solubility, intended use environment is a common one. Many antibi reactivity, resistance to wear, etc.) of the active agent, any otics are highly insoluble in the serum. This problem can be carrier, any coating and any matrix will be considered by a largely mitigated by coating the microstructures with a skilled practitioner. Lumen size selection is also governed coating material in which the active agent has an interme by the desired release profile for the active agent.” diate solubility (i.e., a solubility somewhere between the 0607 U.S. Pat. No. 5,651,976 also discloses that “Such solubility of the active agent in itself and the solubility of the structures may be included in a Surrounding matrix. Such as active agent in the use environment).” a paint or a polymer. After release from the mineral micro 0614 U.S. Pat. No. 5,651,976 also discloses that “A wide structures, the active agent then diffuses through the Sur range of active agents will be suitable for use in the present rounding matrix to interface with the use environment. If the invention. These suitable active agents include pesticides, Surrounding matrix is ablative in the use environment, then antibiotics, antihelmetics, antifouling compounds, dyes, the diffusion distance through the matrix is mitigated or enzymes, peptides, bacterial spores, fungi, hormones, etc.” eliminated by this ablation.” 0615 U.S. Pat. No. 5,651,976 also discloses that “Suit 0608 U.S. Pat. No. 5,651,976 also discloses that “Suit able herbicides include tri-chloro compounds (triox, erg able surrounding matrices will typically be insoluble in the erol), isothiazoline, and chlorothanolil (tufficide). Suitable use environment. These matrices include paints (including pesticides include malathion, spectricide, and rotenone. marine paints), stains, lacquers, shellacs, wood treatment Suitable antibiotics include albacilin, amforol, amoxicillin, products, and all manner of applied coatings.” ampicillin, amprol, ariaprime, aureomycin, aziumycin, chlo 0609 U.S. Pat. No. 5,651,976 also discloses that “In ratetracycline, Oxytetracycline, gallimycin, fulvicin, garacin, another embodiment of the invention, the lumen of the gentocin, liquamicin, lincomix, nitrofurizone, penicillin, US 2006/01 02871 A1 May 18, 2006 49

Sulfamethazine, Sulfapyridine, fulfaquinoxaline, fulfathio of the lump clay deposit and was hydrated in distilled water, Zole, and sulkamycin. Suitable antihelmetics include iver containing 5% by weight Sodium metaphosphate. The clay mictin, Vetisulid, trichorofon, tribrissen, tramisol, topaZone, was then crudely crushed by hand, using a metal hammer to telmin, furox, dichlorovos, anthecide, anaprime, acepro break up the large lumps, and foreign material and rocks mazine, pyrantel tartrate, trichlofon, fanbentel, benzimida were sorted by hand. The sample was then transferred into Zoles, and oxibenZidole. Suitable antifouling agents include a common kitchen blender adding 200 g of the sample to 1 ergerol, triazine, decanolactone, angelicalactone, galac liter of water. The mixture was allowed to agitate at a tilone, any lactone compound, capsicum oil, copper Sul medium speed for a period of 30 minutes. The material in phate, isothiazalone, organochlorine compounds, organotin Suspension was removed and fresh water containing 5% by compounds, tetracyclines, calcium ionophores such as 504, weight Na metaphosphate was added and the process C23 187, tetracycline. Suitable hormones include estrogen, repeated until the clumps would no longer break down. progestin, testosterone, and human growth factor.” Following this step the Suspension was allowed to stand in 0616 U.S. Pat. No. 5,651,976 also discloses that "Car a 3 L graduate cylinder for 10 minutes, and then the riers are selected in view of their viscosity and the solubility suspended portion of the sample was removed for further of the active agent in the carrier. The carrier typically should processing. The gravity settlement allowed further separa possess a sufficiently low viscosity to fill the lumen of the tion of quartz sand particles from the halloysite. The result microstructure. Alternatively, a low viscosity carrier precur ant suspension was spun in an IEC Model C-6000 centrifuge Sor may be used, and the carrier formed in situ. For example, in 1 L bottles and the supernatant removed and replaced with the lumen may be filled with a low viscosity monomer, and fresh distilled water, and the process was repeated an addi this monomer Subsequently may be polymerized inside the tional two cycles. The resultant slurry was then filtered lumen. Accordingly, Suitable carriers include low molecular through a cloth paint filter cone to remove any remaining weight polymers and monomers, such as polysaccharides, large clumps, which were then ground in a mortar and pestle polyesters, polyamides, nylons, polypeptides, polyure and retreated as before. Once the halloysite sample was thanes, polyethylenes, polypropylenes, polyvinylchlorides, found to be substantially free of foreign material, it was spun polystyrenes, polyphenols, polyvinyl pyrollidone, polyvinyl out of the water suspension and allowed to air dry. This alcohol, ethyl cellulose, gar gum, polyvinyl formal resin, yielded a white cake of halloysite that was then powdered in water Soluble epoxy resins, quietol 651/nma/ddsa, aquon/ a mortar and pestle, to yield a friable white powder.” ddsa/nsa, urea-formaldehyde, polylysine, chitosan, and 0621 U.S. Pat. No. 5,651,976 also discloses that “The polyvinylacetate and copolymers and blends thereof.” powder of dry halloysite microcylinders were treated by the 0617 U.S. Pat. No. 5,651,976 also discloses that “Fre following scheme. The active agent which is to be employed quently, skilled practitioners may desire to select a carrier by the first method of entrapment should be a solid at or that has a very highly selective binding affinity for an active below 40°C. In this method both the halloysite and the agent agent of interest. A carrier that has a highly selective binding are heated to a temperature just above the melting point of affinity for an active agent will tend to release that active the agent. The best method should be a vacuum oven, if agent very slowly. Thus, very slow release rates may be possible, under a partial vacuum to aid in removal of achieved by the use of carriers with high binding affinities retained gasses within the core of the microcylinders.” for the active agent to be released. Skilled practitioners will 0622 U.S. Pat. No. 5,651,976 also discloses that “The recognize that a consequence of the extensive research that halloysite was observed to be “wet with the active agent. has been done on surface acoustic wave (SAW) analysis is Following this step the vacuum was released and the result that a large number of polymers have been identified as ant agent/microcylinders complex was suspended in a dis selective adsorbents for particular organic analytes. See persant that was not a solvent for the agent, and was at the generally, D. S. Ballantine, Jr., S. L. Rose, J. W. Grate, H. same temperature as the agent/halloysite. With sufficient Wohltjen, Analytical Chemistry 58 3058-66 (1986), and agitation, the temperature was lowered until the agent references therein, incorporated by reference herein. See became a Solid again. The agitation optionally may be also R. A. McGill et al., “Choosing Polymer Coatings for stopped at this point and the Suspension allowed to settle. Chemical Sensors”, CHEMTECH 24 (9) 27-37, and refer The dispersant was removed and the resultant halloysite/ ences therein, incorporated by reference herein.” agent complex was then Suspended in a solvent for the agent. 0618 U.S. Pat. No. 5,651,976 also discloses that “Pre This resulted in the removal of the exogenous agent from the ferred carriers include polylactate, polyglycolic acid, microcylinder.” polysaccharides (e.g., alginate or chitosan), and mixtures 0623 U.S. Pat. No. 5,651,976 also discloses that “The thereof. Each of these carriers is biodegradable. When used second method employed utilized a suspension of the hal in combination with a naturally occurring mineral microtu loysite and agent in Solution of a Suitable biodegradable bule, such biodegradable carriers provide an environmen polymer Such as a poly-lactic/polyglycolic acid system, tally friendly delivery system.” which was diluted in a suitable solvent such as methanol. 0619 U.S. Pat. No. 5,651,976 also discloses that “Having The resultant Suspension was then injected into a fluidized described the invention, the following examples are given to bed to flash off the solvent and yield a halloysite/agent illustrate specific applications of the invention, including the mixture which had an outer coating of an environmentally best mode now known to perform the invention. These benign coating of degradable polymer.” specific examples are not intended to limit the scope of the 0624 U.S. Pat. No. 5,651,976 also discloses that “The invention described in this application.” third method required the active agent to be miscible with 0620 U.S. Pat. No. 5,651,976 also discloses that, in the polylactic/polyglycolic acid mixture, or that the active Example 1, “The halloysite was obtained as a crude sample agent be very Small particulates (nanoparticulates). This US 2006/01 02871 A1 May 18, 2006 50 mixture was then entrapped in the central core of the when A is monovalent, to about 14.7 A. when A is divalent, microcylinders by a method similar to that in the original and to a value intermediate between 12.0 A. and 14.7 A. method, except that the agent was allowed to flash off in the when A includes both monovalent and divalent cations vacuum at ambient temperatures.” which comprises the steps of forming a reaction mixture by 0625 U.S. Pat. No. 5,651,976 also discloses that “To bringing together a 1:1 clay chosen from the group consist determine the encapsulation efficiency, the microcylinders ing of calcined kaolinite, calcined halloysite, acid-washed were crushed and suspended in a suitable solvent. The calcined kaolinite, acid-washed calcined halloysite, and Suspension was agitated for several hours to ensure full mixtures thereof; a cation or mixture of cations chosen from dissolution of the active agent. The determination of con the group consisting of said A, together with an equivalent centration of active agents was made either by weight or by amount of an anion chosen from the group consisting of Suitable chemical analysis.” hydroxyl and fluoride and mixtures thereof; and water; the 0626 U.S. Pat. No. 5,651,976 also discloses that “Labo relative quantities of said reaction mixture components ratory Determination of Release Rate The microtubules being selected so as to give a molar ratio of SiO2/Al2O3 of were added to a conical 50 ml disposable centrifuge, and 50 between about 1.9 and 3.2; of F-/SiO2 of between about 0.02 ml of deionized H2O was added. Concentration determi and 0.3; and of NH4+/Al2O3 of between about 0.1 and 2.0: nations were made based on absorption in a Perkin Elmer and so as to give a pH of between about 4.5 and 11.5 and a UV/Vis series 6000 spectrophotometer. A peristaltic pump solids/water weight ratio of between about 0.08 to about 0.6; was employed to pump the Solution through a quartz flow and thereafter heating said reaction mixture under hermeti cell where absorption measurements were made each half cally sealed conditions to a temperature within the range of hour. When necessary, the deionized H2O was changed to about 275°C. to about 320°C. and maintaining said mixture prevent Saturation.” within said range for a period of time long enough for said 0627 U.S. Pat. No. 5,651,976 also discloses that “Addi mineral product to form; and thereafter allowing said min tional modification of the release characteristics has been eral product to cool and recovering said mineral product.” achieved through employment of a further layer of the The process described in such claim 1 is described in more degradable polymeric material, where the secondary layer detail at columns 2-4 of such U.S. Pat. No. 3,875,288, was free of any active agent. This provides a barrier coating wherein it is disclosed that “The relative quantities of the to protect against short term exposure to the entrapped agent several reaction mixture components are selected so as to during handling. This coating then degrades in the environ give a molar ratio of silica to alumina, i.e., SiO2/Al2O3, of ment at a rate that is determinable by the degree of cross between about 1.9 and 3.2; of fluoride ion to silica, i.e., linking of the co-polymers or by employment of an addi F-SiO2, of between about 0.02 and 0.3; and of ammonium tional crosslinking agent. This allows for a delayed release ion to alumina, i.e., NH4+/Al2O3, of between about 0.1 and product. By mixing the thickness of the overcoating, the 2.0; and so as to give a pH of between about 4.5 and 11.5; delay has been tailored to initiate release over a considerable and a solids/water weight ratio of between about 0.08 and time period.” about 0.6, i.e., from about 8 percent to about 60 percent solids.” 0628 U.S. Pat. No. 5,651,976 also discloses that “For shorter term release profiles (<300 hr) polysaccharides 0631 U.S. Pat. No. 3,875.288 also discloses that “The (including alginate and chitosan) have provided a carrier and reaction mixture having been formed, it is then placed in a a coating that was biodegradable. Due to the open nature of pressure vessel if indeed not already therein, which is then the gel, the release rate has been rather fast, depending on hermetically sealed and heated to a temperature within the the agent.” range of about 275° C. to about 320°C., about 300° C. being generally preferred. This temperature is maintained until the Synthetic Clay Minerals 2:1 layer-type clay-like mineral product has formed. As will 0629. In one preferred embodiment, the clay mineral be seen from the examples which follow, typical times are used in the composition of this invention is a synthetic clay of the order of three hours for batches of a kilogram or so. mineral, that is, a naturally occurring clay mineral that has This may be compared with typical times set forth in the been modified by one or more human operations. cited Granquist patent of about 1 to 2 days. We have found that in general as the size of the equipment and batch 0630. In one embodiment, the synthetic clay mineral is a increases, the processing times decrease. Thus, in lots of the 2:1 layer-type clay mineral product, as that term is defined order of a ton or So, the Granduist product may often be in U.S. Pat. No. 3,875,288. This patent claims (in claim 1) made in as short a time as 4 or 5 hours; and for the same size '1. The process of producing a 2:1 layer-type clay-like batch the present invention permits a processing time as mineral product having the empirical formula: nSiO2:A12 short as 1 hour.” O3:mAB:XH2 O where the layer lattices comprise said silica, said alumina, and said B, and where n is from 1.7 to 0632 U.S. Pat. No. 3,875.288 also discloses that “The 3.0, m is from 0.2 to 0.6, A is one equivalent of an product having been formed as described, the vessel and exchangeable cation chosen from the group consisting of contents are allowed to cool until the vessel may be safely ammonium, Sodium, calcium, hydrogen, and mixtures opened, and the product is recovered. Any after treatment thereof, and is external to the lattice, B is chosen from the naturally depends upon the use to be made of the product. group of anions which consists of F , OH-, 1/2 O2- and Simple draining of excess liquid with or without drying may mixtures thereof, and is internal in the lattice, and X is from be adequate. Or, the solids may be washed to any desired 2.0 to 3.5 at 50 percent relative humidity, said mineral being degree of freedom from excess salts, and may be base characterized by a d001 spacing at said humidity within the exchanged with any desired cation or mixture of cations, and range which extends from a lower limit of about 12.0 A. ultimately dried and ground if desired.” US 2006/01 02871 A1 May 18, 2006

0633 U.S. Pat. No. 3,875.288 also discloses that “The calcined to order, so that this step need not be carried out by product thus produced in accordance with the invention has the operator of the inventive procedure.” the characteristics described for the product of Granquist U.S. Pat. No. 3,252,757, and discussed therein in coonsid 0639 U.S. Pat. No. 3,875,288 also discloses that “As will erable detail. In particular, quite remarkably the product be evident from the examples to be given hereinbelow, the upon X-ray diffraction no longer exhibits any content of the cation-anion combinations used in the reaction mixture may starting 1:1 clay, but shows itself to be comprised of the quite simply comprise ammonium bifluoride, NH4 F.HF, randomly alternating mixture of interstratified mica-like and also written as NH4 HF2; and ammonium hydroxide, NH4 montmorillonite-like layers, both of which are 2:1 type OH, in preselected proportions to give the desired ratios. phyllosilicates. This terminology is well understood by Calcium ion is conveniently added as calcium oxide, or, if those skilled in the art. Reference may be made to the text included before calcining, as calcium carbonate. Sodium by Ralph Grim: Clay Mineralogy, Ed. 2, New York 1968, may be added as the hydroxide or the fluoride. In general, we and in particular chapters 3, on nomenclature, and 4, on prefer a fluoride/silica ratio of about 0.1; as this ratio structure, which are hereby incorporated herein by refer diminishes, the reaction time tends to be prolonged.” ence. 0640 U.S. Pat. No. 3,875,288 also discloses that “A 0634) “An especial advantage of the present invention is variation in procedure within the broad scope of the inven that it permits the production of the Granquist-type mineral tion comprises the formation of pellets from all or most of product with a wider range of silica-to-alumina ratios than the reaction mixture; or from all of the 1:1 clay and most of originally disclosed. Thus, good syntheses may be made at the other ingredients, with enough water to enable pellets to SiO2/Al2O3 ratios of as small as 1.7. It may be noted that be readily formed using any commercial pelletizer, as is the product in accordance with the invention generally has commonplace in the catalyst industry. A suitable size for the an SiO2/Al2O3 ratio about 0.2 to 0.3 less than that of the pellets is from about one-eighth to three-sixteenths inch in reaction mixture. When this is desired, a kaolinite of diameter, although this range may be exceeded. We have had suitably low silica/alumina ratio may be selected, since there excellent results at one-eighth inch. Kaolinites and hal is some variation in the natural clay. Alternatively, most loysites from different sources tend to have different pellet halloysites have lower ratios than most kaolinites.” izing characteristics, so that in some cases it may be desir 0635 U.S. Pat. No. 3,875,288 also discloses that “In the able to include a binder in the mix fed to the pelletizer. A event that higher ratios are desired, reactive silica is included minor quantity of the mineral product made in accordance in the reaction mixture. This may be polysilicic acid, pro with the invention in a previous run serves admirably; 10 to duced for example in accordance with Hoffman U.S. Pat. 20 percent by weight of the calcined 1:1 clay may be used, No. 3,649,556; or a fumed silica, several of which are for example. Alternatively, or additionally, some of the commercially available and which are characterized by reactive silicas have binding properties and may be included extremely fine particle size, made for example by the silicon for this purpose, especially polysilicic acid.” monoxide or the silicon tetrachloride route as described in 0641 U.S. Pat. No. 3,875,288 also discloses that “While the book by Ralph Iler: The Colloid Chemistry of Silica and the pellets so produced may be used forthwith, we prefer and Silicates, Ithaca 1955, on pages 168-9 and 172-3 thereof; or find best to dry the pellets at about 105° C. to 110° C. and diatomite; or silica-rich tripoli. These are all described in then calcine them at about 600° C. to 700° C., and preferably Chapter VI of the book by Iler just cited, which is hereby at about 650° C. Remarkably, even though in the preferred incorporated herein by reference. The quantity of reactive embodiment the pellets will have been made up with ammo silica admixed may be relatively small or great, but of course nium bifluoride and ammonium hydroxide as already men should not be so great as to exceed the silica/alumina ratio tioned, no additional fluoride ion need be incorporated in the for the reaction mixture already specified herein.” final reaction mixture in spite of the high temperature of 0636 U.S. Pat. No. 3,875.288 also discloses that “Alter calcining. It appears that a semi-solid-state reaction occurs natively, the calcined kaolinite or calcined halloysite may be within the pellets during the drying and calcining, so that acid-washed, which selectively removes alumina by disso when the final conversion to the 2:1 phyllosilicate product is lution, leaving a usable structure with a higher silica/alu made in the autoclave, the conversion time is shortened even mina ratio than the starting clay. Any strong acid may be more so. The calcination of the pellets has the further used, such as sulfuric or hydrochloric, followed by water advantage that they tend to retain their shape during the Washing to remove the residual acid and dissolved alumina. autoclaving, thus permitting ready access of the chemical In general it is more practical and more economical to add solution surrounding them.” reactive silica.” 0642. In one embodiment, the synthetic clay mineal is a 0637 U.S. Pat. No. 3,875,288 also discloses that “As halloysite that has a surface area greater than 85 square already stated, the kaolinite or halloysite or the mixture of meters per gram, as is described in U.S. Pat. No. 4,098,678, both is calcined before use in accordance with the invention. the entire disclosure of which is hereby incorporated by Calcination is carried out within the range 600° to 700° C. reference into this specification. This United States patent preferably about 650° C. The time is not critical, a half-hour claims (in claim 1) “1. A process for the conversion of or hour sufficing at the preferred temperature. Such calcining hydrocarbons, which comprises contacting said hydrocar fundamentally changes the X-ray diffraction pattern of these bons at hydrocarbon converting conditions with a synthetic, clays. If the 1:1 clay is not calcined first, but used as mined, non-acid treated halloysite containing less than 0.05 wt.% then the conversion to the unique 2:1 Granquist-type clay iron and having a surface area greater than 85 sq. meters/ does not take place.” gram.” Claim 2 of this patent describes “2. A process for the 0638 U.S. Pat. No. 3,875,288 also discloses that “It may conversion of hydrocarbons which comprises contacting be noted that many clay firms will supply kaolinite already said hydrocarbons and hydrocarbon converting conditions US 2006/01 02871 A1 May 18, 2006 52 with a synthetic, non-acid treated halloysite having a surface cracking of petroleum feedstocks. Synthetic halloysite con area greater than 85 sq. meters/gram and having the empiri taining nickel, cobalt, palladium, platinum, and the like are cal formula: x Al-3/n (1-x)M2 O3. (2+y) SiO2.2H2O particularly useful for hydrocracking petroleum feedstocks.” where M is a metal selected from Groups IIA, IIIB, VIB and VIII of the Periodic Table; n is valence of M: X is equal to 0646 U.S. Pat. No. 4,098,678 also discloses that “The or less than 1; and y=0 to 1. The preparation of these feedstocks suitable for conversion in accordance with the synthetic halloysties is described at colums 2-4 of such invention include any of the well-known feeds convention patent, wherein it is disclosed that “Preparation of the ally employed in hydrocarbon conversion processes. Usu synthetic halloysite of the invention involves the reaction of ally they will be petroleum derived, although other sources hydrous alumina gel, i.e., Al(OH)3, and a source of silica. such as shale oil are not to be excluded. Typical of such feeds The hydrous alumina gel is prepared in accordance with are heavy and light virgin gas oils, heavy and light Virgin known techniques such as by the reaction of aqueous naphthas, solvent extracted gas oils, coker gas oils, steam mixtures of aluminum chloride or aluminum Sulfate and an cracked gas oils, middle distillates, steam-cracked naphthas, inorganic base such as NH4OH, NaOH or NaAlO2, and the coker naphthas, cycle oils, deasphalted residua, etc.” like. Preparation of alumina gel by use of ammonium 0647 U.S. Pat. No. 4,098,678 also discloses that “The hydroxide is preferable to the use of sodium hydroxide since operating conditions to be employed in the practice of the it is desirable to maintain the soda (Na2O) content to a low present invention are well-known and will, of course, vary level and because the more alkaline gels tend to form with the particular conversion reaction desired. The follow crystalline boehmite.” ing table Summarizes typical reaction conditions effective in 0643 U.S. Pat. No. 4,098,678 also discloses that “The the present invention. . . . . silica source may include those sources which are conven 0648 U.S. Pat. No. 4,098,678 also discloses that “The tionally used for the preparation of crystalline aluminosili halloysite structure of the composition of this invention has cate Zeolites. These include silicic acid, silica Sol, silica gel. been confirmed by X-ray diffraction and electron micros Sodium silicate, etc. Silica Sots are particularly useful. These copy. However, there are a number of significant differences are colloidal dispersions of discrete spherical particles of between naturally occurring halloysite and the synthetic surface-hydroxylated silica such as is sold by E. I. du Pont halloysite of this invention. For example, the synthetic de Nemours & Company, Inc. under the trademark halloysites of the invention have surface areas ranging from “Ludox.’ about 85 sq. meters/gram to about 200 sq. meters/gram (BET Method as used, for example, in U.S. Pat. No. 3,804.741) as 0644 U.S. Pat. No. 4,098,678 also discloses that “The compared to naturally occurring halloysite which has a proportions of the reactants employed in the initial reaction Surface area generally within the range of 40-85 sq. meters/ mixture are determined from the following molar ratio of gram (BET Method). Further, the synthetic halloysite of the reactants. . . . The pH of the reaction mixture should be invention will be substantially iron-free, i.e., less than 0.05% adjusted to a range of about 4 to 10, preferably 6 to 8. The iron, as compared to naturally occurring halloysite which temperature of the reaction mixture should preferably be contains significant amounts of iron. The synthetic and maintained at between about 230° and 270° C., more pref naturally occurring halloysites also differ in that the physical erably 240° to 250° C., for a period from about 2 hours to form of the synthetic halloysite is flakes, while the physical 100 hours or more. The time necessary for crystallization form of the natural halloysite has a tube-like configuration. will depend, of course, upon the temperature of the reaction Furthermore, it has been discovered that the synthetic hal mixture. By way of example, the crystallization of the loysite has considerably better catalytic activity than natural synthetic halloysite occurs in about 24 hours at a tempera halloysite under analogous hydrocarbon conversion condi ture of about 250° C. tions. Although the synthetic halloysite has the same empiri 0645 U.S. Pat. No. 4,098,678 also discloses that “The cal formula as naturally occurring halloysite, the higher catalytic activity of the synthetic halloysites of the invention Surface area, the elimination of iron and the presence of can be improved by incorporating therein metals selected selective metals makes the synthetic halloysite a more from Groups IIA, IIIB, VIB, and VIII of the Periodic Table effective hydrocarbon conversion catalyst.” as given in “Websters Seventh New Collegiate Dictionary', 0649. In one embodiment, the synthetic clay mineral is (1963) published by G. C. Merriam Company. Specific the synthetic halloysite described in U.S. Pat. No. 4,150,099, examples of such metals include, among others, magnesium, the entire disclosure of which is hereby incorporated by lanthanum, molybdenum, cobalt, nickel, palladium, plati reference into this specification. Claim 1 of this patent num and rare earths. Particularly preferred metals include describes “1. A process for preparing halloysite which magnesium, nickel, cobalt and lanthanum. The metals are comprises forming a reaction mixture of aluminum hydrox incorporated into the synthetic halloysite structure by adding ide gel, silica sol and water having a Al(OH)/SiO2 molar soluble salts of the metal to the reaction mixture or by ratio in the range of 0.5 to 1.2 and a H2O/SiO2 molar ratio coprecipitation of the metal hydroxide with Al(OH)3. The in the range of 20 to 60 and maintaining said reaction metals are most conveniently added to the reaction mixture mixture at a pH in the range of 4 to 10 and a temperature of in the form of their hydroxides. The synthetic halloysite of about between 230° and 270° C. for a time Sufficient to the invention, particularly when substituted with the afore permit crystallization of halloysite.” described metals, is useful for catalytic cracking, hydroc racking, desulfurization, demetallization and other hydro 0.650. In one embodiment, the synthetic clay mineral is a carbon conversion processes. For example, Substituted chlorinated clay mineral. Such as a chlorinated halloysite, as halloysites of the invention containing metals such as mag that term is defined in U.S. Pat. No. 4,798,630, the entire nesium, lanthanum and rare earths such as cerium, praseody disclosure of which is hereby incorporated by reference into mium, neodymium, gadolinium, etc. are useful in catalytic this specification. Claim 1 of U.S. Pat. No. 4,798,630 US 2006/01 02871 A1 May 18, 2006 describes a process for chlorinating an aluminosilicate clay 0653. The organophylosilicates of these claims are fur mineralstarting composition, describing “1. A method for ther described in column 1 of U.S. Pat. No. 6,197,849, chlorinating and functionalizing an aluminosilicate clay wherein it is disclosed that “It is known that organophilic mineral starting composition, comprising: reacting a said phyllosilicates prepared, for example, by ion exchange, can clay mineral composition selected from one or more mem be used as fillers for thermoplastic materials and also for bers of the group consisting of clays of the halloysite, illite, thermosets, giving nanocomposites. When Suitable organo kaolinite, montmorillonite, and polygorskite groups in Sub philic phyllosilicates are used as fillers, the physical and stantially dry particulate form with gaseous SiCl4 to activate mechanical properties of the mouldings thus produced are the Surface of said composition, thereby forming a reactive considerably improved. A particular interesting feature is the chloride intermediate, said reaction being conducted at tem increase in stiffness with no decrease in toughness. Nano peratures in the range of from about 56°C. to below 300° C.; composites which comprise the phyllosilicate in exfoliated maintaining said intermediate in a Substantially dry state form have particularly good properties.” until used for further reaction; and thereafter functionalizing 0654 U.S. Pat. No. 6,197,849 also discloses that “U.S. said intermediate with an active organic group.” Pat. No. 4,810,734 has disclosed that phyllosilicates can be 0651. In one preferred embodiment, the synthetic clay treated with a quaternary or other ammonium salt of a mineral is a layered kaolinitic mineral (such as halloysite) primary, secondary or tertiary linear organic amine in the that has undergone cation exchange with a specified cation. presence of a dispersing medium. During this there is ion Such a "cation halloysite' is described, e.g., in claims 22, 28. exchange or cation exchange, where the cation of the and 29 of U.S. Pat. No. 5,530,052, the entire disclosure of ammonium salt becomes embedded into the space between which is hereby incorporated by reference into this specifi the layers of the phyllosilicate. The organic radical of the cation; reference also may be had, e.g., to U.S. Pat. No. absorbed amine makes phyllosilicates modified in this way 5,707,439. As is disclosed in column 1 of U.S. Pat. No. organophilic. When this organic radical comprises func 5.530,052, “Efforts have been disclosed for preparing poly tional groups the organophilic phyllosilicate is able to enter meric nanocomposites. In International Application WO into chemical bonding with a Suitable monomer or polymer. 94/11430, nanocomposites having two essential components However, the use of the linear amines mentioned in U.S. Pat. are described and the two essential components are gamma No. 4,810,734 has the disadvantage that they decompose phase polyamides and layered and fibrillar inorganic mate thermally at the high temperatures of up to 300° C. usually rials which are treated with quaternary ammonium cations. used for thermoplastics processing and can discolour the ... Still other efforts have been made to prepare composite product. The formation of decomposition products can lead materials containing a layered silicate. In U.S. Pat. No. to emissions and to impairment of mechanical properties, for 4.889,885, a composite material having high mechanical example impact strength.” strength and heat resistance which is suitable for use in 0655 U.S. Pat. No. 6,197,849 also discloses that “Sur automotive parts, aircraft parts and building materials is prisingly, it has now been found that organophilic phyllo described. . . . The instant invention is patentably distin silicates which have been prepared by treating phyllosili guishable from the, above-described since, among other cates, i.e. using cation exchange with salts of quaternary or reasons, it is directed to novel layered minerals that have other cyclic amidine compounds, have greater thermal sta undergone a cation exchange with at least one heteroaro bility during processing combined with excellent dispersing matic cation comprising a positively charged organo-Substi effect and interfacial adhesion. When the amidinium com tuted heteroatom and/or a positively charged heteroatom not pounds according to the invention are used in thermosets part of an aromatic ring with at least one bond having a bond there is no change in the Stoichiometry of the reactive order greater than one, and compositions prepared there components, in contrast to the use of linear ammonium salts, from. Additionally, the instant invention is directed to novel and this allows addition to the thermosetting materials of an compositions prepared from low viscosity macrocyclic oli increased proportion of tillers. If the cyclic amidines used gomers.” contain reactive groups the organophilic phyllosilicates pre pared therewith and used as fillers can be covalently linked 0652) In one embodiment, the synthetic clay mineral is to the matrix by grafting. Amidinium ions derived, for the organophilic phylosilicate described by the claims of example, from hydroxyStearic acid or hydroxyoleic acid U.S. Pat. No. 6,197,849, the entire disclosure of which is hereby incorporated by reference into this specification. have surprisingly good layer separation combined with Claim 1 of this patent describes “1. An organophilic phyl excellent adhesion to a wide variety of polymers and fillers. losilicate which has been prepared by treating a naturally In contrast to the prior art alkyl groups with nonterminal occurring or synthetic phyllosilicate, or a mixture of Such hydroxyl groups in particular are useful, as well as alkyl silicates, with a salt of a quaternary or other cyclic amidine substituents with terminal hydroxyl groups. The hydroxyl compound or with a mixture of such salts.” claim 2 describes groups in the alkyl side chain may easily be derivatized in “2. An organophilic phyllosilicate according to claim 1, order to tailor a system-specific property spectrum. The whose preparation uses naturally occurring or synthetic compounds also create excellent dispersing effect and inter Smectite clay minerals, bentonite, Vermiculite and/or hal facial adhesion. It is also Surprising that, despite their bulk, loysite, and preferably montmorillonite, Saponite, beidelite, the heterocyclic amidine salts according to the invention, nontronite, hectorite, Sauconite or Stevensite, and particu with long substituted or unsubstituted alkyl radicals, larly preferably montmorillonite and/or hectorite.” Claim 3 exchange cations efficiently within the spaces between the describes “3. An organophilic phyllosilicate according to layers of the phyllosilicates.” claim 1, which has a distance between layers of from about 0656. In one preferred embodiment, the synthetic clay 0.7 mm-1.2 nm (nanometers) and a cation-exchange capacity mineral is an acidified calcined halloysite, as that term is in the range from 50-200 meq/100 g.” defined in U.S. Pat. No. 6,294,108, the entire disclosure of US 2006/01 02871 A1 May 18, 2006 54 which is hereby incorporated by reference into this specifi palygorskite; and mixed-layer clay minerals in nanosize cation. Claim 1 of this patent refers to “1. A dry solid particulate form which have been intercalated with organic composition for generating chlorine dioxide gas consisting cations. Exemplary cations include onium cations, e.g., essentially of a combination of at least one dry metal chlorite higher (including C4 to C20 alkyl) alkylammonium ions like and at least one dry solid hydrophilic material comprising at laurylammonium, palmitylammonium, and Stearylammo least one inorganic material selected from the group con nium. Desirably the clay from which the organophilic clays sisting of hydrous clays, calcined clays, acidified clays and are prepared have a cation exchange capacity from 50 to 300 acidified calcined clays, wherein said combination is one millieduivalents per 100 grams of clay.” which passes both the Dry Air and Humid Air Tests.” Claim 6 of this patent refers to a “hydrous halloysite, stating “6. 0660 U.S. Pat. No. 6,501,934 also discloses that “The The composition of claim 1 wherein the hydrous clay is intercalation of the layered minerals in the substrate is a selected from the group consisting of bentonite, kaolin, consequence of replacing inorganic ions intercalated attapulgite and halloysite.” Claim 7 refers to "calcined between mineral layers of the clay with organic ions. The halloysite.” stating “7. The composition of claim 1 wherein presence of the intercalated organic cations is believed to the calcined clay is selected from the group consisting of advantageously finely disperse the mineral in the material metakaolin, spinel phase kaolin, calcined bentonite, calcined from which the substrate material of the invention may be halloysite and calcined attapulgite.” Claim 8 refers to “acidi made, e.g., a solution of polyamic acid, which is a polyimide fied halloysite.” stating “8. The composition of claim 1 prepolymer. The Small size, packing and orientation of the wherein the acidified clay is selected from the group con organophilic clay in the film is believed to increase the film sisting of bentonite, kaolin, attapulgite and halloysite that strength and the films ability to act as a heat, gas and have been contacted with one or more acidic solutions moisture barrier, which is not feasible with ordinary filler containing Sulfuric acid, hydrochloric acid, nitric acid or materials.” other acidic compounds so that the pH of the resulting liquid 0661 The term “organophilic clay' is also described in phase of the mixture is below 10.5.” Claim 9 refers to the claims of U.S. Pat. No. 6,617,020, the entire disclosure “acidified, calcined halloysite.” stating “9. The composition of which is hereby incorporated by reference into this of claim 1 wherein the acidified calcined clay is selected specification. Claim 1 of U.S. Pat. No. 6,617,020 describes from the group consisting of metakaolin, spinet phase '1. A composition comprising: at least one elastomer, orga kaolin, calcined bentonite, calcined halloysite and calcined nophilic clay plate-like particles; and at least one non attapulgite that have been contacted with one or more acidic Volatile organophilic exfoliating agent; wherein the compo Solutions containing Sulfuric acid, hydrochloric acid, nitric sition is a hot melt processable pressure sensitive adhesive.” acid or other acidic compounds so that the pH of the Claim 5 describes the “organophilic clay plate-like par resulting liquid phase of the mixture is below 10.5. Any of ticles' as comprising “ . . . organophilically modified ver these forms of halloysite may be used in the composition of sions of hydrated aluminum silicate, kaolinite, atapulgite, this invention. illite, bentonite, halloysite, beidelite, nontronite, hectorite, 0657. In one embodiment, the synthetic clay mineral is hectite, Saponite, montmorillonite, and combinations selected from the group conisisting of organosilicate clay thereof.” Claim 6 describes the “organophilic exfoliating and organophilic clay, as these terms are defined by U.S. Pat. agent as comprising “ . . . a resin having a number average No. 6,501,934, the entire disclosure of which is hereby molecular weight of less than about 20,000 g/mol.” incorporated by reference into this specification. Claim 1 of 0662. The term “organophilic clay' is defined at column this patent describes “An electrophotographic transfer mem 2 of U.S. Pat. No. 6,617,020 as including “ . . . a clay that ber having a substrate comprising a nanosize polymer filler has been surface-modified to convert at least a portion of its material wherein said nanosize polymer material is selected Surface nature from an organophobic state to an organophilic from the group consisting of particulate organosilicate clay state (preferably to a hydrophobic state). For example, in filler material and organophilic clays, wherein the amount of one embodiment, a clay may initially have both organopho said filler in said substrate is lower than about 10% by bic and organophilic sites. However, upon modification weight.” according to the present invention, at least a portion of the organophobic sites are converted to organophilic sites. In 0658). In the embodiment defined by claim 2 of U.S. Pat. other embodiments, a clay initially contains essentially only No. 6,501,934, the “ . . . organosilicate clay filler material is organophobic sites and, upon modification according to the an organically modified talc-type silica (OMTS) in nanosize present invention, at least a portion of the organophobic sites particulate form.” In the embodiment defined by claim 3 of are converted to organophilic sites. Preferably, at least about U.S. Pat. No. 6,501,934, “... wherein said organophilic clay 50% of exchangeable cations on the unmodified organo is an organically modified particulate organically modified philic clay are exchanged with organophilic modifying mica, bentonite; allophane; kaolinite; halloysite; illite; chlo rite; Vermiculite; Sepiolite; attapulgite; palygorskite; and cations.” mixed-layer clay minerals in nanosize particulate form.’ 0663 The term “organophilic exfoliating agent” is defined in column 2 of U.S. Pat. No. 6,617,020 as inlucindg 0659 The organophilic clay is described at column 3 of & G ... an organophilic material capable of separating an U.S. Pat. No. 6,501,934, wherein it is disclosed that “The nanosize polymer material may be an organophilic clay. organophilic clay sheet into plate-like particles and main “Organophilic clay includes layered minerals such as par taining the clay in plate-like particles at the use temperature ticulate organically modified mica, e.g., muscovite, lepido (typically room temperature, i.e., about 21° C.).” lite, phlogopite or glauconite; or organically modified ben 0664) “Organophilic clays” and “organophilic exfoliating tonite, e.g., montmorillonite; allophane; kaolinite; agents' are also described at columns 5-6 of U.S. Pat. No. halloysite; illite; chlorite; vermiculite; sepiolite; attapulgite: 6,617,020, wherein it is disclosed that “Organophilic clay is US 2006/01 02871 A1 May 18, 2006 obtainable by modifying a hydrophilic clay such that the tion. A non-volatile organophilic exfoliating agent is used to clay is organophilic. Conventional hydrophilic clays are exfoliate the organophilic clay. It has been found that the generally not able to be adequately exfoliated according to organophilic clay can be easily exfoliated by exfoliating the present invention. Thus, the present invention utilizes agents, that are low molecular weight resins. Examples of organophilic clays to achieve a higher degree of exfoliation useful low molecular weight resins include, but are not in the clay.” limited to, tackifying agents and low molecular weight block copolymers such as styrene-isoprene block copolymers, 0665 U.S. Pat. No. 6,617,020 also discloses that “The hydrophilic clay to be modified can be any phyllosilicate or styrene-butadiene block copolymers, and hydrogenated other clay that has a sheet-like structure. Examples thereof block copolymers. Such exfoliating agents typically have a include, but are not limited to, hydrated aluminum silicate, number average molecular weight of less than about 20,000 kaolinite, atapulgite, illite, halloysite, beidelite, nontronite, g/mol, preferably less than about 10,000 g/mol, and most hectorite, hectite, bentonite, Saponite, and montmorillonite. preferably less than about 5,000 g/mol.” The Smectite clays Such as, for example, beidelite, nontro 0670 U.S. Pat. No. 6,617,020 also discloses that “Tacki nite, hectorite, hectite, bentonite, Saponite, and montmoril fying agents are the preferred exfoliating agents. However, lonite are preferred.” not all tackifying agents will act as an exfoliating agent in 0666 U.S. Pat. No. 6,617,020 also discloses that “The any given system. For a tackifying agent to function as an organophilic clays useful for the invention may be prepared exfoliating agent according to the present invention, it from commercially available hydrophilic clays. The follow generally needs to be viscous enough to impart shear forces ing is an example of a method of preparing organophilic in the composition upon exfoliation in order to effectively clay: The hydrophilic clay is stirred and dissolved in water exfoliate the organophilic clay. It is also preferred that such to form an exfoliated hydrophilic clay solution. Then, a tackifying agent would mininimize or prevent Substantial depending on the clay, exchangeable ions (e.g., Sodium or agglomeration of the exfoliated particles. Selecting a tacki calcium ions), for example, of the hydrophilic clay are fying agent in which the organophilic clay is compatible exchanged with organophilic modifying cations. Typical helps to accomplish this preferred embodiment. Suitable organophilic modifying cations comprise onium cations. For tackifying agents can be found in the following groups: example, such cations include, but are not limited to, C2 to aliphatic, aromatic-modified aliphatic, aromatic, and at least C60 alkyl primary, secondary, tertiary, and quaternary partially hydrogenated versions and derivatives thereof.” ammonium cations and quaternary phosphonium cations. 0671 U.S. Pat. No. 6,617,020 also discloses that Examples thereof include, but are not limited to, (meth)acry “Examples of tackifying agents that are useful as exfoliating late ammonium cations, such as 2-(dimethylammonium agents include, but are not limited to, rosins, such as wood )ethyl methacrylate cations, octadecylammonium cations, rosins and their hydrogenated derivatives; derivatives of dimethyl dihydrogenated tallow ammonium cations, thiol rosins, such as FORAL 85, a stabilized rosin ester from group functionalized alkyl ammonium cations, and combi Hercules Chemical Co.; Wilmington, Del., the nations thereof. Exchange of the hydrophilic clay ions with SNOWTACK series of gum rosins from Tenneco Corp.; organophlic modifying cations causes the modified clay to Greenwich, Conn., and the AQUATAC series of tall oil precipitate from the water solution. The precipitated clay rosins from Arizona Chemical Co.; Panama City, Fla.: (which is no longer in an exfoliated state) is then dried to terpene resins of various softening points, such as alpha.- remove eXceSS Water. pinene and 13-pinene, available as PICCOLYTE A-115 and 0667 U.S. Pat. No. 6,617,020 also discloses that “Some ZONAREZ B-100 from Arizona Chemical Co.; Panama organophilic clays are commercially available. For example, City, Fla.; petroleum-based resins, such as the ESCOREZ organophilically-modified montmorillonite is available as 1300 series of aliphatic olefin-derived resins and the SCPX CLOISITE 20A, SCPX CLOISITE 15A, SCPX ESCOREZ 2000 series of aromatic/aliphatic olefin-derived CLOISITE 10A, SCPX CLOISITE 6A, SCPX CLOISITE resins from EXXon Chemical Co.; Houston, Tex.; and Syn 30b, and SCPX CLOISITE 2398 from Southern Clay Prod thetic hydrocarbon resins, such as the PICCOLYTE A series ucts; Gonzalez, Tex., and under the trade designation, of aromatic resins such as PICCOTEX LC-55WK; and NANOMER, from Nanocor Inc.; Arlington Heights, Ill.” aliphatic resins, such as PICCOTAC 95, available from Hercules Chemical Co.; Wilmington, Del.” 0668 U.S. Pat. No. 6,617,020 also discloses that “The composition of the invention typically comprises any Suit 0672) U.S. Pat. No. 6,617,020 also discloses that “Par able amount of organophilic clay. Generally, the amount of ticularly preferred are resins derived by polymerization of organophilic clay present is such that the overall composi C5 to C9 unsaturated hydrocarbon monomers, polyterpenes, tion is a pressure sensitive adhesive. Preferably the compo synthetic polyterpenes and the like. Examples of Such com sition includes about 1 to about 40 weight percent of the mercially available resins of this type are WINGTACK organophilic clay plate-like particles, more preferably about PLUS tackifying agents, available from Goodyear Tire and 1 to about 20 weight percent, and most preferably 1 to about Rubber Co.; Akron, Ohio; REGALREZ 1126 tackifying 10 weight percent based on the total weight of the compo agents, available from Hercules Chemical Co.; Wilmington, sition. The exact amount varies depending on, for example, Del.: and ESCOREZ 180, ESCOREZ 1310, and ESCOREZ the type of elastomer and the presence and amount of other 2393 tackifying agents, all available from Exxon Chemical components in the composition.” Co.; Houston, Tex.” 0669 U.S. Pat. No. 6,617,020 also discloses that “The 0673. In one preferred embodiment, the synthetic clay composition of the invention typically comprises about 1 to mineral is clay bridged with a metal compound, as that term about 75 weight percent of a non-volatile organophilic is defined in U.S. Pat. No. 6,674,009, the entire disclosure of exfoliating agent based on the total weight of the composi which is hereby incorporated by reference into this specifi US 2006/01 02871 A1 May 18, 2006 56 cation. As is disclosed in Such patent, and as is described in low filler content, have good mechanical properties and can claim 3 thereof, the bridged clay may be selected from the be processed without problems. By varying the mixing ratio group consisting of “ . . . montmorillonite, laponite, beid of mineral filler to organophilic layer silicate it is possible to ellite, nontronite, Saponite, Sauconite, hectorite, Stevensite, obtain tailored system-specific property profiles.” kaolinite, halloysite, Vermiculite, and Sepiolite, or one of 0677 U.S. Pat. No. 6,683,122 also discloses that “The their synthetic or naturally interstratified mixtures. . . . . As present invention relates to a filler mixture comprising an is disclosed at column 2 of this patent, “The starting clay organophilic layer silicate obtainable by treatment of a treated with a solution of a salt of a metallic compound, natural or synthetic layer silicate with a Swelling agent preferably a solution of iron and/or aluminum salt. After selected from Sulfonium, phosphonium and ammonium drying and heat treatment, a bridged clay is obtained.” compounds (salts of melamine compounds and cyclic ami 0674) In one preferred embodiment, the synthetic clay dine compounds being excluded as ammonium compounds) mineral used in the process of this invention is an organo and a mineral filler different therefrom.” philic layer silicate as that term is defined in U.S. Pat. No. 0678 U.S. Pat. No. 6,683,122 also discloses that “As 6,683,122, the entire disclosure of which is hereby incor layer silicates for the preparation of the organophilic layer porated by reference into this specification. Claim 1 of this patent describes “1. A filler mixture comprising an (a) silicates of the filler mixtures according to the invention organophilic layer silicate obtainable by treatment of a there come into consideration especially natural and Syn natural or synthetic layer silicate with a Swelling agent thetic Smectite clay minerals, more especially bentonite, selected from the group consisting of Sulfonium, phospho Vermiculite, halloysite, Saponite, beidellite, nontronite, hec nium and ammonium compounds (salts of melamine com torite, Sauconite, Stevensite and montmorillonite. Montmo pounds and cyclic amidine compounds being excluded as rillonite and hectorite are preferred.” ammonium compounds); and (b) a mineral filler different 0679 U.S. Pat. No. 6,683,122 also discloses that “The from component (a).” Claim 2 of this patent “2. A filler layer silicate montmorillonite, for example, corresponds mixture according to claim 1, wherein the natural or syn generally to the formula Al2(OH)/Si4 O10).nH2O, it thetic layer silicate is selected from the group consisting of being possible for some of the aluminium to have been bentonite, Vermiculite, halloysite, Saponite, beidellite, non replaced by magnesium. The composition varies according tronite, hectorite, Sauconite, Stevensite and montmorillo to the silicate deposit. A preferred composition of the layer nite.” This filler mixture is described at columns 1-3 of U.S. silicate corresponds to the formula (A13.15 Mg0.85)Si3.00 Pat. No. 6,683,122, wherein it is disclosed that “The prepa O20 (OH)4 X11.8.nH2O, wherein X is an exchangeable ration of organophilic layer silicates by treatment of layer cation, generally sodium or potassium, and some of the silicates with onium salts, e.g. quaternary ammonium salts, hydroxyl groups may have been replaced by fluoride ions. in the presence of a dispersion medium is known from U.S. By exchanging hydroxyl groups for fluoride ions, synthetic Pat. No. 4,810,734. In that treatment an exchange of ions layer silicates are obtained.” takes place, the cation of the onium salt being inserted into 0680 U.S. Pat. No. 6,683,122 also discloses that “The the interlayer space of the layer silicate. Layer silicates Sulfonium, phosphonium and ammonium compounds modified in that manner become organophilic as a result of required as Swelling agents for the preparation of the orga the organic radical of the inter-calated amine. When that nophilic layer silicates are known and some of them are organic radical contains functional groups, the organophilic commercially available. They are generally compounds hav layer silicate is capable of forming chemical bonds with ing an onium ion, for example trimethylammonium, trim Suitable monomers or polymers.” ethylphosphonium and dimethylsulfonium, and a functional 0675 U.S. Pat. No. 6,683,122 also discloses that “WO group that is capable of reacting or bonding with a polymeric 96/08526 describes the use of such organophilic layer sili compound. Suitable ammonium salts can be prepared, for cates as filler materials for epoxy resins, there being example, by protonation or quaternisation of corresponding obtained nanocomposites having improved physical and aliphatic, cycloaliphatic or aromatic amines, diamines, mechanical properties. It is of special interest that there is an polyamines or aminated polyethylene or polypropylene gly increase in rigidity while the toughness at least remains the cols (JeffamineR M series, D series or T series).” same. Especially good properties are exhibited by nano 0681 U.S. Pat. No. 6,683,122 also discloses that “Special composites that contain the layer silicate in exfoliated form. preference is given to layer silicates in which the layers have However, the addition of such organophilic layer silicates a layer spacing of about from 0.7 nm to 1.2 nm and which gives rise not only to an improvement in rigidity but also to have a cation exchange capacity in the region of 50 to 200 a reduction in tensile strength.” med./100 g (milliequivalents per 100 grams). After treat 0676 U.S. Pat. No. 6,683,122 also discloses that “It has ment with the Swelling agent (Sulfonium, phosphonium or been found, Surprisingly, that a combination of organophilic ammonium compound), the layer spacing in the organo layer silicates and mineral fillers can yield considerably philic layer silicates so obtained is preferably at least 1.2 nm. better mechanical properties than the individual compo Such layer silicates are described, for example, in A. D. nents. In thermosetting resins, the addition of the filler Wilson, H. T. Posser, Developments in Ionic Polymers, mixtures according to the invention results in a considerable London, Applied Science Publishers, Chapter 2, 1986. Syn increase in rigidity as compared with the use of pure mineral thetic layer silicates can be obtained, for example, by fillers at the same total filler content, while the substantial reaction of natural layer silicates with sodium hexafluoro reduction in tensile strength which occurs when organo silicate and are commercially available inter alia from the philic layer silicates are used alone is prevented. The filler CO-OP Chemical Company, Ltd., Tokyo, Japan.” mixtures according to the invention therefore allow the 0682) U.S. Pat. No. 6,683,122 also discloses that “For the preparation of filled resins which, while having a relatively preparation of the organophilic layer silicates, the Swelling US 2006/01 02871 A1 May 18, 2006 57 agent is first advantageously dispersed or dissolved, with 0690 U.S. Pat. No. 6,683,122 also discloses that “In stirring, in a dispersion medium, preferably at elevated especially preferred filler mixtures, the proportion of orga temperature of about from 40°C. to 90°C. The layer silicate nophilic layer silicate is from 2.0 to 50.0% by weight, is then added and dispersed, with stirring. The organophilic especially from 4.0 to 30.0% by weight, and the proportion layer silicate so obtained is filtered off, washed with water of mineral filler is from 50.0 to 98.0% by weight, especially and dried. It is, of course, also possible to prepare the from 70.0 to 96.0% by weight.” dispersion of the layer silicate as initial batch and then to add the solution or dispersion of the Swelling agent.” 0691 U.S. Pat. No. 6,683,122 also discloses that “The filler mixtures according to the invention can be prepared 0683 U.S. Pat. No. 6,683,122 also discloses that “Suit prior to application in customary manner by mixing the able dispersion media are water, methanol, ethanol, pro components together using known mixing apparatus (e.g. panol, isopropanol, ethylene glycol, 1,4-butanediol, glyc stirrers, rollers).” erol, dimethyl sulfoxide, N,N-dimethylformamide, acetic acid, formic acid, pyridine, aniline, phenol, nitrobenzene, 0692 U.S. Pat. No. 6,683,122 also discloses that “It is acetonitrile, acetone, 2-butanone, chloroform, carbon disul also possible, however, to incorporate one of the compo fide, propylene carbonate, 2-methoxyethanol, diethyl ether, nents into the resin or into one of the resin components and tetrachloromethane and n-hexane. Preferred dispersion then to add the other component prior to the polymerisation media are methanol, ethanol and especially water.” or curing.” 0684 U.S. Pat. No. 6,683,122 also discloses that “The 0693 U.S. Pat. No. 6,683,122 also discloses that “In one Swelling agent brings about a widening of the interlayer embodiment, the synthetic clay mineral used is an organo spacing of the layer silicate, so that the layer silicate is able clay, as that term is described in U.S. Pat. No. 6,831,123, the to take up monomers into the interlayer space. The Subse entire disclosure of which is hereby incorporated by refer quent polymerisation, polyaddition or polycondensation of ence into this specification. Claim 1 of this patent describes the monomer or monomer mixture results in the formation “A composition comprising at least one ionomeric polyester of a composite material, a nanocomposite.” resin and at least one organoclay, wherein the organoclay is not preswollen before combination with ionomeric polyester 0685 U.S. Pat. No. 6,683,122 also discloses that “In the resin.” The organoclay is further described in claim 10, filler mixtures according to the invention it is preferable to which recites that “10. The composition of claim 1 wherein use layer silicates that have been pre-treated with a poly the organoclay comprises at least one member selected from merisable monomer prior to swelling. When the swelling is the group consisting of kaolinite, halloysite, dickite, nacrite, complete, the compositions are polymerised. Such mono montmorillonite, nontronite, beidellite, hectorite, Saponite, mers are, for example, acrylate monomers, methacrylate hydromicas, phengite, brammallite, glaucomite, celadonite, monomers, caprolactam, laurinlactam, aminoundecanoic kenyaite, magadite, bentonite, Stevensite, muscovite, Sauco acid, aminocaproic acid or aminododecanoic acid. The resin nite, Vermiculite, Volkonskoite, laponite, mica, fluoromica, component or the hardener component of an epoxy resin and smectite.” These organoclays are further described in system or the components of a polyurethane system can colum 1 of such United States patent, wherein it is disclosed likewise be such monomers.” that "Organoclays typically consist of particles comprised of several layers of alumino-silicate plates held together by 0686 U.S. Pat. No. 6,683,122 also discloses that “Suit electrostatic interactions with organic moieties containing able mineral fillers that can be used in the filler mixtures metal cations or alkyl ammonium ions intercalated between according to the invention are, for example, glass powder, the plates. Such clays have been used as fillers in resinous glass beads, semi-metal and metal oxides, e.g. SiO2 (aero compositions. In certain cases they may increase properties sils, quartz, quartz powder, fused silica), corundum and Such as heat resistance, and/or mechanical strength, or they titanium oxide, semi-metal and metal nitrides, e.g. silicon may beneficially decrease properties such as electrical con nitride, boron nitride and aluminium nitride, semi-metal and ductivity or permeability to gases such as oxygen or water metal carbides (SiC), metal carbonates (dolomite, chalk, vapor.” CaCO3), metal Sulfates (barite, gypsum), powdered miner als and natural or synthetic minerals primarily from the 0694 U.S. Pat. No. 6,831,122 also discloses that “The silicate series, e.g. talcum, mica, kaolin, wollastonite etc. It benefit of organoclays over other mineral fillers in resinous is also possible to use the untreated layer silicates that are compositions is obtained when the alumino-silicate plates used for the preparation of organophilic layer silicates.” comprising the clay are separated from one another and dispersed in the polymer matrix. Since these plates have a 0687 U.S. Pat. No. 6,683,122 also discloses that “Pre very high aspect ratio, they may provide property enhance ferred mineral fillers are quartz powder, mica, kaolin, wol ment such as reinforcement and improvement in modulus lastonite, chalk and talcum.” compared to traditional mineral fillers on a per weight of 0688 U.S. Pat. No. 6,683,122 also discloses that “The total inorganic content. In order to separate the layers of the quantity ratio of the components can vary within wide limits clay and obtain maximum reinforcement in a resinous according to the property profile desired in the filler mix composition, it is typically necessary that polymer adsorb tures according to the invention.” between the layers of the clay causing exfoliation (separa tion) of the layers. Typically, hydrophilic polymers such as 0689) U.S. Pat. No. 6,683,122 also discloses that “Pref. polyamides or water-soluble polymers have been used in erence is given to filler mixtures in which the proportion of compositions with organoclays since they may have an organophilic layer silicate is from 1.0 to 60.0% by weight affinity for the clay Surface promoting exfoliation. It has and the proportion of mineral filler is from 40.0 to 99.0% by been found, however, that intimately mixing typically weight.” hydrophobic polyester resins and organoclays does not US 2006/01 02871 A1 May 18, 2006

allow for full exfoliation of the clay. Thus properties of the layered minerals which are classified as layered double compositions such as modulus may be only marginally hydroxides, as well as layered minerals having little or no better than those properties obtained when traditional fillers charge on their layers provided that they are capable of are used in typical polyester resins. There is a need to undergoing cation exchange with cations and/or onium prepare compositions of normally hydrophobic polyester compounds comprising organic moieties to produce orga resins with organoclay fillers which achieve optimum ben noclays, and in the form of organoclays they are capable of eficial property improvement.” producing an increase in modulus in a composition contain 0695 U.S. Pat. No. 6,831,123 also discloses that “PCT ing an ionomeric polyester resin compared to a similar Patent Application WO99/32403 suggests the preparation of composition containing essentially the same non-ionomeric an expanded organoclay using a Sulfonated polyester as an polyester resin.” expanding agent. Following the expansion step, the expanded organoclay is combined in a separate step with a 0700 U.S. Pat. No. 6,831,123 also discloses that “In non-ionomeric polyester resin to form a composition with up addition to the clays mentioned above, admixtures prepared to 30 weight% expanded organoclay, the clay containing 20 therefrom may also be employed as well as accessory to 80 weight '% expanding agent.” minerals including, for instance, quartz, biotite, limonite, 0696) The organoclays of U.S. Pat. No. 6,831,123 are hydrous micas, fluoromicas, feldspar and the like.’ also described at columns 5-6 of such patent, wherein it is 0701 U.S. Pat. No. 6,831,123 also discloses that “Pre disclosed that “The compositions of the present invention ferred layered clays comprise particles containing a plurality contain at least one organoclay. As used herein, “organo of silicate platelets having a thickness of about 7-15. Ang clay comprises a layered clay, usually a silicate clay, stroms. bound together at interlayer spacings of about typically derived from a layered mineral and in which 4.Angstroms. or less, and containing exchangeable cations organic moieties have been chemically incorporated, ordi narily by ion exchange and especially cation exchange with Such as Na+, Ca+2, K+, Al--3, and/or Mg+2 present at the organic-containing ions and/or onium compounds. Illustra interlayer Surfaces. They typically have a cation exchange tive organic ions are mono- and polyammonium cations capacity of about 50-200 milliequivalents per 100 grams.” such as trimethyldodecylammonium and N,N'-didode 0702 U.S. Pat. No. 6,831,123 also discloses that “The cylimidazolium.” layered clay is cation exchanged with organic-containing 0697 U.S. Pat. No. 6,831,123 also discloses that “There ions and/or onium compounds to produce organoclay. Suit is no particular limitation with respect to the layered clays able organic-containing ions and/or onium compounds that may be employed in this invention other than that they include ammonium cations, pyridinium cations, phospho are capable of undergoing cation exchange with cations nium cations, or Sulfonium cation represented, respectively, and/or onium compounds comprising organic moieties to by the general formulas NHx Ry+, PyR+, PyR+, and SR2+. produce organoclays, and in the form of organoclays they wherein R is an aromatic group, an alkyl group, an aralkyl are capable of producing an increase in modulus in a group, or a mixture thereof, and the Sum of X and y is 4: composition containing an ionomeric polyester resin com preferably R is an alkyl group. Other Suitable organic pared to a similar composition containing essentially the containing ions and/or onium compounds include proto same non-ionomeric polyester resin. Illustrative of Such nated amino acids and salts thereof containing about 2-30 layered clays that may be employed in this invention carbon atoms. Other examples of Suitable organic-contain include, for instance, Smectite and those of the kaolinite ing ions and/or onium compounds and processes for group Such as kaolinite, halloysite, dickite, nacrite and the employing them are disclosed in U.S. Pat. Nos. 4,810,734; like.’ 4,889,885; and 5,530,052 which are incorporated herein by reference. 0698 U.S. Pat. No. 6,831,123 also discloses that “The layered clays are preferably natural or synthetic phyllosili 0703 U.S. Pat. No. 6,831,123 also discloses that “Suit cates, particularly Smectic clays. Illustrative examples able specific commercially available or easily prepared include, for instance, halloysite, montmorillonite, nontron organoclays which are illustrative of those which may be ite, beidellite, Saponite, Volkonskoite, laponite, Sauconite, employed include CLAYTONE HY, a montmorillonite magadite, kenyaite, bentonite, Stevensite, and the like. It is which has been cation exchanged with dimethyldi(hydroge also within the scope of the invention to employ organoclays nated tallow)ammonium ion available from Southern Clay comprising minerals of the illite group, including hydromi Products, and montmorillonite which has been cation cas, phengite, brammallite, glaucomite, celadonite and the exchanged with Such ions as dodecylammonium, trimethyl like. Often, the preferred layered minerals include those dodecylammonium, N,N'-didodecylimidazolium, N,N'- often referred to as 2:1 layered silicate minerals, including ditetradecylbenzimidazolium, methyl bis(hydroxyethyl)(hy muscovite, Vermiculite, Saponite, hectorite and montmoril drogenated tallow)ammonium, or methyl bis(2- lonite, the latter often being most preferred. The clays may hydroxyethyl)octadecylammonium.' be synthetically produced, but most often they comprise 0704 U.S. Pat. No. 6,831,123 also discloses that “The naturally occurring minerals and are commercially avail compositions of the invention may also contain conven able. Mixtures of clays for example as described above are tional additives. Suitable additives include flame retardants, also suitable. A more detailed description of suitable clays anti-drip agents, stabilizers, resinous impact modifiers, other can be found in U.S. Pat. No. 5,530,052, the disclosure of fillers such as extending fillers, pigments, dyes, antistatic which is incorporated by reference herein.” agents, crystallization aids and mold release agents. Since 0699) U.S. Pat. No. 6,831,123 also discloses that “It is these are well known in the art, they will not be dealt with also within the scope of the instant invention to include in detail herein.” US 2006/01 02871 A1 May 18, 2006 59

Preparation of a Composite Containing Nanomagnetic may be obtained from the Secretary of the Mineralogical Material and Mineral Material Society, Dr. Steve Hillier, Secretary of the Clay Minerals Group, Environmental Science Group, Macaulay Institute, 0705 FIG. 24 is a schematic illustration of a nanocom posite assembly 1100 comprised of tubules 1102 and granu Craigi9ebuckler, Aberdeen, AB158OH. Scotland. lar material 1104. These tubules 1102, and their properties, 0711. In one preferred embodiment, the composition are described elsewhere in this specification and in U.S. Pat. 1100 (see FIGS. 24 and 25) contains at least 80 weight No. 4,358,300 (residual oil processing catalysts), U.S. Pat. percent of the tubules 1102 and, more preferably, at least 90 No. 4.364,857 (fibrous clay mixtures), U.S. Pat. No. 4,421, weight percent of the tubules 1102. In one aspect of this 699 (method of producing a cordierite body), U.S. Pat. No. embodiment, the composition 1100 contains at least 95 4,877,501 (process for fabrication of lipid microstrucutres), weight percent of tubules 1102. U.S. Pat. No. 4,911,981 (metal clad lipid microstrucutres), U.S. Pat. No. 5,049.382 (cating and composition contaiing 0712 FIG. 26 is a schematic illustration of a composition lipid microstructure toxin dispenses), U.S. Pat. No. 5.492. 1101 that is comprised of such tubules 1102 and, coated on 696 (controlled relase microstructures), U.S. Pat. No. 5,651, the outer surfaces 1105 thereof, a multiplicity of particles of 976 (controlled release of active agents using inorganic nanomagnetic material 1106; this nanomagnetic material tubules), U.S. Pat. No. 5,705,191 (sustained delivery of 1106, and means for its preparation and coating onto the active compounds from tubules, with rational control), U.S. tubules 1102, are described elsewhere in this specification. Pat. No. 5,744,337 (internal gelation method for forming In one aspect of this embodiment, the tubules 1102 are multilayer microspheres), U.S. Pat. No. 5,858,081 (kaolin halloysite microtubules. In this aspect, it is preferred to derivatives), U.S. Pat. No. 6,013,206 (formation of high incorporate the composition comprised of halloysite tubules aspect ratio lipid microtubules), U.S. Pat. No. 6,280,759 into one or more of the polymeric, resinous, elastomeric, (method of controlled release and controlled release micro and/or ceramic compositions described elsewhere in this structures), U.S. Pat. No. 6.511,533 (non-calcined lead of a specification. colored pencil), and the like; the entire disclosure of each of 0713. In one embodiment, not shown, some or all of the these United States patents is hereby incorporated by refer granular halloysite material 1104 is replaced by other granu ence into this specification. The term tubular halloysite has lar material Such as, e.g., the nanomagnetic material the meaning described elsewhere in this specification, and/or described elsewhere in this specification. One aspect of this in the aforementioned United States patents. embodiment is illustrated in FIGS. 26 and 27. 0706. In one preferred embodiment, the tubules 1102 are 0714 FIG. 27 is a schematic illustration of a tubule inorganic tubules, and the granular material 1104 is inor assembly 1103 comrpising a tubules 1102 onto which and ganic granular material. In one aspect of this embodiment, into which nanomagnetic material 1106 has been incorpo the inorganic tubules are halloysite tubules. rated. Such incorporation of the nanomagnetic material into 0707 FIG. 25 is a sectional view of the nancomposite the microtubule 1102 may be done by conventional means. assembly 1100 of FIG. 24, showing the granular material Reference may be had, e.g., to U.S. Pat. No. 4,877,501 1104 disposed both between the tubules 1102 as well as (process for fabrication of lipid microstrucutres), U.S. Pat. within the tubules 1102. In another embodiment, not shown, No. 4,911,981 (metal clad lipid microstrucutres), U.S. Pat. the granular material 1104 is disposed between the tubules No. 5,049.382 (cating and composition contaiing lipid 1102 but not within the tubules 1102. In yet another embodi microstructure toxin dispenses), U.S. Pat. No. 5,492,696 ment, not shown, the granular material 1104 is disposed (controlled relase microstructures), U.S. Pat. No. 5,651,976 within the tubules 1102 but not between the tubules 1102. (controlled release of active agents using inorganic tubules), U.S. Pat. No. 5,705,191 (sustained delivery of active com 0708. When the tubular material 1100 is mined (such as, pounds from tubules, with rational control), U.S. Pat. No. e.g., when halloysite is ined), it generally contains from 5,744,337 (internal gelation method for forming multilayer about 5 to about 95 weight of tubular material 1102; and it microspheres), U.S. Pat. No. 6,013,206 (formation of high often contains from about 5 to about 50 weight percent of aspect ratio lipid microtubules), U.S. Pat. No. 6,280,759 tubular material 1102. However, as is well-known to those (method of controlled release and controlled release micro skilled in the art, the as-mined mineral (such as, e.g., as structures), and the like. The entire disclosure of each of mined halloysite) may be purified to increase its concentra these United States patent is hereby incorporated by refer tion of the tubular form 1102 of the mineral. ence into this specification. 0709. It is preferred that the as-mined mineral matter be 0715) In the embodiment depicted in FIG. 28, the tubule purified by conventional means to concentrate the long 1102 is coated with a multiplicity of nano-sized particles tubules 1102. Such conventional means may include, e.g., 1106 (Such as, e.g., nanomagnetic particles that are Smaller electrostatic means, ultrasonic means, centrifugal means, than about 100 nanometers and, more preferably, smaller and/or sieving. than about 50 nanometers). In the embodiment depicted, the nanomagnetic particles 1106 adhere to both themselves and 0710. As is known to those skilled in the art, halloysite to the tubules 1102, thereby forming a continuous film 1108 has been obtained thatcontains at least 95 weight percent of on the outer surface of the tubule 1102. the tubular form 1102. Reference may be had, e.g., to tubular halloysite from Yunnan China and, in particular, to a pho 0716. As will b seen by reference to the preferred tograph thereof that appears in the “Mineral Gallery of the embodiment depicted in FIG. 26, the preferred composite Clay Minerals Group of the Mineralogical Society. This material 1101 comprised of tubular halloysite 1102 and photograph was published on the website of the Mineral nanomagnetic particles 1106 affixed to the outside surface of ogical Society (www.minerSoc.org). Information about it the tubules 1102. In the emboidmen depicted in FIG. 26, the US 2006/01 02871 A1 May 18, 2006 60 composite material 1103 is comprised of nanomagnetic and they form a continuous film. The term “continuous film' materials disposed on both the inside and outside Surfaces of is well known to those skilled in the art and is described, e.g., the tubules 1102. In one aspect of the embodiment depicted at page 521 of N. Irving Sax et al’s “Hawley's Condensed in FIG. 27, the tubules 1102 are preferably filled in accor Chemical Dictionary.” Eleventh Edition, Van Nostrand dance with the procedures described in one or more of the Reinhold Company, New York, N.Y., 1987. As is disclosed Price patents mentioned elsewhere in this specification. in Such work, a film is an “ . . . extremely thin continuous sheet of a Substance which may or may not be in contact with 0717 The coated halloysite material 1101, and/or the a substrate. There is no precise upper limit of thickness, but coated halloysite material 1103, may be incorporated into a a reasonable assumption is 0.010 inch. The protective value matrix that is either polymeric, resinous, elastomeric, or of a film depends on its being 100% continuous, i.e., without ceramic and thereafter shaped into a formed object. It may holes or cracks, since it must form an efficient barrier to be used, in whole or in part, as the inorganic material in any molecules of atmospheric water vapor, oxygen, etc. . . . ' or all of the compositions described elsewhere in this Reference also may be had, e.g., to U.S. Pat. No. 4.243,699 specification in which naturally-occurring halloysite has (method of powder coating the inside of pipes with a been used or could have been used. When so used, the continuous flim of plastic material), U.S. Pat. No. 4,435, shaped objects formed from such matrix/modified halloysite 141 (multicomponent continuous film die), U.S. Pat. No. composite material preferably having a shielding factor 4.466.872 (method of and apparatus for depositing a con greate than 0.5. tinuous film of minimum thickness), U.S. Pat. No. 4,505,699 0718 The term "shielding factor” is described in U.S. (apparatus for making enylopes from a continuous film Pat. No. 6,713,671, the entire disclosure of which is hereby sheet), U.S. Pat. No. 4,741,811 (process and apparatus for incorporated by reference into this specification. Referring electrolytically depositing in a moving mode a continuous to FIG. 6 of U.S. Pat. No. 6,713,671, the film 104 is adapted film of nickel on metal wire), U.S. Pat. No. 4,816.297 to reduce the magnetic field strength at point 108 (which is (method of powder coating the inside of pipes with a disposed less than 1 centimeter above film 104) by at least continuous film of plstic material), U.S. Pat. No. 5.273,611 about 50 percent. Thus, if one were to measure the magnetic (apparatus for applying a continuous film to a pipeline), U.S. field strength at point 108, and thereafter measure the Pat. No. 5,358,736 (method of forming a thin and continu magnetic field strength at point 110 (which is disposed less ous film of conductive material), U.S. Pat. No. 5,544,840 than 1 centimeter below film 104), the latter magnetic field (continuous film take-up apparatus), U.S. Pat. No. 5,914, 184 strength would be no more than about 50 percent of the (breathable laminate including filled film and continuous former magnetic field strength. Put another way, the film 104 film), and the like; the entire disclosure of each of these has a magnetic shielding factor of at least about 0.5. United States patents is hereby incorporated by reference into this specification. 0719. The shielding factor of the shaped object com prised of the modified halloysite material described herein 0723. In one embodiment, the continuous film formed by above is measured by the same method, and it preferably is the nanomagnetic particles 106 has an average surface at least about 0.6. In one embodiment, the shaped object roughness of less than about 50 nanometers and, more (which may be, e.g., a film, a fiber, a fabric, etc) has a preferably, less than about 10 nanometers. AS is discussed magnetic shielding factor of at least about 0.9. Thus, e.g., elsewhere in this specification, the average Surface rough and referring again to such U.S. Pat. No. 6,713,671, the ness of a thin film is preferably measured by an atomic force magnetic field strength at point 110 is no greater than about microscope (AFM). Reference may be had, e.g., to U.S. Pat. 10 percent of the magnetic field strength at point 108. Thus, No. 5,420,796 (method of inspecting planarity of wafer e.g., the static magnetic field strength at point 108 can be, surface), U.S. Pat. Nos. 6,610,004, 6,140,014, 6,548,139, e.g., one Tesla, whereas the static magnetic field strength at 6,383,404, 6,586,322, 5,832,834, and 6,342,277. The entire point 110 can be, e.g., 0.1 Tesla. Furthermore, the time disclosure of each of these United States patents is hereby varying magnetic field strength of a 100 milliTesla would be incorporated by reference into this specification. reduced to about 10 milliTesla of the time-varying field. 0724. In one embodiment, the continuous film enhances 0720) Referring again to FIGS. 26 and 27, and without the mechanical strength of the tubules 1102 to which which wishing to be bound to any particular theory, applicants it is affixed. This increase in mechanical strength may be believe that the incorporation of nanomagnetic particles measured by the process described in U.S. Pat. No. 6,290, 1106 into and/or onto the halloysite tubules 1102 improves 771, the entire disclosure of which is hereby incorporated by the physical properties of such halloysite tubules 1102. This reference into this specification. is illustrated in FIG. 28. 0725) The continuous film on the outer surface 1108 of 0721. In the preferred embodiment depicted in FIG. 28, the tubule 1102 provides several distinct advantages. In tubule 1102 (which is preferably a halloysite tubule but addition to providing adaptive shielding (discussed later in could be, e.g., a lipid microtubule or a carbon nanotube) is this specification) and potentially modifying the thermal coated with a multiplicity of nano-sized particles 1106 that characteristics of such tubule 1102, it also improves the are contiguous with the outer surface 1108 of the tubule mechanical properties of such tubule 1102. 1102. The nanomagnetic particles 1106 preferably have an 0726) The film 1108 of nanomagnetic particles 1106 average particle size of less than about 100 nanometers and, preferably has a surface roughness of less than about 50 more preferably, less than about 10 nanometers. nanometers and, more preferably, less than about 10 nanom 0722. In the preferred embodiment illustrated in FIG. 28, eters. AS is known to those skilled in the art, the average the nanomagentic particles 1106 preferably adhere both to Surface roughness of a thin film is preferably measured by an themselves and to the outer surface 1108 of the tubule 1102, atomic force microscope (AFM). Reference may be had, US 2006/01 02871 A1 May 18, 2006

e.g., to U.S. Pat. No. 5,420.796 (method of inspecting the present invention (Example 1) has an increase of 14.9% planarity of wafer surface), U.S. Pat. Nos. 6,610.004, 6,140, of the conventional mortar (Comparative Example 1) in 014, 6,548,139, 6,383,404, 6,586,322, 5,832,834, and 6,342, flexural strength. The mortar using unactivated kaolin 277. The entire disclosure of each of these United States (Comparative Example 2) shows a decrease of 27.3% of the patents is hereby incorporated by reference into this speci conventional mortar (Comparative Example 1) in flexural fication. Reference may also be had to the discussion of strength.” Surface roughness that appears elsewhere in this specifica 0733 U.S. Pat. No. 6,290,771 also discloses that (in tion. column 7) “Compressive strengths were measured accord 0727. Referring again to FIG. 28, and in the preferred ing to KSL 5105. The applied force was 80 kg. multidot embodiment depicted therein, the coated tubules 1107 pref ..force per second. After measurement of the flexural erably comprise a continuous film 1108 of nanomagnetic strength, six specimens per Example were tested. The com particles 1106 on the outer surface of such tubules 1102; and pressive strengths of the specimens were shown in Table 7. such tubules 1102 have improved compressive strength and ... As shown in Table 7, the mortar according to the present flexural strength properties. When a composition comprised invention (Example 1) has an increase of 25.8% of the of at least 80 weight percent of such coated tubules 1107 conventional mortar (Comparative Example 1) in compres (and, preferably, at least about 90 weight percent of such sive strength. The mortar using unactivated kaolin (Com coated tubules 1107) is tested in accordance with the pro parative Example 2) shows a decrease of 8.9% of the cedure described in U.S. Pat. No. 6,290,771, the compres conventional mortar (Comparative Example 1) in compres sive strength obtained is at least 2,000 kilograms per square sive strength.” centimeter, and the flexural strength obtained is at least 0734 The best flexural strength obtainable in the experi about 200 kilograms per square centimeter. ments reported in U.S. Pat. No. 6,290,771 was 89.1 kilo 0728 U.S. Pat. No. 6,290,771 describes an “Activated grams per square centimeter (see Table 6. Example 1). By kaolin powder compound for mixing with cement . . . ; the comparison, when the experiments of U.S. Pat. No. 6,290, entire disclosure of this United States patent is hereby 771 are repeated using 50 grams of a composition that incorporated by reference into this specification. In contains at least 80 weight pecent of the tubules 1107 (see Examples 1 and 2 of this patent, a description is presented FIG. 28), the flexural strength obtained is at least 200 of a method for determining the compressive strength and kilograms per square centimeter. In one embodiment, the the flexural strength of various mineral compositions. flexural strength so obtained is at least 300 kilograms per square centimeter. The term “flexural strength,” as used in 0729) The “Example 1 of U.S. Pat. No. 6,290,771 this specification (and in the claims of this case), refers to the appears at column 7 of Such patent. It discloses that "Cement value obtained when 50 grams of the composition in ques of 450 g, activated kaolin of 50 g. sands of 1,500 g, water tion is used in the test specified in U.S. Pat. No. 6,290,771. of 250 g and superplasticizer of 5 g were mixed together. 0735. The best compressive strength obtainable in the Specimens of mortar of 40x40x160 mm were prepared from experiments reported in U.S. Pat. No. 6,290,771 was 958 the mixture. The specimens were wet-cured in a 3-in-1 mold kilograms per square centimeter (see Table 7. Example 1). for 24 hours, and water-cured for 28 days. Three specimens By comparison, when the experiments of U.S. Pat. No. (Specimens I, II and III) were prepared.” 6,290.771 are repeated using 50 grams of a composition that 0730. The “Comparative Example 1 of U.S. Pat. No. contains at least 80 weight percent of the tubules 1107 (see 6,290,771 was also disclosed at such column 7. In such FIG. 28), the compressive strength obtained is at least 2,000 column 7, it was stated that “A conventional mortar was kilograms per square centimeter. In one embodiment, the prepared. Cement of 500 g, sands of 1,500 g, water of 250 flexural strength so obtained is at least 3,000 kilograms per g and Superplasticizer of 5 g were mixed together. Speci square centimeter. The term "compressive strength,” as used mens of mortar of 40x40x160 mm were prepared from the in this specification (and in the claims of this case), refers to mixture. The specimens were wet-cured in a 3-in-1 mold for the value obtained when 50 grams of the composition in 24 hours, and water-cured for 28 days. Three specimens question is used in the test specified in U.S. Pat. No. (Specimens I, II and III) were prepared.” 6,290,771. 0731. The “Comparative Example 2 of U.S. Pat. No. 0736. In addition to improving the physical properties of 6,290,771 also appeared in such column 7, wherein it was the tubules 1102, the coating/film 1108 also improves the disclosed that “Comparative Example 2 was performed as in shielding properties of a composition that contains at least Example 1 with the exceptions that unactivated kaolin of 50 80 weight percent of the tubules 1107. Such a composition g was employed instead of the activated kaolin of 50 g. has shielding factor of at least 0.5 and, preferably, at least Three specimens (Specimens I, II and III) were prepared. . about 0.9. Such a shielding factor is discussed elsewhere in . . Flexural strength, compressive strength and water per this specification. meability were measured for the specimens of Example 1 0737 Referring again to FIG. 28, the film 1108 engages and Comparative Examples 1 and 2. . . . Flexural strengths in “adaptive shielding, i.e., it changes its electrical prop were measured according to Korean Industrial Standard KS erties as it senses electromagnetic radiation. L 5105. The distance of points was 100 mm and the applied 0738 FIGS. 29 and 30 illustrate why this “adaptive force was 5 kg.multidot...force per second. The strengths of shielding occurs. FIG. 29 illustrates the response of a the specimens were shown in Table 6.” nanomagnetic coating in response to an alternating current 0732. The results of these experiments were discussed at electromagnetic field. FIG. 30 illustrates the response of columns 7-8 of U.S. Pat. No. 6,290,771, wherein it was Such coating to both an alternating current electromagnetic disclosed that “As shown in Table 6, the mortar according to field and a direct current magnetic field 1138. US 2006/01 02871 A1 May 18, 2006 62

0739 Referring to FIG. 29, when there is no direct vacuum magnetron Sputtering method and apparatus for current magnetic field 1138, you will produce a hysteresis precision optical coatings), U.S. Pat. No. 6,083.364 (mag loop 1130 that is comprised of a set of minor loops 1132, netron sputtering apparatus for single Substrate processing), 1134, and 1136. When a d.c. magnetic field 1138 is also U.S. Pat. No. 6,315,874 (method of depositing a thin film of present (see FIG. 30), you will obtain a major loop 1140 and metal oxide by magnetron sputtering) U.S. Pat. No. 6,365, minor loops 1142 and 1144. 509 (combined RF-DC magnetron sputtering method), U.S. Pat. No. 6,494,999 (magnetron sputtering apparatus with an 0740. As will be apparent to those skilled in the art, the integral cooling and pressure relieving cathode), U.S. Pat. slope of the curve(s) obtained is the susceptibility, and it will No. 6,620.299 (process and device for the coating of sub vary depending upon the value of the applied alternating strates by means of bipolar pulsed magnetron Sputtering), current field and the applied direct current field. U.S. Pat. No. 6,679,981 (inductive plasma loop enhancing 0741. As the slopes of the curves change, as the suscep magnetron Sputtering), and the like. The entire disclosure of tibility changes, the magnetization changes; and as the each of these United States patents is hereby incorporated by magnetization of the coating 1108 changes, the electromag reference into this specification. netic properties of the nanomagnetic coating changes. 0745) Referring again to FIG. 31, and to one preferred 0742 Thus, the electromagnetic properties of the nano aspect of the embodiment described therein, a Kurt J. Lesker magnetic coating will depend, at least in part, on the Supere System III deposition system outfitted with Lesker properties and intensity of the a.c. fields and/or d.c. fields to Torus magnetrons is preferably used in the process. The which it is exposed. It will also depend, in part, on the vauum chamber 1202 is preferably cylindrical, with a diam concentrations of the 'A', 'B', and “C” moieties discussed eter of about one meter and a height of about 0.6 meters. elsewhere in this specification and with reference to U.S. 0746. It is preferred that the base pressure be less than Pat. No. 6,765,144 (see FIG. 37), the entire disclosure of about 0.2 microTorr. The target 1204 is preferably a disc which is hereby incorporated by reference into this specifi with a diameter of about 0.07 meters. The sputtering gas is cation. argon, and is is preferably fed at a flow rate of from about A Preferred Process for Preparing Particles of Nanomagentic 15 to about 35 sccm in the direction of arrow 1206 through Material. line 1208. To fabricate the nanomagnetic powders, it is preferred to use a pulsed D.C. power source 1210 at a power 0743 FIG. 31 is a schematic of a preferred process 1200 level of from about 4.5 to about 11 watts per square for preparing particles of nanomagneic material. In the centimeter. Thus, e.g., to achieve a power level of 8.6 watts preferred process, the particles are fabricated by PVD mag per square cemtimeter, one may use a target with a diameter netron sputtering. of 3 inches and a power level of 500 watts. 0744 Magnetron sputtering is well known to those 0747. In the process depicted in FIG. 31, the magnetron skilled in the art. Reference may be had, e.g., to U.S. Pat. polarity preferably Switches from negative to positive at a No. 4,162.954 (planar magnetron sputtering device), U.S. frequency of 100 kilohertz, while the pulse width for the Pat. No. 4,179,351 (cylindrical magnetron sputtering positive or negative duration can be adjusted to yield Suit source), U.S. Pat. No. 4,198.283 (magnetron sputtering able sputtering results. Different weight ratios for the con target and cathode assembly), U.S. Pat. No. 4,299.678 centrations of iron and aluminum in the targets are prefer (magnetic target plate for use in magnetron sputtering of ably used for FeAlN coatings. The reactive gas, which magnetic films), U.S. Pat. No. 4.324,631 (magnetron sput preferably is nitrogen, is fed in the direction of arrow 1210 tering of magnetic materials), U.S. Pat. No. 4,428,816 via line 1212. (focusing magnetron Sputtering apparatus), U.S. Pat. No. 4,606,802 (planar magnetron sputtering with modified field 0748. The reactive gas is preferably supplied in an argon/ configuration), U.S. Pat. No. 4.714,536 (planar magnetron nitrogen ratio that varies from approximately 25/15 to 35/25 sputtering device with combined circumferential and radial and a chamber 1202 pressure between 1.8 mtorr (0.24 Pa) movement of magnetic fields), U.S. Pat. No. 4,746,417 and 6.5 mtorr (0.87 Pa), depending on composition. In (magnetron Sputtering cathode for vacuum coating appara general, the high the iron concentration desired, the greater tus), U.S. Pat. No. 4,747.926 (conical-frustrum sputtering the pressure required is to maintain a plasma within the target), U.S. Pat. No. 4,865,708 (magnetron sputtering cath system. ode), U.S. Pat. No. 4,879,017 (multi-rod type magnetron sputtering apparatus), U.S. Pat. No. 5,106,470 (method and 0749 Referring again to FIG. 31, the powder collected device for controlling an electromagnet for a magnetron used is a fused silica bowl 1214, with a diameter of about 16 sputtering source), U.S. Pat. No. 5,120,417 (magnetron centimeters and a height of about 8 centimeters. The bowl sputtering apparatus and thin film depositing method), U.S. 1214 is placed on a substrate holder 1216 disposed within Pat. No. 5,171.415 (cooling method and apparatus for mag the vacuum chamber 1202. The distance between the target netron sputtering), U.S. Pat. No. 5,178,743 (cylindrical 1204 and the bottom of the powder collector 1214 is about magnetron sputtering system), U.S. Pat. No. 5,188,717 15 centimeters. (Sweeping method and magnet track apparatus for magne 0750. In one embodiment, and referring again to FIG. 31, tron sputtering), U.S. Pat. No. 5,334.302 (sputtering gun), the pressure of the main chamber 1202 is reduced to a base U.S. Pat. No. 5,354,446 (ceramic rotatable magnetron sput pressure of 100 mtorr (13.3 Pa) using a dry pump. The tering cathode target), U.S. Pat. No. 5,399.252 (apparatus for pressure of the main chamber 1202 is further reduced to 0.2 coating a Substrate by magnetron sputtering), U.S. Pat. No. microtoff (2.7x10 Pa) using a 10" cryogentic pump Initial 5,525, 199 (low pressure reactive magnetron sputtering FeAlN depositions are preferably conducted at an argon apparatus and method), U.S. Pat. No. 5,656,138 (very high flow rate of 35 sccm and a nitrogen flow rate of 15 sccm. The US 2006/01 02871 A1 May 18, 2006 pumping speed is preferably then redued to increase the 0757. The reactive gas is preferably supplied in an argon/ chamber 1202 pressure to about 5 mtorr (0.67 Pa). These nitrogen ratio that varies from approximately 25/15 to 35/25 parameters are preferably used so that the deposited film is and a chamber 1202 pressure between 1.8 mtorr (0.24 Pa) tensile stressed and does not adhere to the silica bowl. and 6.5 mtorr (0.87 Pa), depending on composition. In 0751. In one preferred embodiment, a Fischer Chiller general, the high the iron concentration desired, the greater 1220 is used to cool the substrate holder 1216. In this the pressure required is to maintain a plasma within the embodiment, silicone fluid, cooled to a temperature of about system. minus 90 degrees Celsius, is circulated through the substrate 0758 Referring again to FIG. 33, and to the preferred holder 1216 via line 1222. In one aspect of this embodiment, embodiment depicted therein, the halloysite pellets 1230 are a copper heat exchanger with a flat bottom plate is fabricated placed upon a substrate holder 1232 disposed within the such that the silica bowl 1214 is completely surrounded by vacuum chamber 1202. The distance between the target copper. 1204 and the pellets 1230 is about 15 centimeters. Coating of a Mineral Composition with Nanomagnetic Mate 0759. In one embodiment, and referring again to FIG.33, rial the pressure of the main chamber 1202 is reduced to a base 0752 FIG. 32 is a schematic illustration of a die assem pressure of 100 mtorr (13.3 Pa) using a dry pump. The bly 1250 that can be used to prepare pellets of mineral matter pressure of the main chamber 1202 is further reduced to 0.2 that thereafter can be coated with nanomagnetic material. microtorr (2.7x10 Pa) using a 10" cryogentic pump Initial The die assembly 1250 is comprised of a cylindraceous main FeAlN depositions are preferably conducted at an argon body 1252 with an inner diameter of 1 inch, a plunger 1254 flow rate of 35 sccm and a nitrogen flow rate of 15 sccm. The with a diameter of 1 inch, and a pellet sample extractor 1256 pumping speed is preferably then reduced to increase the with a diameter of 1 inch to facilitate sample removal. chamber 1202 pressure to about 5 mtorr (0.67 Pa). 0753. The die assembly can be utilized prepare pellets A Nanomagnetic Composition with Improved Echo Ampli comprised of one or more of the mineral materials described tude Response elsewhere in this specification. Thus, by way of illustration and not limitation, and when a halloysite composition is the 0760. In this section of the specificiation, applicants will mineral matter, one may place the main body 1252 with the describe a preferred composition with an improved echo extractor 1256 stably on the sample holder stage of a manual amplitude response. This composition is similar in some Carver Hydraulic Press Unit. About 0.25 ounces of hal respects to the composition disclosed in U.S. Pat. No. loysite powder are charged into the hole of the main body 6,720,074, the entire disclosure of which is hereby incor 1252 if a halloystie pellet with a thickness oabout 0.2 inches porated by reference into this specification. is desire. Thereafter, the plunger 1254 is inserted into the 0761. At column 7 of U.S. Pat. No. 6,720,074, starting at hole 1258 in the direction of arrow 1260 while the sample line 29 thereof, certain “NMR experiments’ were discussed. holder 1256 is moved in the direction of arrow 1260. A force It was disclosed that “NMR experiments. Co spin-echo of from 4 to 5 pounds is applied and maintained until the NMR experiments were carried out at 4.2 K using a Matec force becomes stable. Thereafter, the sample extractor 1256 7700 NMR. FIGS. 7a and 7b show the Co NMR spectra is lowered, the die is removed, and the halloysite pellet is of n-COs/(SiO)so annealed at 400° C. and 900°C., respec then removed to be used in the process depicted in FIG. 33. tively. For the sample annealed at 400° C., the NMR 0754) In the process depicted in FIG.33, a Kurt J. Lesker spectrum consists of a single peak centered at 223 MHz. Supere System III deposition system outfitted with Lesker This means the Co particle is smaller than 75 nm and has Torus magnetrons is preferably used. The Vauum chamber single domain structure. The very broad spectrum is also an 1202 is preferably cylindrical, with a diameter of about one indication of the smallness of the particle. For the sample annealed at 900° C., instead of the main peak at 223 MHz, meter and a height of about 0.6 meters. there are two satellites centered at 211 and 199 MHz, which 0755. It is preferred that the base pressure be less than correspond to the Co atoms having 1 and 2 Si atoms, about 0.2 microTorr. The target 1204 is preferably a disc respectively, as nearest neighbors. This demonstrates that Si with a diameter of about 0.07 meters. The sputtering gas is enters the Co lattice when annealing at temperatures higher argon, and is is preferably fed at a flow rate of from about than 900° C.” The experiment described in column 7 of this 15 to about 35 sccm in the direction of arrow 1206 through patent was also illustrated in FIGS. 7a and 7b thereof. line 1208. To fabricate the nanomagnetic powders, it is preferred to use a pulsed D.C. power source 1210 at a power 0762. As will be seen by reference to FIGS. 7a and 7b of level of from about 4.5 to about 11 watts per square U.S. Pat. No. 6,720,074, at a frequency of 223 megahertz, centimeter. Thus, e.g., to achieve a power level of 8.6 watts and for the COso? (SiO2)so composition described herein per square cemtimeter, one may use a target with a diameter above, and at a temperature of 4.2 degrees Kelvin, a peak of of 3 inches and a power level of 500 watts. echo amplitidue was obtained. These FIGS. 7a and 7b are 0756. In the process depicted in FIG. 33, the magnetron described in such U.S. Pat. No. 6,720,074 as follows: “FIG. polarity preferably Switches from negative to positive at a 7 is a typical Co NMR spectrum of Co/(SiO.) nanostruc frequency of 100 kilohertz, while the pulse width for the tured composite annealed (a) at 400° C. in H showing all positive or negative duration can be adjusted to yield Suit the Co nanostructured particles are in a ficc single domain able sputtering results. Different weight ratios for the con state and no Si atoms in the Co lattice, and (b) at 900° C. in centrations of iron and aluminum in the targets are prefer He showing Co particle being in a fcc single domain state, ably used for FeAlN coatings. The reactive gas, which but some Si atoms having entered the Co lattice.” preferably is nitrogen, is fed in the direction of arrow 1210 0763) Applicants have disovered a composition that will via line 1212. have a spin echo peak at a frequency of from about 30 US 2006/01 02871 A1 May 18, 2006 64 toabout 400 megahertz and, more preferably from about 60 and/or the B moieity and/or the B moieties, and/or the C to about 140 megahertz. This spin echo peak will be present moiety and/or the C moieties, one can vary the frequency at at the aforementioned frequency (which may be, e.g., 64 which the optimal spinehco response is obtained. Similarly, megahertz, 128 megahertz, etc.) when measured at an ambi one also can vary the particle size of the ABC moiety to ent temperature. obtain the desired response. 0764. The composition that will achieve this desired 0771 FIG. 34 is a graph 1300 of the amplituide of the result has the basic “ABC formula described elsewhere in spin echo response vesus frequency. The frequency 1302 this specification, provided that, in one embodiment, the A preferably is either 64 megahertz or 128 megahertz. The moiety contains both iron and cobalt. In one aspect of this resulting amplitude 1304 will vary with inversely with embodiment, at least 5 mole percent of cobalt, by total moles temperature, the amplitude 1304 at 4.3 degrees Kelvin being of iron and cobalt, are present in the A moiety. It is preferred greater than the amplitude 1304 at room temperature. to have at least about 10 mole percent of such cobalt. 0772 U.S. Pat. No. 6,720,074 contains an excellent bib 0765. In another embodiment, the A moiety consists liography citing articles that are relevant to both their work essentially of cobalt. In another embodiment, the A moiety and applicants’ composition. Reference may be had, e.g. to is compried of at least 5 mole percent of cobalt and, articles by T. D. Xiao, K. E. Gonsalves and P. R. Strutt additionally, an element selected from the group consisting (“Synthesis of Aluminum Nitride/Boron Nitride Composite of iron, nickel, Samarium, gadolinium, and one or more of Materials,” J. Am. Ceram. Soc. 76,987-92, 1993), and by the other A elements mentioned elsewhere in this specifica Wang, et. al (“Preparation and Magnetic properties of tion; in this embodiment, it is preferred that the A moiety Fe100.alpha. Nix-SiO2 Granular Alloy Solid Using a Sol contain less than about 20 mole percent of cobalt; and it is Gel Method: Journal of Magnetism and Magnetic Materials also preferred that, in the ABC composition, the A moiety 135, 1994). represents from about 5 to about 20 mole percent of the total A Composition with a Specified Ferromagnetic Resonance composition. Frequency 0766. In one embodiment, in the preferred ABC compo 0773. In this section of the specification, applicants will sition, it is preferred that the A moieties represent from about discuss a preferred composition with a specified ferromag 5 to about 20 weight percent of the A and B moieties. Put netic resonance frequency. As is known to those skilled in another way, the total weight of all of the A moieties is from the art, ferromagnetic resonance is the magnetic resonance about 5 to about 20 percent of the total weight of all of the of a ferromagnetic material. Reference may be had, e.g., to A moieties and the B moieties combined. page 7-98 of E.U. Condon et al.’s “Handbook of Physics.” (McGraw-Hill Book Company, New York, N.Y., 1958). 0767. In one embodiment, in the preferred ABC compo Reference also may be had, e.g., to U.S. Pat. Nos. 4,263.374; sition, the C moiety or moieties is/are present at a concen 4,269,651; 4.853,660; 6,362.533; 6,362.543; 6,501,971; and tration of at least about 5 mole percent and, preferably, at the like. The entire disclosure of each of these United States least about 10 mole percent. patents is hereby incorporated by reference into this speci 0768. The particle size of the ABC moiety will affect its fication. spin echo response. In one embodiment, Such particle size is 0774. By way of illustration and not limitation, and from 1 nanometer to about 100 nanometers and will opti referring to U.S. Pat. No. 4,853,660, it is disclosed in such mally vary depending upon the frequency at which one patent that “The arrangement shown in FIG. 2 provides a desires the spin echo peak to occur. In general, the high the simple band stop or band reject filter 20. It is generally frequency at which Such peak is desired, the Smaller the preferred that the width W26 of the composite strip con particle size is. ductor 26 is chosen in conjunction with the thickness of the dielectric substrate 22 to provide the microstip transmission 0769. In one embodiment, the ABC composition used is line media with a desired characteristic impedance here 50 heat treated in Substantial accordance with the process ohms. Since the orientation of the composite strip conductor disclosed in U.S. Pat. No. 6,720,074, but at a lower tem 26 with respect to the crystalline axes of the gallium arsenide perature. The heat treatment process of Such patent is Substrate is chosen Such that the microStrip line is parallel to described in column 7 thereof, wherein it is disclosed that a selected one of the in-plane “easy axis of the Fe film, (that the composition of such patent is “ . . . annealed at 400° C. is either the <010> or <001> axis), when a DC magnetic and 900° C. . . . . As is known to those skilled in the art, field is applied parallel to the microStrip conductor as shown annealing is a process in which the material is heat treated in FIG. 2 the strength of this field will determine the to affect its physical properties. In applicants’ process, it is frequency at which the microstrip conductor has a maximal preferred to anneal applicants preferred “ABC composi ferromagnetic absorption. For a thin film as shown in FIG. tions' at a temperature of less than 400 degrees Celsius for 2, the ferromagnetic frequency (fres) is related to the applied less than one hour. In one aspect of this embodiment, the magnetic field H, the anisotropy field Han, the Saturation composition is heat treated for about 20 to about 40 minutes magnetization 4 MS and the gyromagnetic ratio gamma. by at a temperature of from about 200 to about 350 degrees the equation: 2. pi. fres=gamma. {(H+Han)(H+Han+ Celsius. The heat treatment may be omitted as long as, 4pi.Ms)}1/2Equation 1. For an iron film at room tempera during the formation of the “ABC composition, the com ture 4-pi. Ms=22,000 Oe; Han 550 Oe; and gamma./2.pi.= position formed in situ (as it is sputtering) and, thus, has the 2.8 MHz/Oe. This implies that for H=0 the resonant desired physical properties which are described in U.S. Pat. frequency of the structure shown in FIG. 2 is approximately No. 6,720,074. 986 GHz. 0770. As will be apparent, by varying the composition 0775. In one embodiment of this invention, the afore and/or the concentration of the A moiety or the A moieties, mentioned ABC composition has a ferromagnetic resonance US 2006/01 02871 A1 May 18, 2006 frequency of from about 100 megahertz to about 15 giga Nitinol, for example, often increases its length by at least hertz and, preferably, from about 1 gigahetz to about 10 about 2 percent per degree increase in temperature. gigahertz. In one aspect of this embodiment, the ferromag 0784 Referring again to FIG. 36, in the embodiment netic resonance frequency is from about 9 gigahertz to about 1330 the stent assembly has not been subjected to the field 10 gigahertz. 1338 for a period of time sufficient to raise its temperature 0776. In one preferred embodiment, illustrated in FIG. and change its dimensions. By comparison, in the embodi 35, the ABC composition is disposed as a coating 1310 on ment 1331, the stent has encountered substantial heating due a substrate 1312. The coating 1310 preferably has a thick to the absorption of electromagnetic radiation 1338 and has ness 1314 of from about 10 nanometers to about 2 microme Substantially increased its dimensions. ters and, more preferably, from about 50 nanometers to 0785 Referring again to FIG. 36, and in one embodiment about 1,000 nanometers. Without wishing to be bound to any thereof, the radiation source 1340 is a source of microwave particular theory, applicants believe that thicker coatings do energy produced by a horn antenna (for improved direction not produce the desired degree of spin alignment and/or ality). In another embodiment, the microwave energy is magnetic moment alignment. produced a dipole. In yet another embodiment, the micro 0777. In the embodiment depicted in FIG.35, the surface wave energy is produced by a phased array assembly. 1316 of the substrate is substantially flat. Thus, the magnetic 0786. In one preferred embodiment, a coated stent is moments 1318 and 1320 of the coating 1310 tend to align in expanded during MRI guided Surgery to afford better access the direction of the surface 1316. to the interior of the stent and/or the Surrounding area (Such 0778 To obtain the preferred ferrogmagnetic resonance as, e.g., a heart Valve). frequency of from about 9 to about 10 gigahertz, it is 0787 FIG. 37 is a sectional view of a coated tubule preferred that the particle size of the ABC composition be assembly 1400 comprised of a tubule 1402 (such as, e.g., a from about 1 to about 50 nanometers and, more preferably, halloysite tubules) coated with nanomagnetic material 1404 from about 3 to about 10 nanometers. In one embodiment, on its inside and outside Surfaces. Disposed within the inner the C moiety or moieties present in the ABC composition lumen 1406 of the tubule 1402 is a biologically active comprise from about 5 to 20 molar percent, by total moles material 1408 that elutes from at least one end 1410 of the of A, B, and C moieties. tubule 1402 when the biologically active material is heated. 0779). In one embodiment, the ABC compositon com The extent to which such biologically active material elutes prises Fe—AlN in which the aluminum nitride acts as good depends upon the extent to which (time and temperature) thermal conductor to conduct heat from the coating 1310 to Such biologically active material is heated. the substrate 1312. In this embodiment, the ABC composi 0788. In the preferred embodiment depicted, the coated ton is preferably comprised of at least about 50 mole percent tubule assembly 1400 is comprised of a polymeric matrix of AlN, by total moles of Fe and AlN. 1412 in which the coated tubule 1402 is disposed. When the 0780. One may make and test the desired composition by assembly 1400 is subjected to microwave radiation 1414, at means well known to those skilled in the art. Reference may least some of Such microwave radiation is preferentially be had to a paper by Xingwu Wang et al., “Nano-magnetic absorbed by the nanomagentic material 1404 which prefer FeAl and FeAlN thin films via Sputtering,” 27" Interna ably has a ferromagnetic resonance frequency of from about tional Cocoa Beach Conference on Advanced Ceramics and 1 to about 10 gigahertz. At least Some of the energy so Composites A. American Ceramic Society, Westerville, absorbed is converted to heat, and at least some of such heat Ohio, 2003, at page 629. is used to heat up the biologically active material 1408, thereby increasing the elution rate of such material 1408 out 0781 FIG. 36 illustrates a coated stent assembly 1330 of end 140 of tubule 1402. comrpised of coated strucutural members 1332. By way of illustration, coatings 1334 are shown disposed on structural An Assembly Comprised of the Nanocomposite of FIG. 37 members 1336. For the sake of simplicity of representation, 0789. The coated tubule assembly of FIG.37, either with such coatings 1334 have not been shown for all of the or without biological material disposed therein, may be used structural members 1336. with a biological organism to provide either diagnosis of one 0782. When the coated structural members 1332 are or more of the properties of such biological organism and/or exposed to an external electromagnetic field 1338 produced a therapeutic agent (Such as a drug and/or radiation) to Such by field generator 1340, the coatings 1334 will tend to biological organism. Implantable devices which may be absorb that portion of the field 1338 that is at a frequency modified in accordance with applicants invention to per near its ferromagnetic resonance frequency. When, e.g., the form either or both of such functions are well known to those coatings 1334 have a frerromagnetic resonance frequency of skilled in the art. Reference may be had, e.g., to U.S. Pat. between 9 and 10 gigahertz, and the field 1338 is comprised No. 5.292.342 (low cost implantable medical device), U.S. of an alternating current field with a frequency of between Pat. No. 5,645,580 (implantable medical device lead assem 9 and 10 gigahertz, the coatings 1334 will absorb energy and bly having high efficiency, flexible electrode head), U.S. Pat. convert part or all of such energy to heat. This heat will be No. 5,697.958 (electromagnetic noise detector for implant able medical device), U.S. Pat. No. 5,702,431 (enhanced transmitted, at least in part, to the structural members 1336. transcutaneous recharging Sytem for battery powered 0783. In one preferred embodiment, the structural mem implantable medical device), U.S. Pat. No. 5,722.998 (appa bers 1336 will have a positive coefficient of thermal expan ratus for the control of an implantable medical device), U.S. sion that will cause a change in dimension per degrees Pat. No. 5,722.999 (system and method for storing and Celsius in temperature increase of at least about 1 percent. displaing historical medical data measured by an implant US 2006/01 02871 A1 May 18, 2006 66 able medical device), U.S. Pat. No. 5,733,312 (system and able medical device telemetry processor), U.S. Pat. No. method for modulating the output of an implantable medical 6.738,671 (externally worn transceiver for use with an device I response to circadian variations), U.S. Pat. No. implantable medical device), U.S. Pat. No. 6,754,533 5,733,313 (RF coupled, implantable medical device with (implantable medical device configured for diagnostic emu rechargeable back-up power source), U.S. Pat. No. 5,861, lation), U.S. Pat. No. 6,763,269 (frequency agile telemetry 019 (implantable medical device microstrip telemetry system for implantable medical device), U.S. Pat. No. 6,766, antenna), U.S. Pat. No. 5,941,904 (electromagnetic accel 200 (magnetic coupling antennas for implantable medical eration transducer for implantable medical device), U.S. Pat. devices), U.S. Pat. No. 6,774.278 (coated implantable medi cal device), U.S. Pat. No. 6,795,729 (implantable medical No. 6,044.297 (posture and device orientation and calibra device having flat electrolytic capacitor), U.S. Pat. No. tion for implantable medical devices), U.S. Pat. No. 6,125, 6,795,732 (implantable device employing sonomicrometer 290 (tissue overgrowth detector for implantable medical output signals), U.S. Pat. No. 6,804,552 (MEMS switching device), U.S. Pat. No. 6,141,583 (implantable medical circuit and method for an implantable medical device), U.S. device incorporating performance based adjustable power Pat. No. 6,804,558 (system and method for communicating supply), U.S. Pat. No. 6,167,310 (downlink telemetry sys between an implantable medical device and a remote com tem for implantable medical device), U.S. Pat. No. 6,167, puter system or health care provider), U.S. Pat. No. 6,807, 312 (telemetry system for implantable medical devices), 439 (system for detecting dislodgment of an implantable U.S. Pat. No. 6,184.160 (hermetically sealed implantable medical device), U.S. Pat. No. 6,805,898 (surface features of medical device), U.S. Pat. No. 6,234,973 (implantable medi an implantable medical device), U.S. Pat. No. 6,809,701 cal device for sensing absolute blood pressure and baromet (circumferential antenna for an implantable medical device), ric pressure), U.S. Pat. No. 6,247,474 (audible sound com and the like. The entire disclosure of each of these United munication from an implantable medical devie), U.S. Pat. States patents is hereby incorporated by reference into this No. 6.292,698 (world wide patient location and data telem specification. The implantable medical devices described in etry system for implantable medical devices), U.S. Pat. No. these patents may be used in conjunction with, or modified 6,415,181 (implantable medical device incorporating adia to incorporate, applcicants’ coated tubule assembly of FIG. batic clock-powered logic), U.S. Pat. No. 6,438,408 (implantable medical device for monitoring congestive heart 37. failure), U.S. Pat. No. 6,453.201 (implantable medical 0790. Similarly, applicants’ coated tubule assembly of device with voice resonding and recording capacity), U.S. FIG. 37 may be used in conjunction with one or more of the Pat. No. 6,456,887 (low energy consumption RF telemetry ingestible medical devices described in the prior art. Refer control for an implantable medical device), U.S. Pat. No. ence may be had, e.g., to U.S. Pat. No. 3,971,362 (miniature 6,470,213 (implantable medical device), U.S. Pat. No. ingestible telemeer devices to measure deep-body tempera 6,482,154 (long rante implantable medical device telem ture), U.S. Pat. No. 3,993.563 (gas ingenstion and mixing etray system with positive patient identification), U.S. Pat. device), U.S. Pat. No. 5,866,165 (method and device for No. 6,505.077 (implantable medical device with external dispensing an ingestible soluble material for further dis recharging coil electrical connection), U.S. Pat. No. 6,539, solveing in a liquid), U.S. Pat. No. 6,632.216 (ingestible 253 (implantable medical device incorporating integrated device), and the like. The entire disclosure of each of these circuit notch filters), U.S. Pat. No. 6,551.345 (protection United States patents is hereby incorporated by reference apparatus for implantable medical device), U.S. Pat. No. into this specification. 6.580.947 (magnetic field sensor for an implantable medical device), U.S. Pat. No. 6,580,948 (interface devices for 0791 U.S. Pat. No. 6,632.216 is of interest with regard to instruments in communication with implantable medical Such ingestible devices. AS is disclosed at columns 1-2 of devices), U.S. Pat. No. 6,591,134 (implantable medical Such patent, “The present invention relates to an ingestible device), U.S. Pat. No. 6,644.322 (human languae translation device. In particular the invention relates to such a device in of patient session information from implantable medical the form of a capsule that is intended to release a controlled devices), U.S. Pat. No. 6,647.550 (patient programmer for quantity of a Substance, such as a pharmaceutically active implantable medical device with audio locator signal), U.S. compound, foodstuff, dye, radiolabelled marker, vaccine, Pat. No. 6,671,550 (system and method for determining physiological marker or diagnostic agent at a chosen loca location and tissue contact of an implantable medical device tion in the gastrointestinal (GI) tract of a mammal. Such a within the body), U.S. Pat. No. 6,671,552 (system and capsule is sometimes referred to as a “Site-Specific Delivery method for determining remaining battery life), U.S. Pat. Capsule', or SSDC.” No. 6,675,045 (split-can dipole antenna for implantable 0792 U.S. Pat. No. 6,632.216 also discloses that medical device), U.S. Pat. No. 6,689,117 (drug delivery “SSDC's have numerous uses. One use of particular interest system for implantable medical device), U.S. Pat. No. 6,675, to the pharmaceutical industry involves assessing the 049 (apparatus for automatic implantable medical lead rec absorption rate and/or efficacy of a compound under inves ognition and configuration), U.S. Pat. No. 6,681,135 (system tigation, at various locations in the GI tract. Pharmaceutical for employing temperature measurements to control the companies can use data obtained from Such investigations, operation of an implantable medical device), U.S. Pat. No. e.g. to improve commercially produced products.” 6,687.547 (apparatus for communicating with an implant able medical device with DTMF tones), U.S. Pat. No. 0793 U.S. Pat. No. 6,632,216 also discloses that “Sev 6,708,065 (antenna for implantable medical device), U.S. eral designs of SSDC are known. One design of capsule Pat. No. 6,716.444 (barriers for polymer-coated implantable intended for use in the GI tract of a mammal is disclosed in medical devices), U.S. Pat. No. 6,738,667 (implantable “Autonomous Telemetric Capsule to Explore the Small medical device for treating cardiac mechanical dysfunction Bowel, Lambert et al. Medical & Biological Engineering by electrical stimulation), U.S. Pat. No. 6,738,670 (implant and Computing, March 1991. The capsule shown therein US 2006/01 02871 A1 May 18, 2006 67 exhibits several features usually found in such devices, SAR (specific energy absorption rate). In general terms the namely: a reservoir for a Substance to be discharged into the induced current dominates up to 2 MHZ above which the GI tract; an on-board energy source; a mechanism, operable SAR effects take over.’ under power from the energy source, for initiating discharge 0796 U.S. Pat. No. 6,632.216 contains several indepen of the substance from the reservoir; a switch, operable dent claims that describe devices and/or processes that can remotely from outside the body of the mammal, for initiating advantageously be used in conjunction with applicants the discharge; and a telemetry device for transmitting data nancomposite material. Thus, e.g., claim 1 of Such patent indicative of the status, location and/or orientation of the describes “1. An ingestible device for delivering a substance capsule Also, of course, the dimensions of the capsule are to a chosen or identifiable location in the alimentary canal of Such as to permit its ingestion via the oesophagus; and the a human or animal, comprising an openable reservoir, for the external components of the capsule are such as to be Substance, that is sealable against leakage of the Substance; biocompatible for the residence time of the capsule within an actuator mechanism for opening the reservoir; an energy the body.” Source, operatively connected for powering the actuator mechanism; a releasable latch for controllably switching the 0794 U.S. Pat. No. 6,632.216 also discloses that “The application of power to the actuator from the energy source: capsule disclosed by Lambert etal suffers several disadvan and a receiver of electromagnetic radiation, for operating the tages. Principal amongst these is the complexity of the latch when the receiver detects radiation within a predeter device. This means that the capsule is expensive to manu mined characteristic range, the receiver including an air core facture. Also the complexity means that the capsule is prone having coiled therearound a wire; characterised in that the to malfunction. For example, the capsule disclosed by coiled wire lies on or is embedded in an outer wall of the Lambert et al includes a telemetry device that is initially device. retracted within a Smooth outer housing, to permit Swallow 0797. By way of yet further illustration, independent ing of the capsule via the oesophagus. Once the capsule claim 9 of U.S. Pat. No. 6,632,216 describes “9. An ingest reaches the stomach, gastric juice destroys a gelatin seal ible device for delivering a substance to a chosen or iden retaining the telemetry device within the housing. The tifiable location in the alimentary canal of a human or telemetry device then extends from the housing and presents animal, comprising an openable reservoir, for the Substance, a rotatable star wheel that engages the wall of the GI tract. that is sealable against leakage of the Substance; an actuator Rotations of the star wheel generate signals that are trans mechanism for opening the reservoir, an energy source, mitted externally of the capsule by means of an on-board RF operatively connected for powering the actuator mechanism: transmitter powered by a battery within the capsule housing. a releasable latch for controllably switching the application This arrangement may become unreliable when used in of power to the actuator from the energy source; and a mammals whose GI motility is poor or whose gastric juice receiver of electromagnetic radiation, for operating the latch composition is abnormal. There is a risk of malfunction of when the receiver detects radiation within a predetermined the rotating part of the telemetry device, and the method of characteristic range, the device including a ferrite core operation of the capsule is generally complex. The space having coiled therearound a wire for coupling received needed to house the telemetry device within the capsule electromagnetic radiation to the releasable latch, character during Swallowing/ingestion is unusable for any other pur ised in that the device comprises an elongate, hollow hous pose when the telemetry device is extended. Therefore the ing, the ferrite core being elongate with its longitudinal axis Lambert etal capsule is not space-efficient. This is a serious aligned with the longitudinal axis of the hollow housing.” drawback when considering the requirement for the capsule 0798. By way of yet further illustration, independent to be as Small as possible to aid ingestion.” claim 17 of U.S. Pat. No. 6,632,216 describes “17. A method 0795 U.S. Pat. No. 6,632,216 also discloses that “Also of operating an ingestible device for delivering a Substance the Lambert et al disclosure details the use of a high to a chosen or identifiable location in the alimentary canal of frequency (>100 MHz) radio transmitter for remotely trig a human or animal, causing a mammal to ingest an ingestible gering the release of the Substance from the capsule into the device comprising an openable reservoir, for the Substance, GI tract. The use of Such high frequencies is associated with that is sealable against leakage of the Substance; an actuator disadvantages, as follows: When power is transmitted to the mechanism for opening the reservoir, an energy source, capsule whilst it is inside the GI tract the energy must pass operatively connected for powering the actuator mechanism; through the tissue of the mammal that has swallowed the a releasable latch for controllably switching the application capsule. The transmission of this power through the body of of power to the actuator from the energy source; and a the mammal may result in possible interactions with the receiver of electromagnetic radiation, for operating the latch tissue which at Some power levels may lead to potential when the receiver detects radiation within a predetermined damage to that tissue. The higher the frequency of energy characteristic range; the receiver being capable of extracting transmission the higher the coupled power for a given field energy from an oscillating magnetic field and the method strength. However, as the frequency is increased the absorp comprising: at a chosen time, generating at least one axial, tion of the energy by the body tissue also increases. The oscillating magnetic field and directing the field at the guidelines for the exposure of humans to static and time abdomen of the mammal whereby the receiver intercepts the varying electromagnetic fields and radiation for the UK are said field and triggers the latch to cause opening of the given in the National Radiological Protection Board (NRPB) reservoir; and simultaneously inhibiting the generation of publication “Occupational Exposure to Electromagnetic long wave radio waves and short wave electrostatic radiation fields: Practical Application of NRPB Guidance” NRPB in the vicinity of the said abdomen.” R301. This describes two mechanisms of interaction: 0799. By way of yet further illustration, independent induced currents and direct heating measured in terms of the claim 54 of U.S. Pat. No. 6,632,216 describes “54. An US 2006/01 02871 A1 May 18, 2006 ingestible device for delivering a Substance to a chosen or shape being of a greater internal diameter than the outer identifiable location in the alimentary canal of a human or diameter of the second said cylinder-like shape and the first animal, comprising an openable reservoir, for the Substance, cylinder-like shape encircling the second cylinder.” that is sealable against leakage of the Substance; an actuator mechanism for opening the reservoir, an energy source, 0802. By way of yet further illustration, independent operatively connected for powering the actuator mechanism; claim 89 of U.S. Pat. No. 6,632,216 describes “89. An a releasable latch for controllably switching the application ingestible device for delivering a Substance to a chosen or of power to the actuator mechanism from the energy source: identifiable location in the alimentary canal of a human or a receiver of electromagnetic radiation, for operating the animal, comprising an openable reservoir, for the Substance, latch when the receiver detects radiation within a predeter that is sealable against leakage of the Substance; an actuator mined characteristic range; and a transmitter of electromag mechanism for opening the reservoir, an energy source, netic radiation for transmitting a signal indicative of opera operatively connected for powering the actuator mechanism; tion of the device, the said reservoir including an exit a releasable latch for controllably switching the application aperture, for the Substance, closed by a closure member that of power to the actuator from the energy source; and a is sealingly retained relative to the aperture, the exit aperture receiver of electromagnetic radiation, for operating the latch being openable on operation of the actuator mechanism; when the receiver detects radiation within a predetermined wherein: (i) the latch is thermally actuated; (ii) the energy characteristic range; the energy source including a com Source is held in a potential energy State until the latch pressed spring the expansion of which is initiatable by the operates; and (iii) the device includes a heater for heating the latch and the work of the expansion of which causes latch whereby, on the receiver detecting the said radiation operation of the actuator mechanism, characterised in that the receiver operates to power the heater and thereby release the spring comprises a stack of resiliently deformable discs, the latch, permitting expulsion of the Substance from the the periphery of each disc having formed therein a series of reservoir, characterised in that: the device also includes a waves, the waves of respective said discs connecting Such restraint operable to limit operation of the actuator mecha that the peak of each wave contacts the trough of a wave of nism; and in that, on release of the latch, the restraint an adjacent said disc.” operates a Switch to activate the transmitter for transmission 0803. By way of yet further illustration, independent of a said signal.” claim 100 of U.S. Pat. No. 6,632,216 describes “100. An 0800 By way of yet further illustration, independent ingestible device for delivering a Substance to a chosen or claim 64 of U.S. Pat. No. 6,632,216 describes “64. An identifiable location in the alimentary canal of a human or ingestible device for delivering a Substance to a chosen or animal, comprising: an openable reservoir, for the Substance, identifiable location in the alimentary canal of a human or that is sealable against leakage of the Substance; an actuator animal, comprising an openable reservoir, for the Substance, mechanism for opening the reservoir, an energy source, that is sealable against leakage of the Substance; an actuator operatively connected for powering the actuator mechanism; mechanism for opening the reservoir, an energy source, a releasable latch for controllably switching the application operatively connected for powering the actuator mechanism; of power to the actuator from the energy source: a receiver a releasable latch for controllably switching the application of electromagnetic radiation, for operating the latch when of power to the actuator from the energy source; and a the receiver detects radiation within a predetermined char receiver of electromagnetic radiation, for operating the latch acteristic range; and a transmitter of electromagnetic radia when the receiver detects radiation within a predetermined tion for transmitting a signal indicative of operation of the characteristic range; the energy source including a com device; the said reservoir including an exit aperture, for the pressed spring capable of acting on the actuator mechanism Substance, closed by a closure member that is sealingly the expansion of which is initiatable by the latch and the retained relative to the aperture, the exit aperture being work of the expansion of which causes operation of the openable on operation of the actuator mechanism; wherein actuator mechanism, characterised in that the spring, in its (i) the latch is thermally actuated; (ii) the energy source is uncompressed state, has a minimum helical angle of 15°.” held in a potential energy state by the latch until the latch operates; and (iii) the device includes a heater for heating the 0801 By way of yet further illustration, independent latch whereby, on the receiver-detecting the said radiation claim 76 of U.S. Pat. No. 6,632,216 describes “76. An ingestible device for delivering a Substance to a chosen or the receiver operates to power the heater and thereby release identifiable location in the alimentary canal of a human or the latch, permitting expulsion of the Substance from the animal, comprising an openable reservoir, for the Substance, reservoir; characterised in that the device also includes (a) a that is sealable against leakage of the Substance; an actuator restraint operable to limit operation of the actuator mecha mechanism for opening the reservoir, an energy source, nism; (b) a Switch for Switchably operating the transmitter; operatively connected for powering the actuator mechanism; and (c) a Switch member operatively interconnecting the a releasable latch for controllably switching the application actuator mechanism and the Switch Such that operation of of power to the actuator from the energy source; and a the actuator mechanism causes the Switch member to oper receiver of electromagnetic radiation, for operating the latch ate the said Switch.” when the receiver detects radiation within a predetermined 0804. By way of yet further illustration, independent characteristic range; the energy source including a com claim 110 of U.S. Pat. No. 6,632,216 describes “110. A pressed spring capable of acting on the actuator mechanism method of operating an ingestible device for delivering a the expansion of which is initiatable by the latch and the Substance to a chosen or identifiable location in the alimen work of the expansion of which causes operation of the tary canal of a human or animal, the device including an actuator mechanism, characterised in that the spring openable reservoir, for the Substance, that is sealable against includes a pair of wires each coiled in loops to define a pair leakage of the Substance; an actuator mechanism for opening of hollow cylinder-like shapes, a first said cylinder-like the reservoir; an energy source that is operatively connected US 2006/01 02871 A1 May 18, 2006 69 for powering the actuator mechanism; a releasable latch for tromagnetic radiation, for operating the latch when the controllably Switching the application of power to the actua receiver detects radiation within a predetermined character tor mechanism from the energy source; a receiver of elec istic range; and a transmitter of electromagnetic radiation for tromagnetic radiation, for operating the latch when the transmitting a signal indicative of operation of the device, receiver detects radiation within a predetermined character the said reservoir including an exit aperture, for the Sub istic range; and a transmitter of electromagnetic radiation for stance, that is initially closed by a closure member that is transmitting a signal indicative of operation of the device, sealingly retained relative to the aperture, the exit aperture the said reservoir including an exit aperture, for the Sub being openable on operation of the actuator mechanism, the stance, that is initially closed by a closure member that is method comprising the steps of charging the reservoir with sealingly retained relative to the aperture, the exit aperture a said Substance; setting the latch; causing ingestion of the being openable on operation of the actuator mechanism, the device by a human or animal; and causing the receiver to method comprising the steps of charging the reservoir with detect electromagnetic radiation in the predetermined char a said Substance; setting the latch; causing ingestion of the acteristic range, thereby causing expulsion of the Substance device by a human or animal; and causing the receiver to from the reservoir via the exit aperture, the method including detect electromagnetic radiation in the predetermined char the steps of causing expansion from an initial, compressed acteristic range, thereby causing expulsion of the Substance state a spring, that defines the said energy source, including from the reservoir via the exit aperture, the method including a stack of resiliently deformable discs, the periphery of each the steps of causing expansion from an initial, compressed disc having formed therein a series of waves, the waves of state a helical spring defining the said energy source and respective said discs connecting such that the peak of each having, in its uncompressed State, a minimum helical angle wave contacts the trough of a wave of an adjacent said disc.” of 15.O. 0807 As will be apparent to those skilled in the art, the 0805. By way of yet further illustration, independent substance to be delivered by the processes and/or devices of claim 115 of U.S. Pat. No. 6,632,216 describes “115. A U.S. Pat. No. 6,632.216 may be one or more of the nan method of operating an ingestible device for delivering a composite materials described in, e.g., the claims of the Substance to a chosen or identifiable location in the alimen instant application. tary canal of a human or animal, the device including an openable reservoir, for the Substance, that is sealable against A Composition Comprised of Magnetic Material and Poly leakage of the Substance; an actuator mechanism for opening meric Material the reservoir; an energy source that is operatively connected 0808. As is disclosed elsewhere in this specification, one for powering the actuator mechanism; a releasable latch for may prepare a composition comprised of both the nanomag controllably Switching the application of power to the actua netic material of this invention and polymeric material. tor mechanism from the energy source: a receiver of elec tromagnetic radiation, for operating the latch when the 0809. The term polymer, as used herein, refers to a receiver detects radiation within a predetermined character member of a series of polymeric compounds that are com istic range; and a transmitter of electromagnetic radiation for posed of very/large molecules which consist essentially of transmitting a signal indicative of operation of the device, recurring, long-chain structural units; these structural units the said reservoir including an exit aperture, for the Sub distinguish polymers from other types of organic molecules stance, that is initially closed by a closure member that is and confer on them tensile strength, deformability, sealingly retained relative to the aperture, the exit aperture being openable on operation of the actuator mechanism, the elasticity, and hardness. See, e.g., page 534 of Julius Grants method comprising the steps of charging the reservoir with “Hackh's Chemical Dictionary. Fourth Edition (McGraw a said Substance; setting the latch; causing ingestion of the Hill Book Company, New York, N.Y., 1972). device by a human or animal; and causing the receiver to 0810. In one embodiment, the composition of this inven detect electromagnetic radiation in the predetermined char tion is comprised of Such nanomagnetic material. Such acteristic range, thereby causing expulsion of the Substance polymeric material, and one or more of the mineral materials from the reservoir via the exit aperture, the method including described hereinabove. In the remainder of this section of the steps of causing expansion from an initial, compressed the specification, various polymeric materials that may be state a spring, that defines the said energy source, including used in Such "magnetic mineral composition' will be a pair of wires each coiled in loops to define a pair of described by way of illustration and not limitation. cylinder-like shapes, a first said cylinder-like shape being of a greater internal diameter than the outer diameter of the 0811. The polymeric material used in the magnetic min second said cylinder-like shape and the first cylinder-like eral composition of the instant invention may be comprised shape encircling the second cylinder.” of one or more resins such as, e.g., the phenol-formaldehyde resin disclosed in U.S. Pat. No. 3,467,618, the entire dis 0806 By way of yet further illustration, independent closure of which is hereby incorporated by reference into claim 116 of U.S. Pat. No. 6,632,216 describes “116. A this specification. This patent claims (in claim 1) a molded method of operating an ingestible device for delivering a article comprised of a cured phenol-formaldehyde resin and Substance to a chosen or identifiable location in the alimen about 10 to 75 weight percent of halloysite clay.” tary canal of a human or animal, the device including an openable reservoir, for the Substance, that is sealable against 0812. The polymeric material used in the magnetic min leakage of the Substance; an actuator mechanism for opening eral composition of the instant invention may be a polya the reservoir, an energy source that is operatively connected mide-containing resin, Such as the polyamide material for powering the actuator mechanism; a releasable latch for described in U.S. Pat. No. 4,894,411, the entire disclosure of controllably Switching the application of power to the actua which is hereby incorporated by reference into this specifi tor mechanism from the energy source: a receiver of elec cation. This polyamide resin is described in column 1 of US 2006/01 02871 A1 May 18, 2006 70 such patent, wherein it is disclosed that “Various attempts impact resistance improving materials comprising olefin have been made So far to incorporate an organic polymeric copolymers containing 0.01 to 10 mole % of acid groups; material with an inorganic material Such as calcium carbon and mpact resistance improving materials comprising block ate, clay mineral, and mica for the improvement of its copolymers, containing 0.01 to 10 mole % of acid groups, mechanical properties. As the result of Such attempts, the obtained from vinyl aromatic compounds and conjugated present inventors developed a composite material composed diene compounds, hydrogenated products of said block of a resin containing a polyamide and a layered silicate copolymers or mixtures thereof, wherein there are 5 to 70 having a layer thickness of 7-12 ANG. uniformly dispersed parts by weight (c) per 100 parts by weight of (A).” therein, with the polymer chain of said polyamide being partly connected to said silicate through ionic bond. (See 0815. The polymeric material used in the magnetic min Japanese Patent Laid-open No. 74957/1987 (which corre eral composition of this invention may be a polyimide Such sponds to U.S. Pat. No. 4,739,007).) This composite material as, e.g., the polyimide disclosed in U.S. Pat. No. 6,164,660, has a high elastic modulus and heat resistance because of its the entire disclosure of which is hereby incorporated by unique structure; that is, silicate having an extremely high reference into this specification. Claim 1 of this patent aspect ratio are uniformly dispersed in and connected to a describes “1. A polyimide composite material which com polyamide resin through ionic bond. This composite mate prises a polyimide-containing resin, organic monoonium rial, however, is subject to brittle fracture even at room ions and a layered clay mineral, said layered clay mineral temperature under a comparatively small load. Therefore, it being intercalated with the organic monoonium ions not is not necessarily satisfactory in mechanical strength.” bonding with said polyimide and uniformly dispersed in said polyimide.” The preparation of the polyimide material of 0813 U.S. Pat. No. 4,894,411 also discloses that “In the this patent is described, e.g., in column 4 of Such patent, meantime, the crystalline polyamide resin as a typical engi wherein it is disclosed that “The polyimide in the present neering plastics exemplified by nylon-6 and nylon-66 finds invention is produced from any dianhydride and diamine use as automotive parts and electric and electronic parts on which are known as monomers for polyimide. Examples of account of its high melting point and high rigidity. A the dianhydride include pyromellitic dianhydride, 3,3', 4,4'- disadvantage of the crystalline polyamide resin is that it is biphenyltetracarboxylic dianhydride, and 3,3', 4,4'-ben opaque on account of its crystalline structure. This leads to Zophenonetetracarboxylic dianhydride. Examples of the a problem arising from the fact that automotive parts such as diamine include 4,4'-diaminodiphenyl ether, 3,4'-diamino reservoir tanks, radiator tanks, and fuel tanks made of diphenyl ether, and p-phenylenediamine. They may be used polyamide resin make the liquid level invisible from outside alone for homopolymerization or in combination with one and the electronic parts such as connectors made of polya another for copolymerization. They may be copolymerized mide resin prevent the detection of conductor breakage with a dicarboxylic acid and a diol or their respective therein. Unlike the crystalline polyamide resin, the amor derivatives to give polyamideimide, polyesteramideimide, phous polyamide resin having the aromatic skeleton struc or polyesterimide.” ture is transparent. An example of the amorphous polyamide resin is “Trogamid’ made by Dynamit Nobel Co., Ltd. 0816 U.S. Pat. No. 5,164,460 also discloses that “The Unfortunately, it is extremely expensive and cannot be a polyimide in the present invention is also produced from a Substitute for aliphatic nylons such as nylon-6 and nylon-66. prepolymer which is exemplified by poly(amic acid). Usu Moreover, the aliphatic nylon extremely decreases in ally, a polyimide resin cannot be mixed in its molten state strength and heat resistance when it is made amorphous. with the intercalated clay mineral because it decomposes at Under these circumstances, there has been a demand for a a temperature lower than the temperature at which it begins polyamide resin which has high clarity without decrease in to flow. But, if the temperature of fluidization is lower than crystallinity.” that of decomposition, the polyimide composite material can 0814) Another polyamide resin that may be used as the be produced by this melt-mixing method.” polymeric material in the magnetic mineral composition of 0817 The polymeric material used in the magnetic min this invention is desribed in U.S. Pat. No. 5,164,440, the eral composition of this invention may be a polypropylene entire disclosure of which is hereby incorporated by refer material Such as, e.g., the polypropylene thermoplastic resin ence into this specification. This patent claims “1. A polya composition disclosed in U.S. Pat. No. 5,206,284, the entire mide resin composition comprising (A) at least one polya disclosure of which is hereby incorporated by reference into mide resin component selected from the group consisting of this specification. Claim 1 of this patent describes “1. A a polyamide resin and a resin composition comprising (i) at polypropylene thermoplastic resin composition comprising: least 80 weight% of a polyamide resin and (ii) the remainder being another thermoplastic resin selected from the group 0818 95-5% by weight of (a) a modified polypropylene consisting of polypropylene, an ABS resin, polycarbonate, obtained by grafting a crystalline polypropylene with 0.05 to polyethyleneterephthalate and polybutyleneterephthalate: 5% by weight of at least one compound selected from the (B) a layered silicate having a thickness of 6 to 20. ANG., a group consisting of an unsaturated carboxylic acid, an length of one side of 0.002 to 1 Lum and being uniformly unsaturated carboxylic acid anhydride, an unsaturated car dispersed in the component (A) with a weight ratio of 0.05 boxylic ester, an unsaturated carboxylate salt and an unsat to 30 parts by weight of (B) per 100 parts by weight of (A): urated carboxylic acid amide, or a crystalline polypropylene and respective layers of silicate being positioned apart from comprising at least 5% by weight of said modified polypro each other by 20. ANG. or more on an average; and (C) an pylene, and 5-95% by weight of (b) a modified polyamide impact resistance improving material selected from the obtained by partially or wholly modifying a polyamide with group consisting of impact resistance improving materials 0.05 to 10% by weight of a clay mineral.” A discussion of comprising copolymers obtained from ethylene, unsaturated crystalline polypropylenes is presented at column 1 of Such carboxylic acid and unsaturated carboxylic acid metal salt; patent, wherein it is disclosed that “Crystalline polypropy US 2006/01 02871 A1 May 18, 2006 lenes are Superior in mechanical properties and moldability weight of the layer of polyethylene terephthalate, each of the and used in wide applications, but are not satisfactory in heat plurality of Smectite particles having a thickness of between resistance and impact resistance when used in industrial 9 Angstroms and 100 nanometers, and an aspect ratio of parts. It has conventionally been conducted to add an between 100 and 2000, the layer of polyethylene terephtha inorganic filler to a crystalline polypropylene to improve the late having a thickness range of approximately 100 microns heat resistance of the latter, or to add an ethylene-alpha.- to approximately 2000 microns. Reference may also be had olefin copolymer rubber or a polyethylene to a crystalline to related U.S. Pat. No. 5,972,448, the entire disclosure of polypropylene to improve the impact resistance of the latter; which is hereby incorporated by reference into this specifi however, the addition of an inorganic filler significantly cation. reduces the impact resistance of polypropylene and the addition of an ethylene-alpha.-olefin copolymer rubber of a 0822. The polymeric material used in the magnetic min polyethylene reduces the rigidity, heat resistance and oil eral composition of this invention may be a melt processable resistance of polypropylene. Even the combined addition of polymer, as that term is defined in U.S. Pat. No. 5,962.53, an inorganic filler and an ethylene-alpha.-olefin copolymer the entire disclosure of which is hereby incorporated by rubber or a polyethylene to a polypropylene does not give an reference into this specification. Claim 1 of U.S. Pat. No. 5.962.553 describes “1. A method of making a composite, effect more than the sum of addition effects of respective comprising the steps of: (a) providing 100 parts by weight of additives, and accordingly provides no sufficient method for melt processable polymer which is a fluoroplastic selected improvement of polypropylene in heat resistance and impact from the group consisting of ethylene-tetrafluoroethylene resistance.” copolymer, perfluorinated ethylene-propylene copolymer, 08.19 U.S. Pat. No. 5,206.284 also discloses that “Mean and tetrafluoroethylene-perfluoro(propyl vinyl ether) while, there was made an attempt of adding a polyamide to copolymer; (b) providing between 1 and 80 parts by weight a polypropylene to improve the heat resistance, oil resis of a modified layered clay, the modified layered clay being tance, etc. of polypropylene without reducing the impact a layered clay having negatively charged layers and modi resistance or polypropylene. However, since there is no fied so as to have organophosphonium cations intercalated compatibility between polypropylene and polyamide, they between the negatively charged layers, the organophospho cause delamination and no desired material can be obtained nium cations having the structure R1 P+(R2)3 wherein R1 is when they are melt mixed as they are. Hence, there was a C8 to C24 alkyl or arylalkyl group and each R2, which used, in place of a polypropylene, a modified polypropylene may be the same or different, is an aryl, arylalkyl, or a C1 obtained by grafting a polypropylene with an unsaturated to C6 alkyl group; and (c) melt-blending together the melt carboxylic acid or a derivative of an unsaturated carboxylic processable polymer and the modified layered clay to form acid (Japanese Patent Publication No. 30945/1970). This the composite.” approach makes a polypropylene and a polyamide to be compatible with each other and can improve the heat resis 0823. Some of the “melt processable polymers’ that may tance of polypropylene without reducing the impact resis be used in the process of U.S. Pat. No. 5,962,553 are tance of polypropylene.” described at columns 4-5 of such patent, wherein it is disclosed that "Suitable melt processable polymers prefer 0820 U.S. Pat. No. 5,206,284 also discloses that “How ably have a melt processing temperature of at least about ever, even in the above improvement of polypropylene by 250° C., preferably at least about 270° C. Typically, a melt addition of polyamide, the improvement effect is not satis processable polymer is melt processed at a temperature factory as long as there is used, as the polyamide, an which is at least about 20 to 30° C. above a relevant ordinary polyamide Such as nylon-6, nylon-6.6, nylon-112 transition temperature, which can be either a Tm or a Tg, in or the like. Recently there has been made a proposal of order to attain complete melting (or softening) of the poly adding araromatic polyamide and a glass fiber to a polypro mer and to lower its viscosity. Further, even if a polymer is pylene to obtain a material of high strength and low water nominally melt-processed at a temperature Such as 240°C., absorbability Japanese Patent Application Kokai (Laid shear heating can increase the actual localized temperature Open) No. 203654/1985). This proposal is not sufficient experienced by the modified layered clay to rise above 250° when viewed from the improvement of polypropylene in C. for extended periods. Thus, a melt processable polymer both heat resistance and impact resistance. In order to having a melt processing temperature of at least about 250 significantly improve the heat resistance and impact resis C. will have a Tm or Tg of at least about 220° C. tance of polypropylene by addition of polyamide thereto, the dispersibility of polyamide particles in polypropylene and 0824 U.S. Pat. No. 5,962,553 also discloses that “One the cohesiveness among polyamide particles are very impor class of melt processable polymers which can be used are tant. The improvement of polyamide particles in these crystalline thermoplastics having a crystalline melting tem properties has been necessary.” perature (Tm) of at least about 220° C., preferably at least about 250° C., and most preferably at least about 270° C. Tm 0821. The polymeric material used in the magnetic min may be measured by the procedure of ASTM standard eral composition of this invention may be a polyester, Such E794-85 (Reapproved 1989). For the purposes of this speci as poly(ethylene terephthalate), as is disclosed in U.S. Pat. fication, Tm is the melting peak Tm as defined at page 541 No. 5,876,812, the entire disclosure of which is hereby of the standard. Either a differential scanning calorimeter incorporated by reference into this specification. Claim 1 of (DSC) or a differential thermal analyzer (DTA) may be used, Such patent describes “1. A transparent container for a as permitted under the standard, the two techniques yielding flowable food product having a decreased permeability for gases, the transparent container consisting essentially of a similar results.” layer of polyethylene terephthalate integrated with a plural 0825 U.S. Pat. No. 5,962,553 also discloses that ity of synthetic smectite particles between 0.1% and 10% “Another class of melt processable polymers which can be US 2006/01 02871 A1 May 18, 2006 72 used are amorphous polymers having a glass transition third monomer, where present, is typically present in an temperature (Tg) of at least about 220°C., preferably at least amount of 5% or less by weight of the polymer and may be, about 250° C., and most preferably at least about 270° C. Tg for example, perfluoro(methyl vinyl ether), perfluoro(ethyl may be measured according to ASTM E 1356-91 (Reap vinyl ether), perfluoro(butyl vinyl ether), or any other suit proved 1995), again using either DSC or DTA.” able monomer. A representative PFA has about 90 to 99 0826 U.S. Pat. No. 5,962,553 also discloses that “Turn (preferably 96 to 98) weight % tetrafluoroethylene derived ing now to specific types of melt processable polymers repeat units and about 1 to 10 (preferably 2 to 4) weight % which can be used, these include fluoroplastics, poly(phe perfluoro(propyl vinyl ether) derived repeat units. A repre nylene ether ketones), aliphatic polyketones, polyesters, sentative crystalline melting point is about 302 to 305° C. poly(phenylene sulfides) (PPS), poly(phenylene ether sul PFA is available from E.I. du Pont de Nemours under the fones) (PES), poly(ether imides), poly(imides), polycarbon tradename Teflon PFA. ate, and the like. Fluoroplastics are preferred. The organo 0831 U.S. Pat. No. 5,962.553 also discloses that “Suit phosphonium modified clays of this invention can also be able poly(phenylene ether ketones) are disclosed in Dahl, used to make nanocomposites with polymers having lower U.S. Pat. No. 3,953,400 (1976); Dahl et al., U.S. Pat. No. melting temperatures, such as aliphatic polyamides (nylons), 3,956,240 (1976); Dahl, U.S. Pat. No. 4,111,908 (1978); but since the conventional quaternary ammonium salts can Rose et al., U.S. Pat. No. 4,320,224 (1982); and Jansons et also be used, no special advantage is obtained in Such al., U.S. Pat. No. 4,709,007 (1987); the disclosures of which instance.” are incorporated herein by reference. Typically, they have 0827 U.S. Pat. No. 5,962,553 also discloses that “A Tms in excess of 300° C. Exemplary poly(phenylene ether preferred fluoroplastic is ethylene-tetrafluoroethylene ketones) comprise one or more of the following repeat units: copolymer, by which is meant a crystalline copolymer of Figure ethylene, tetrafluoroethylene and optionally additional 0832 U.S. Pat. No. 5,962.553 also discloses that “Suit monomers. Ethylene-tetrafluoroethylene copolymer is also able aliphatic polyketones have a repeat unit Figure alone known as ETFE or poly(ethylene-tetrafluoroethylene), and or in combination with a repeat unit Figure An exemplary herein the acronym ETFE may be used synonymously for disclosure of Such aliphatic polyketones is found in convenience. The mole ratio of ethylene to tetrafluoroeth Machado et al., ANTEC’95, pp. 2335-2339 (1995), the ylene can be about 35-60:65-40. A third monomer may be disclosure of which is incorporated herein by reference. present in an amount Such that the mole ratio of ethylene to Aliphatic polyketones are believed to be crystalline with tetrafluoroethylene to third monomer is about 40-60:15 Tms of 220° C. or above.’ 50:0-35. Preferably the third monomer, if present, is so in an amount of about 5 to about 30 mole %. The third monomer 0833 U.S. Pat. No. 5,962,553 also discloses that “A may be, e.g., hexafluoropropylene; 3,3,3-trifluoropropylene suitable polyester is poly(ethylene terephthalate) (PET), 1; 2-trifluoromethyl-3,3,3-trifluoropropylene-1; or perfluo having the repeat unit Figure PET is available commer ro(alkyl vinyl ether). The melting point varies depending on cially from a variety of suppliers. It is believed to be the mole ratio of ethylene and tetrafluoroethylene and the crystalline, with a Tm in the range of about 250 to about presence or not of a third monomer. Commercially available 265O C. ETFE's have melting points between 220 and 270° C., with 0834 U.S. Pat. No. 5,962,553 also discloses that “A the grades having melting points above 250° C. being most suitable poly(phenylene sulfide) has the repeat unit Figure appropriate for this invention.” It has a Tm of about 285° C. and is available under the 0828 U.S. Pat. No. 5,962,553 also discloses that “ETFE tradename Ryton from Phillips.” for use in this invention is available from various Suppliers, 0835 U.S. Pat. No. 5,962.553 also discloses that “Suit including from E.I. du Pont de Nemours under the trade able poly(phenylene ether sulfones) have the repeat units name Tefzel (e.g., grades 280, 2181 and 2129) and from such as Figure or Figure Daikin Industries under the tradename Neoflon (e.g., grades 0836 U.S. Pat. No. 5,962.553 also discloses that “Suit 540, 610 and 620).” able poly(ether imides) are disclosed in Wirth et al., U.S. 0829 U.S. Pat. No. 5,962,553 also discloses that Pat. No. 3,838,097 (1974); Heath et al., U.S. Pat. No. “Another fluoroplastic suitable for use in this invention is 3,847,867 (1974); and Williams, III et al., U.S. Pat. No. perfluorinated ethylenepropylene copolymer (also known as 4,107,147 (1978); the disclosures of which are incorporated FEP), by which is meant a copolymer of tetrafluoroethylene herein by reference. Poly(ether imide) is available under the (TFE), hexafluoropropylene (HFP), and optionally addi tradename Ultem from General Electric. A preferred poly tional monomers. Preferably, FEP is predominantly random (ether imide) has the repeat unit: Figure and has a relatively low HFP content, between about 1 and about 15 weight % based on the total weight of TFE and 0837 U.S. Pat. No. 5,962,553 also discloses that “A HFP. Preferably the molecular weight is between about Suitable polyimide is a thermoplastic Supplied under the 100,000 and about 600,000. A preferred FEP is available tradename Aurum by Mitsui Toatsu Chemical, Inc. It has a from E.I. du Pont de Nemours under the trade name Teflon Tg of about 250° C. and a Tm of about 388° C.” FEP. The melting point of FEP is about 260° C.” 0838 U.S. Pat. No. 5,962,553 also discloses that “A 0830 U.S. Pat. No. 5,962,553 also discloses that “Yet suitable polycarbonate has the repeat unit Figure and is another suitable fluoroplastic is tetrafluoroethylene-perfluo available from General Electric Company.” ro(propyl vinyl ether) copolymer (also known as PFA), by 0839. The polymeric material used in the magnetic min which is meant a copolymer of tetrafluoroethylene, perfluo eral composition of this invention may be a mixture of two ro(propyl vinyl ether), and optionally a third monomer. The or more polymers such as, e.g., the mixture disclosed in U.S. US 2006/01 02871 A1 May 18, 2006

Pat. No. 6,117,932, the entire disclosure of which is hereby peratures below a softening or melting point. In addition, incorporated by reference into this specification. Claim 1 of major difficulties have been encountered in attempts to this patent describes “1. A resin composite comprising, an dissolve the high molecular weight polymer.” organophilic clay and a polymer, wherein said polymer 0843 U.S. Pat. No. 6,136,909 also discloses that “One comprises: component (a) two or more polymers, at least known method to improve the processibility of polyaniline one of which is poly(phenylene oxide), or component (b) a is by employing a protonic acid dopant containing a long copolymer comprising at least one oxazoline functional chain Sulfonic group in the polymerization of aniline to form group.” an emulsified colloidal dispersion. However, this method 0840 The polymeric material used in the magnetic min requires a large quantity of long-chain dopants, which eral composition of this invention may be a polymerized decrease the conductivity and mechanical properties of aminoaryl lactam monomer, as is described in U.S. Pat. No. polyaniline. In addition, high aspect ratios of polyaniline are 6,136,908, the entire disclosure of which is hereby incor unavailable through this method. In conventional guest-host porated by reference into this specification. Claim 1 of this methods for preparing polyaniline/layered inorganic com patent describes “1. A method for producing a thermoplastic posites, aniline monomers are interposed between layered nanocomposite, comprising the steps of contacting a hosts, and then Subjected to oxidative polymerization to swellable layered silicate with a polymerizable N-aminoaryl form composites with highly ordered polymer matrices. The Substituted lactam monomer to achieve intercalation of said polyaniline composite thus obtained, however, commonly lactam monomer between adjacent layers of said layered has a conductivity lower than 10-2 S/cm. Moreover, they do silicate; and “admixing the intercalated layered silicate with not give nanoscale structures. The interlayer spacing a thermoplastic polymer, and heating the admixture to (d-spacing) of the inorganic layers is less than 15. Ang provide for flow of said polymer and polymerization of the stroms. intercalated lactam monomer to cause exfoliation of the 0844. The polymeric material used in the magnetic min layered silicate, thereby forming a thermoplastic nanocom eral composition of this invention may be a benzoaxazine posite having exfoliated silicate layers dispersed in a ther polymer as described, e.g., in claim 1 of U.S. Pat. No. moplastic polymer matrix. The lactam monomer used in 6,323,270, the entire disclosure of which is hereby incor Such process is described in column 2 of the patent as being porated by reference into this specification. Claim 1 of this “. . . an N-aminoaryl Substituted lactam monomer, which patent describes “1. A nanocomposite composition compris can be prepared via a one-step synthesis by coupling an ing clay and a benzoxazine monomer, oligomer, and/or aromatic amino acid with a lactam having a cyclic ring polymer in amount effective to form nanocomposite. “The system containing 1 to 12 carbonatoms. Illustrative example preparation of these polymers is described in column 5 of the of Such aminoaryl lactams are N-(p-aminobenzoyl)capro patent, wherein it is disclosed that “Benzoxazines are pre lactam, N-(p-aminobenzoyl)butyrolactam, N-(p-aminoben pared by reacting a phenolic compound with an aldehyde Zoyl)Valerolactam, and N-(p-aminobenzoyl)dodecanelac and an amine, desirably an aromatic amine. The conven tam.' tional phenolic reactants for benzoxazines include, for 0841. The polymeric material used in the magnetic min instance, mono and polyphenolic compounds having one or eral composition may be a conducting polymer, as that term more phenolic groups of the formula Figure in which R1 is described in U.S. Pat. No. 6,136,909, the entire disclosure through R5 can independently be H; OH: halogen; linear or of which is hereby incorporated by reference into this branched aliphatic groups having from 1 to 10 carbon atoms; specification. Claim 1 of this patent describes a process for mono, di, or polyvalent aromatic groups having from 6 to 12 preparing a conductive polymeric nanocomposite, disclos carbon atoms; or a combination of said aliphatic groups and ing “1. A method for producing a conductive polymeric said aromatic groups having from 7 to 12 carbon atoms; nanocomposite, comprising the steps of: (a) forming a mono and divalent phosphine groups having up to 6 carbon reaction mixture comprising water, an aniline monomer, a atoms; or mono, di and polyvalent amines having up to 6 protonic acid, an oxidizing agent, and a layered silicate carbon atoms. In one embodiment, at least one of the ortho which has been subjected to an acid treatment or is inter positions to the OH is unsubstituted, i.e. at least one of R1 calated with polyethylene glycol; and (b) Subjecting said to R5 is hydrogen. In polyphenolic compounds, one or more reaction mixture to oxidative polymerization to form a of the R1 through R5 can be an oxygen, an alkylene Such as conducive polymeric nanocomposite having said layered methylene or other hydrocarbon connecting molecule, etc. silicate dispersed in a polymeric matrix of polyaniline, Further nonhydrogen and nonhalogen R1 through R5 groups as described above less one or more hydrogens or a P=O wherein said nanocomposite has a conductivity of greater can serve to connect two or more phenolic groups creating than 10 S/cm.” a polyphenolic compound which can be the phenolic com 0842) Conducting polymers are discussed in column 1 of pound. Example of mono-functional phenols include phe U.S. Pat. No. 6,136,909, wherein it is disclosed that “In the nol; cresol; 2-bromo-4-methylphenol; 2-allyphenol; 1,4- past decade, conducting polymers have been used in many aminophenol; and the like. Examples of difunctional fields, such as batteries, displays, optics, EMI shielding, phenols (polyphenolic compounds) include phenol LEDs, sensors, and the aeronautical industry. High molecu phthalane; biphenol: 4-4'-methylene-di-phenol: 4-4'-dihy lar weight polyaniline has emerged as one of the more droxybenzophenone; bisphenol-A; 1,8-dihydroxyan promising conducting polymers because of its excellent thraquinone; 1,6-dihydroxnaphthalene; 2,2'- chemical stability combined with respectable levels of elec dihydroxyazobenzene: resorcinol; fluorene bisphenol; and trical conductivity of the doped or protonated material. the like. Examples of trifunctional phenols comprise 1,3,5- Processing of polyaniline high polymers into useful objects trihydroxybenzene and the like. Polyvinyl phenol is also a and devices, however, has been problematic. Melt process Suitable component for the benzoxazine compounds that ing is not possible, since the polymer decomposes at tem constitute the subject of the invention.” US 2006/01 02871 A1 May 18, 2006 74

0845 The polymeric material used in the magnetic min product is powdery interlayer compound which cannot be eral composition may be a polyphenylene ether resin as is used as moldings. In addition, it is also preferable that the disclosed, e.g., in U.S. Pat. No. 6,350,804, the entire dis composite material of this invention be such that the inter closure of which is hereby incorporated by reference into layer distance is at least 30 Angstroms. The greater the this specification. Claim 1 of this patent describes “1. A interlayer distance is, the better the mechanical strength will composition comprising: about 30 to about 70 parts by be.’ weight of a polyphenylene ether resin; about 20 to about 60 parts by weight of an alkenylaromatic compound, wherein 0850 U.S. Pat. No. 6,410,142 also discloses that “Next, the alkenylaromatic compound is a high impact polystyrene; the process for manufacturing composite material of this invention is described below. The first step is to bring a and about 1 to about 10 parts by weight of an organoclay; cation-type surfactant into contact with a clay material wherein the parts by weight of the polyphenylene ether, the having a cation-exchange capacity of about 50 to 200 alkenylaromatic compound, and the organoclay Sum to med/100 g, thereby adsorbing the Surfactant on the clay 100. material. This can be accomplished by immersing the clay 0846. The polymeric material used in the magnetic min material in an aqueous solution containing the Surfactant, eral composition may be a syndiotactic polystyrene, as that followed by washing the treated clay material with water to term is defined in the claims of U.S. Pat. No. 6,410,142, the remove excess ions, thereby effecting ion-exchange opera entire disclosure of which is hereby incorporated by refer tion. ence into this specification. Claim 1 of this patent describes 0851 U.S. Pat. No. 6.410,142 also discloses that “The “A syndiotactic polystyrenefclay nanocomposite compris clay material used in this invention can be any clay material ing: a polymer matrix comprising syndiotactic polystyrene (both natural and synthesized) having a cation exchange (sPS); and a layered clay material uniformly dispersed in the capacity of about 50 to 200 meq/100 g. Typical examples polymer matrix, said layered clay material being intercalated include Smectite clays (e.g., montmorillonite, Saponite, beid with an organic onium cation, and the interlayer distances of ellite, nontronite, hectorite, and Stevensite), Vermiculite, said layered clay material being at least 20 angstroms. The halloysite, sericite, and mica. With a clay material whose nanocomposite described in Such claim 1 is further cation-exchange capacity exceeds 200 meg/100 g, its inter described at columns 2-3 of U.S. Pat. No. 6,410,142, layer bonding force is too strong to give intended composite wherein it is disclosed that “The spS/clay nanocomposite of materials of this invention. If the capacity is less than 50 this invention comprises a polymer matrix containing Syn med/100g, on the other hand, ion exchange or adsorption of diotactic polystyrene (sPS), and a layered clay material surfactant will not be sufficient, making it difficult to pro uniformly dispersed in the polymer matrix, said layered clay duce composite materials as intended by this invention.” material being intercalated with an organic onium cation, and the interlayer distances of said layered clay material 0852 U.S. Pat. No. 6.410,142 also discloses that “The being at least 20. ANG. Optionally, the layered clay material cation-type surfactant serves to expand the interlayer dis may be intercalated with a polymer or oligomer which is tance in a clay material, thus facilitating the formation of compatible or partially compatible with spS. The amount of polymer between the silicate layers. The surfactants used in the optionally intercalated polymer or oligomer is preferably the present invention are organic compounds containing in the range from 0.5 to 50 parts by weight per 100 parts by onium ions which-are capable of forming a firm chemical weight of the clay material.” bond with silicates through ion-exchange reaction. Particu larly preferred Surfactants are ammonium salts containing at 0847 U.S. Pat. No. 6,410,142 also discloses that “The least 12 carbon atoms, such as n-hexadecyl trimethylammo polymer matrix in the composite material of this invention nium bromide and cetyl pyridinium chloride.” is a resin containing spS, namely, a spS or a mixture thereof with other polymers. The molecular weight of the spS to be 0853 U.S. Pat. No. 6,410,142 also discloses that used in the present invention is not specifically limited, but “Optionally, the surface modified clay material may be is preferably within the range from about of 15,000 to intercalated with a polymer or oligomer, which is compat 800,000 in terms of weight-average molecular weight ible or partially compatible with spS, as a subsequent (Mw).” modification. For example, this can be accomplished by admixing the modified clay material with a styrene mono 0848 U.S. Pat. No. 6,410,142 also discloses that “The mer or 2,6-Xylenol monomer, and polymerizing the mono layers of clay material in the composite material of this mer to obtain atactic polystyrene (apS) or poly(2,6-dim invention, which are intended to impart the polymeric mate ethyl-1,4-phenylenen oxide) (PPO) intercalated in the rial with high mechanical strength, have a thickness of about modified clay material, respectively.” 7 to 12 Angstroms. Also, it has been found that the nano dispersed clay material unexpectedly increases the crystal 0854 U.S. Pat. No. 6.410,142 also discloses that “The lization rate and crystallization temperature of spS. The next step in the process of this invention is to mix a styrene greater the proportion of the clay material in the spS matrix, monomer with the modified clay material, which may be intercalated with a polymer or oligomer other than spS and the more marked the effects achieved.” is compatible or partially compatible with spS, and to 0849 U.S. Pat. No. 6,410,142 also discloses that “The polymerize the mixture by using a catalyst composition amount of the clay material dispersed in the composite containing metallocene, thereby giving an intended compos material of this invention is preferably in the range from ite material of this invention. Typically, the polymerization about 0.1 to 40 parts by weight per 100 parts by weight of of syndiotactic polystyrene requires a catalyst composition the polymer matrix. If this amount is less than 0.1 parts, a containing a metallocene catalyst and a methyl aluminoxane sufficient reinforcing effect cannot be expected. If the (MAO) co-catalyst. The concerted action of the metallocene amount exceeds 40 parts, on the other hand, the resulting and the methyl aluminoxane allows syndiotactic polystyrene