USOO588O237A United States Patent (19) 11 Patent Number: 5,880,237 Howland et al. (45) Date of Patent: Mar. 9, 1999

54 PREPARATION AND UTILITY OF WATER- 4.885,345 12/1989 Fong. SOLUBLE POLYMERS HAVING PENDANT 5,071,933 12/1991 Muller et al.. DERIVATIZED AMIDE, ESTER OR ETHER 5,084.520 1/1992 Fong FUNCTIONALITIES AS CERAMICS 5,209,885 5/1993 Quadir et al.. 5,266.243 11/1993 Kneller et al.. DSPERSANTS AND BINDERS 5,358,911 10/1994 Moeggenborg et al.. 5,393,343 2/1995 Darwin et al.. 75 Inventors: Christopher P. Howland, St. Charles; 5,487,855 1/1996 Moeggenborg et al.. Kevin J. Moeggenborg. Naperville; 5,525,665 6/1996 Moeggenborg et al.. John D. Morris, Plainfield, all of Ill., 5,532,307 7/1996 Bogan. Peter E. Reed, Puyallup, Wash.; 5,567,353 10/1996 Bogan. Jiansheng Tang, Naperville, Ill., Jin-Shan Wang, Rochester, N.Y. FOREIGN PATENT DOCUMENTS O5009232 A2 1/1993 Japan. 73 Assignee: Nalco Chemical Company, Naperville, 05070212 A2 3/1993 Japan. III. 05294712 A2 11/1993 Japan. 06072759 A2 3/1994 Japan. 06313004 A2 11/1994 Japan. 21 Appl. No.: 982,590 07010943 A2 1/1995 Japan. 22 Filed: Dec. 4, 1997 07101778 A2 4/1995 Japan. 07133160 A2 5/1995 Japan. Related U.S. Application Data 07144970 A2 6/1995 Japan. Primary Examiner-Paul R. Michl 63 Continuation-in-part of Ser. No. 792,610, Jan. 31, 1997, Pat. Attorney, Agent, or Firm Elaine M. Ramesh; Thomas M. No. 5,726.267. Breininger (51) Int. Cl...... C08F 20/58 57 ABSTRACT 52 U.S. Cl...... 526/304; 526/307 58 Field of Search ...... 526/304, 307 Methods for dispersing and binding ceramic materials in aqueous media are disclosed. The methods utilize water 56) References Cited Soluble polymers having pendant derivatized amide, ester or U.S. PATENT DOCUMENTS ether functionalities for. dispersing and binding various classes of ceramic materials. 4,680,339 7/1987 Fong. 4,731,419 3/1988 Fong. 4 Claims, No Drawings 5,880,237 1 2 PREPARATION AND UTILITY OF WATER non-volatile Solid. The liquid is vaporized by direct contact SOLUBLE POLYMERS HAVING PENDANT with a drying medium, usually air, in an extremely short DERIVATIZED AMIDE, ESTER OR ETHER retention time, on the order of about 3 to about 30 seconds. FUNCTIONALITIES AS CERAMICS The primary controlling factors in a Spray drying proceSS are particle size, particle size distribution, particle shape, Slurry DISPERSANTS AND BINDERS density, Slurry Viscosity, temperature, residence time, and This application is a continuation-in-part of application product moisture. The viscosity of the slurry must be suitable for handling Ser. No. 08/792,610, filed Jan. 31, 1997 entitled “Prepara and Spray-drying. Although spray-drying equipment condi tion and Utility of Water-Soluble Polymers having Pendant tions may be adjusted to handle a variety of Viscosities, Derivatized Amide, Ester or Ether Functionalities as Ceram larger particles will usually result from higher Viscosity ics Dispersants and Binders”, now U.S. Pat. No. 5,726,267. Slurries. Those of ordinary skill in the art are familiar with the FIELD OF THE INVENTION Spray-drying proceSS used in the production of ceramic Methods for dispersing and binding ceramic materials in materials, and will be able to optimize the control factors of aqueous media are disclosed. The methods utilize water 15 Spray-drying to best advantage. Alternatively, the Spray Soluble polymers having pendant derivatized amide, ester or drying process may be replaced by other well known drying ether functionalities for dispersing and binding various methods, Such as granulation, tape casting and Slip casting. classes of ceramic materials. Spray drying of the slurry produces Substantially dry, free-flowing powder particles which contain the ceramic, the BACKGROUND OF THE INVENTION binder and the optional materials described above. The dry Ceramic materials are commonly prepared by mixing particles are granules which are generally Spheroidal in powdered ceramic oxides Such as magnesia, alumina, titania shape and have an effective diameter of about 50 to about and Zirconia, in a slurry along with additives, Such as 300 micrometers. Typically, about 0.5 percent to about 8 dispersants and binders. The Slurry may be spray dried to 25 percent of the binder, based on the dry weight of the ceramic produce ceramic particles. The particles are pressed into an powder, is present in the dry particles. aggregate structure, called a "green ceramic, having a In granulation, a mixture of dry powder or powderS is desired shape and Subsequently Subjected to a Severe heat mixed or rolled, commonly in a barrel shaped apparatus. treatment known as Sintering. The Sintering proceSS converts Water and/or a binder Solution is sprayed into the mixing the green ceramic into a cohesive “fired ceramic', having a powder causing aggregation of the Small particles into larger nearly monolithic polycrystalline ceramic phase. granules. The size of the granules is controlled by the The binder serves to hold the ceramic particles of the amount of material sprayed into the powders and the Speed green ceramic in the desired shape after pressing. The binder with which it is sprayed. Granulated powderS may be can also provide lubrication while the particles are pressed. Screened to a desired size and pressed to shape in a pressing Preferably, the binder combusts or vaporizes completely 35 operation prior to Sintering. Alternatively, the granules them during the Sintering proceSS leaving no trace of the binder in Selves may be the desired product and may be sintered the fired ceramic. In performing these functions, binders directly. Significantly affect the properties of the fired ceramics which Tape casting is commonly used to produce thin Substrates are ultimately produced. for the computer industry. In the process, a thick ceramic In commercial practice, poly(Vinyl alcohols) are widely 40 Slurry containing ceramic powder, dispersant and binderS is used as ceramic binders. Additionally, poly(ethylene oxide) prepared. This slurry is cast onto a Smooth Surface Such as and ethylene-Vinyl acetate copolymerS reportedly have been a Mylar or plastic sheet and the thickness is controlled by used as binders for particulate material, Such as granular passing the sheet under a blade which Smoothes the slurry Silica gel. Surface and Scrapes off exceSS material. The Slurry tape is 45 dried to a plastic State and cut and shaped to specification. For example, polymeric binders containing Substantially The amount of binders present in tape casting is very high, hydrolyzed copolymers made from monomers having ester typically on the order of 15 to 20 wt.% of the ceramic or amide functional groups, poly(Vinylformamide) or a powder mass. copolymer of vinyl alcohol and vinyl amine are disclosed in In fluidized bed spray drying, Small “Seed' particles are U.S. Pat. Nos. 5,358,911; 5.487,855 and 5,525,665. 50 placed in a column and hot air is blown into the Seed powder Furthermore, polymeric treatments have been disclosed in from below Suspending the particles in the column. A U.S. Pat. Nos. 4,680,339; 4,731,419; 4.885,345 and 5,084, ceramic slurry is sprayed onto the Seed particles from above, 520. Utility for the treatments has been disclosed to be as causing them to grow. When the particles reach a large dispersants in water treatment, Scale inhibitors in industrial enough size, they are siphoned out of the dryer while more and natural waters, flocculants, coagulants and thickeners, 55 Seed particles are introduced. This process can produce but ceramicS applications of binding and disperSancy have powder for further forming processes, or the powder itself not been disclosed. may represent the desired product, in which case it would be Although commercially available binders are Satisfactory Sintered to produce the final ceramic. for many applications, a need exists for improved binders The dry particles are compacted to produce an aggregate, which provide Still greater Strength and/or increased density 60 green ceramic structure. Preferably, the particles are com in green ceramic materials. Greater green Strength reduces pacted by pressing in dies having an internal Volume which breakage during handling of the green ceramics and, approximates the shape desired for the final fired ceramic generally, is associated with higher quality fired ceramics. product. Alternatively, the particles are compacted by roll Preferably, the improved binders would be cheaper and more compacting or other well-known compacting methods. The Versatile than previously known binders. 65 Spray dried blend of powder, binder, and optional Surfactants Spray drying is an evaporative process in which liquid is and lubricants is relatively free flowing So that it can enter removed from a slurry containing a liquid and a Substantially and closely conform to the shape of the pressing dies. 5,880,237 3 4 Inside the dies, the dry particles are Subjected to a to produce a fired ceramic material. Alternatively, the par pressure which is typically in the range of about 5000 to ticles can be formed into an aggregate, green ceramic about 50,000 psi. Pressing the particles produces an aggre Structure by roll compaction or other well-known methods. gate Structure, called a green ceramic, which retains its Although commercially available binders are Satisfactory shape after removal from the die. for many applications, a need exists for improved binders One forming technique used for Spray dried or granulated which provide Still greater Strength and/or high density in material is roll compaction, also referred to as roll pressing. green ceramic materials. Greater green Strength reduces This technique takes a dry powder and crushes it between breakage during handling of the green ceramics and, two rollers in a continuous process. This proceSS produces generally, is associated with higher quality fired ceramics. sheets of ceramic of various widths and thicknesses. These Preferably, the improved binders would be cheaper and more sheets can be cut to shape and Sintered to produce the final Versatile than previously known binders. ceramic body. The process is commonly used to produce The present invention also relates to a method for dis ceramic Substrates for the electronics industry. persing ceramic materials. In particular, the present inven Dry pressing involves filling a shaped die with Spray dried tion relates to a method for dispersing one or more ceramic or granulated powder and pressing it at high preSSures. The 15 materials in an aqueous medium by using a polymeric pressing occurs through movable pistons at the top and/or dispersant formed from acid-containing monomers and bottom of the die cavity. The process can be used to produce hydroxy functional monomers. fairly complex geometries in a Single forming Step. The Ceramic materials are often used to prepare lightweight, ceramic body that results is ejected from the die and Sintered Strong, thermally and chemically resistant products. Because to produce a final ceramic product. of difficulties associated with the handling of Solid ceramic ISOStatic pressing is Similar to dry pressing in that a materials, it is desirable for the ceramic materials to be in the ceramic powder is pressed in a die cavity. In isostatic form of an aqueous dispersion. Aqueous dispersions of pressing, however, all or part of the die wall consists of a ceramic materials are, however, often unstable, exhibiting flexible material. After filling the die cavity with powder, the Sediment formation upon Standing. Upon Standing, the dis die is Submerged in a liquid pressure chamber and pressure 25 persion agglomerates and becomes non-homogeneous, and is applied to Squeeze the die and compact the powder. Unlike creates difficulty in handling. These agglomerates may also dry pressing, no movable parts are involved. Isostatic preSS damage pipes, pumps, and other dispersion handling ing is commonly used on large or very long parts to mechanical equipment. The use of dispersants overcomes minimize cracking or lamination of the final ceramic green these difficulties, and also improves Strength and density of body. formed ceramic parts, particularly those made by dry press, Extrusion involves the pushing of a concentrated, plastic, Slip casting, and tape casting processes. Slurry through an orifice. The orifice is of the Size and shape Polymers are known for use as dispersants for ceramic of the desired ceramic body. This proceSS is commonly used materials. Typical polymeric dispersants for ceramic mate to produce ceramic tubes or similarly shaped pieces. The rials include polymers formed from acid-containing mono Slurry used is prepared from dry powders which are mixed 35 merS Such as, for example, poly(acrylic acid) and poly with water, organic binders and lubricants, and a coagulant. (methacrylic acid). For example, anionic polymers produced This slurry is usually predried in a filter preSS or similar by hydrolyzing a terpolymer of maleic anhydride, apparatus to remove excess water and thicken the Slurry to N-vinylpyrrolidinone and a vinyl compound selected from a plastic material. The material is then extruded through a the group consisting of acrylic acid, acrylamide, methyl press which is either piston or screw driven. The extruded 40 methacrylate and butyl vinyl ether is disclosed in U.S. Pat. material is cut to length, dried, and Sintered. No. 5,266,243. Additionally, polymeric dispersants consist Jiggering is commonly used in the whiteware industry to ing of from 5 to 95 percent by weight of one or more shape an extruded or filter pressed ceramic slurry. Typically, hydroxy functional monomers and from 95% to 5% by a portion of the plastic Slurry is placed on a rotating wheel 45 weight of one or more acid-containing monomers are dis and shaped by rollers and/or knife blades to a desired closed in U.S. Pat. Nos. 5,567,353 and 5,532,307. The geometry. This body is then dried and Sintered. hydroxy functional monomer is Selected from the group Another ceramic forming method, that is used for parts of consisting of hydroxypropyl acrylate, hydroxypropyl complex shape, is slip casting. In Slip casting, a concentrated methacrylate, hydroxyethyl acrylate, hydroxyethyl ceramic slurry (slip) is poured into a mold with an internal 50 methacrylate, allyl alcohol, allyloxyethanol, allyl shape of the desired ceramic body. The slurry used must be propoxylate, Vinyl acetate, 1-butene-3,4-diol and 3-allyloxy highly concentrated to prevent Settling of particles and/or 1,2-propane diol. excessive shrinkage during drying. At the same time, the Slip Furthermore, imidized acrylic polymers have been dis must be fluid enough to completely fill the mold and allow closed for the increase of flowability in cement compositions escape of air bubbles. The presence of a polymeric binder 55 in U.S. Pat. No. 5,393,343. adds strength to the cast body preventing breakage during While Such polymers perform adequately in dispersing mold removal and handling of the body prior to Sintering. Some ceramic materials, certain ceramic materials are more Heating the aggregate Structure drives off volatile mate difficult to disperse, and conventional polymeric dispersants rials. Such as water, and burns off organic materials, Such as are not adequate. Ceramic materials which present particular binders or surfactants. When a sufficiently high temperature 60 difficulty in forming dispersions include nitrides Such as, for is reached, the particles of the aggregate Structure begin to example, boron nitride. U.S. Pat. No. 5,209,885 describes fuse, but do not fuse completely, and become fastened to one dispersing Silicon nitride for extrusion by the use of a graft another to reproduce a relatively strong fired ceramic mate copolymer comprising a polyoxyalkylene backbone with rial having essentially the desired shape. polyacrylate Side chains. The Slurry is, for example, Spray dried to produce Sub 65 The present invention seeks to provide a method for Stantially dry particles. The particles are preferably pressed dispersing ceramic material, including Several ceramic to produce an aggregate, green ceramic structure and heated materials known to be difficult to disperse. 5,880,237 S 6 SUMMARY OF THE INVENTION for example, by using distilled, deionized, partially distilled or partially deionized water, by controlling the level of Methods for dispersing and binding ceramic materials in contaminants introduced into the dispersion by the various aqueous media are disclosed. The methods utilize water components of the dispersion or by adding one or more Soluble polymers having pendant derivatized amide, ester or conventional chelating agents to the dispersion. Preferably, ether functionalities for dispersing and binding various the water hardness of the dispersion which is attributable to classes of ceramic materials. multivalent cations is below about 600 parts per million (“ppm) expressed as Cat", most preferably below about DESCRIPTION OF THE INVENTION 500 ppm. Generally, the higher the pH of the dispersion, the lower the quantity of dispersant required. For purposes of Each of the five classes of polymers described herein may the present invention, it is preferred that the pH not be below also have utility for mining applications Such as dust control 6. The polymeric dispersant of the present invention works and red mud flocculation; for cooling water treatment Such particularly well at a pH of about 8 to 11. as Scale and corrosion inhibition, Such as for calcium car bonate and calcium phosphonate Scale inhibition; for ceram Ceramic materials useful in forming a dispersion accord ics applications Such as green machining and core forming 15 ing to the method of the present invention include oxide, process of gypsum wall board; for the preparation of gyp nitride, and carbide ceramics, in particular: alumina, alumi Sum Slurries, for reverse osmosis System treatment Such as num nitride, aluminum titanate, lead titanate, boron nitride, desalination Scale inhibition, for oilfield applications Such as Silicon, Silicon carbide, Sialon, Zirconium nitride, Zirconium reverse emulsion breakers and barium Sulfate and calcium carbide, Zirconium boride, boron carbide, tungsten carbide, carbonate Scale inhibition; for treatment of pulp and paper tungsten boride, tin oxide, ruthenium oxide, yttrium oxide, Systems. Such as Scale control, Sizing agents, dry Strength magnesium oxide, calcium oxide, chromic oxide, ferrites, additives and release agents and as a treatment for Solids/ and mixtures thereof among others. liquids Separation. Such structures can be used in many AS used herein, "ceramic materials” include ferrites. The applications Such as dispersants in water treatment, Scale ferrites are ferrimagnetic oxides. The classes of ferrites inhibitors in natural and industrial waters, flocculants, 25 include Spinel ferrites, which are oxides having the general coagulants, and thickeners among others. formula MO.FeO, where “M” represents a divalent metal ion or a mixture of ions. Particular examples of Spinel The present invention relates to polymeric binders for ferrites are FeO and NiFe O. Another class of ferrites is preparing ceramic materials. The method can be used to the orthoferrites, with the general formulas MFe0, MCoO, produce fired ceramic materials from ceramic powders. or MMnO, where M represents La, Ca, Sr, Ba Y, or a rare Suitable powders include but are not limited to: aluminum earth ion. Another class of ferrites is the hexagonal ferrites, oxide, Silicon nitride, aluminum nitride, Silicon carbide, with the general formula ABOo, where A is a divalent Silicon oxide, magnesium oxide, lead oxide, Zirconium metal and B is a trivalent metal. Examples of hexagonal oxide, titanium oxide and neodymium oxide. Aluminum oxide is presently preferred. The powder can have a weight ferrites include PbFeO. averaged median particle size in the range of a few nanom 35 The term clays as used herein denotes materials utilized in eters to about 72 millimeter. Powders having a median size whiteware manufacture. Examples are kaolin and ball clay in the range of about 0.5 to about 10 micrometers are among others. preferred. The polymers described herein for the practice of this invention may range in molecular weight from about 1,000 In one aspect, the ceramic powder is mixed with an 40 to about 1,000,000. Preferably, the molecular weight will be aqueous Solution containing a polymer to produce a Slurry. from about 5,000 to about 100,000. For the polymers defined Preferably, the Solution is prepared using deionized water. herein, the mer units defined by formulas I-IV will range The Slurry may also contain lubricants, plasticizers and from 5 to 75% of the total number of mer units in the Surfactants, Such as dispersants and anti-foaming agents. polymer. Preferably, the mer units defined as formulas I-IV It is also recognized that the properties of a ceramic Such 45 will be at least 30% of the total number of mer units in the as, but not limited to, green density, Surface quality or polymer. milling characteristics, may be varied as desired by adjust The polymer classes described herein contain amide, ester ing the ratio of the different monomers in a copolymer, the and ether mer units which are functionalized with pendant degree of hydrolysis of a copolymer and the molecular groups. These pendant groups confer favorable properties to weight of the polymer used in the binder composition. 50 the polymer for use as a binder for ceramic materials. The Several factors may affect the preferred quantity of the polymers may be produced by polymerization using Specific polymeric dispersant to be used in forming a dispersion of monomers, Such as might be produced by the copolymer a ceramic material. Because of the range of ceramic mate ization of acrylic acid with a poly(ethylene glycol) meth rials that might be used for particular applications, and acrylate comonomer. The polymer So produced would con because different applications may require different Solids 55 tain a hydrophilic backbone with pendant groups comprised levels, the amount of dispersant may range from 0.01 of poly(ethylene glycol). Alternatively, pendant groups percent to 3 percent by weight based on powder mass. For could be introduced into the polymer after polymerization. example, the morphology of the ceramic material may affect For example, polyacrylic acid could be amidated with an the optimum level of dispersant. Generally, the more spheri ethoxylated/propoxylated amine, Such as those available cal the particles, the leSS dispersant is required. The Surface 60 from Texaco under the trade name Jeffamine Series, to area of the ceramic material may also affect the optimum produce a polymer with a hydrophilic backbone and quantity of dispersant. The higher the Surface area of a ethyleneoxy/propyleneoxy pendant groups. During the ami ceramic material, generally the more dispersant is required. dation process, cyclic imide Structures might form between The ionic strength (or water hardness) of the dispersion two adjacent carboxylate or carboxamide units on the poly may also affect the optimum level of dispersant. Dispersions 65 mer backbone. These imide Structures are not expected to having higher ionic Strength generally require more disperS have an adverse effect on the performance of the polymers ant. The ionic Strength of the dispersion can be controlled, as a ceramic processing aid. 5,880,237 7 8 The invention is a binder for ceramic materials that pane Sulfonic acid, Vinyl alcohol, Vinyl acetate, N-Vinyl comprises a water Soluble polymer having: pyrrollidone, maleic acid, and combinations thereof. A) a mer unit of the formula The invention is also a method for preparing a ceramic material, which comprises the Steps of R6 I 5 A) mixing a ceramic powder with an aqueous Solution containing a water-Soluble polymer to produce a slurry, Said --CH water-Soluble polymer having: i) a mer unit of the formula

I R 1O (CHR2CHR3Het! (- CHR2CHR3Het2 , R4 wherein R is selected from the group consisting of hydrogen, and C-C alkyl, p and q are integers from 1-10; (=o R° and Rare selected from the group consisting of hydro gen and C-C alkyl; Het' and Het’ selected from the group 15 R consisting of O and NH with the proviso that Het' and Het (CHR2CHR3Het! (- CHR2CHR3Het2 , R4 are not both oxygen; R" is selected from the group consisting wherein R' is selected from the group consisting of of hydrogen, phosphate, Sulfate and C-Co alkyl; RandR hydrogen, and C-C alkyl, p and q are integers from are Selected from the group consisting of hydrogen, 1-10; R and Rare selected from the group consisting carboxylate, C-C alkyl, and a cycloalkyl group of 1 to 6 of hydrogen and C-C alkyl; Het' and Het selected carbon atoms formed by the linkage of R and Ras a ring; from the group consisting of O and NH with the proviso and that Het' and Het? are not both oxygen; R is selected B) amer unit Selected from the group consisting of acrylic from the group consisting of hydrogen, phosphate, acid, methacrylic acid, acrylamide, maleic anhydride, ita sulfate and C-C alkyl; R and Rare selected from conic acid, Vinyl Sulfonic acid, Styrene Sulfonate, 25 the group consisting of hydrogen, carboxylate, C-C, N-tertbutylacrylamide, butoxymethylacrylamide, N,N- alkyl, and a cycloalkyl group of 1 to 6 carbon atoms dimethylacrylamide, Sodium acrylamidomethyl propane Sul formed by the linkage of R and R as a ring; and fonic acid, Vinyl alcohol, Vinyl acetate, N-Vinyl pyrrolidone, ii) a mer unit Selected from the group consisting of acrylic maleic acid, and combinations thereof. acid, methacrylic acid, acrylamide, maleic anhydride, AS used herein, the monomerS described above may be in itaconic acid, Vinyl Sulfonic acid, Styrene Sulfonate, either their salt or acid forms. N-tertbutylacrylamide, butoxymethylacrylamide, N,N- The invention is also an unfired, ceramic precursor mate dimethylacrylamide, Sodium acrylamidomethyl pro rial comprising a mixture of: pane Sulfonic acid, vinyl alcohol, Vinyl acetate, N-Vinyl A. a ceramic powder Selected from the group consisting pyrrollidone, maleic acid, and combinations thereof; of aluminum oxide, Silicon nitride, aluminum nitride, Silicon 35 B) drying the slurry by a process Selected from the group carbide, Silicon oxide, magnesium oxide, lead oxide, Zirco consisting of fluidized bed spray drying, and Spray drying to nium oxide, titanium oxide, Steatite, barium titanate, lead produce particles which include Said copolymer; Zirconate titanate, clays, ferrite, yttrium oxide, Zinc oxide, C) compacting the particles by a process selected from the tungsten carbide, Sialon, neodymium oxide and combina group consisting of dry pressing, roll compaction and isos tions thereof and 40 tatic pressing to produce an aggregate Structure; and B. a water Soluble polymer having: D) heating the aggregate structure to produce a fired i) a mer unit of the formula ceramic material. Moreover, for the practice of this invention, the particles R6 I may be produced by granulation and the Step of compacting 45 the particles to produce an aggregate Structure may be --CH Selected from the group consisting of dry pressing and isostatic pressing. Alternatively, other methods of making ceramics which R are Suitable for the purposes of this invention include (CHR2CHR3Het! (- CHR2CHR3Het2 , R4 50 extrusion, jiggering, tape casting and slip casting. wherein R' is selected from the group consisting of The invention is a binder for ceramic materials that hydrogen, and C-C alkyl, p and q are integers from comprises a water Soluble polymer having: 1-10; R and Rare selected from the group consisting A) a mer unit of the formula of hydrogen and C-C alkyl, Het and Het selected 55 from the group consisting of O and NH with the proviso R5 R6 I that Het' and Het? are not both oxygen; R is selected from the group consisting of hydrogen, phosphate, sulfate and C-C alkyl; R and Rare selected from CO the group consisting of hydrogen, carboxylate, C-C, 60 O alkyl, and a cycloalkyl group of 1 to 6 carbon atoms formed by the linkage of R and R as a ring; and (CHRCHROR ii) a mer unit Selected from the group consisting of acrylic wherein p is an integer from 1-10; R and R are selected acid, methacrylic acid, acrylamide, maleic anhydride, from the group consisting of hydrogen and C, alkyl; R' itaconic acid, vinyl Sulfonic acid, Styrene Sulfonate, 65 is Selected from the group consisting of hydrogen, N-tertbutylacrylamide, butoxymethylacrylamide, N,N- phosphate, Sulfate and C-Cao alkyl; R and Rare selected dimethylacrylamide, Sodium acrylamidomethyl pro from the group consisting of hydrogen, carboxylate, C-C, 5,880,237 9 10 alkyl, and a cycloalkyl group of 1 to 6 carbon atoms formed C-C alkyl; R is selected from the group consisting by the linkage of R and R as a ring, with the proviso that of hydrogen, phosphate, Sulfate and C-C alkyl, R when p=1, R,R,R, R and Rare not all hydrogens, and and R are selected from the group consisting of with the proviso that when p=1, R is not methyl; and hydrogen, carboxylate, C-C alkyl, and a cycloalkyl B) a water-Soluble mer unit Selected from the group group of 1 to 6 carbon atoms formed by the linkage of consisting of acrylic acid, methacrylic acid, acrylamide, RandR as a ring, with the proviso that when p=1, R, maleic anhydride, itaconic acid, Vinyl Sulfonic acid, Styrene R. R", R and Rare not all hydrogens, and with the Sulfonate, N-tertbutylacrylamide, butoxymethylacrylamide, proviso that when p=1, R is not methyl; and N,N-dimethylacrylamide, Sodium acrylamidomethyl pro ii) a water-Soluble mer unit Selected from the group pane Sulfonic acid, vinyl alcohol, N-Vinyl pyrrolidone, consisting of acrylic acid, methacrylic acid, maleic acid, and combinations thereof. acrylamide, maleic anhydride, itaconic acid, Vinyl Sul AS used herein, the monomerS described above may be in fonic acid, Styrene Sulfonate, N-tertbutylacrylamide, either their salt or acid forms. butoxymethylacrylamide, N,N-dimethylacrylamide, The invention is also an unfired, ceramic precursor mate Sodium acrylamidomethyl propane Sulfonic acid, Vinyl rial comprising a mixture of alcohol, N-Vinyl pyrrollidone, maleic acid, and combi A. a ceramic powder Selected from the group consisting 15 nations thereof; of aluminum oxide, Silicon nitride, aluminum nitride, Silicon B) drying the slurry by a process Selected from the group carbide, Silicon oxide, magnesium oxide, lead oxide, Zirco consisting of fluidized bed spray drying, and Spray drying to nium oxide, titanium oxide, Steatite, barium titanate, lead produce particles which include Said copolymer; C) compacting the particles by a process selected from the Zirconate titanate, clays, ferrite, yttrium oxide, Zinc oxide, group consisting of dry pressing, roll compaction and isos tungsten carbide, Sialon, neodymium oxide and combina tatic pressing to produce an aggregate Structure; and tions thereof and D) heating the aggregate structure to produce a fired B. a water Soluble polymer having: ceramic material. i) a mer unit of the formula Moreover, for the practice of this method, the particles 25 may be produced by granulation and the Step of compacting R5 R6 II the particles to produce an aggregate Structure may be Selected from the group consisting of dry pressing and isostatic pressing. CO Alternatively, other methods of making ceramics which are Suitable for the purposes of this invention include extrusion, jiggering, tape casting and slip casting. (CHRCHRO-R' The invention is also a method for dispersing one or more ceramic materials in an aqueous medium, comprising uti wherein p is an integer from 1-10; R and R are lizing an effective dispersing amount of a polymeric dis Selected from the group consisting of hydrogen and persant comprising a water Soluble polymer having: C-C alkyl; R is selected from the group consisting 35 of hydrogen, phosphate, Sulfate and C-Cao alkyl; R A) a mer unit of the formula and R are selected from the group consisting of I hydrogen, carboxylate, C-C alkyl, and a cycloalkyl group of 1 to 6 carbon atoms formed by the linkage of 40 RandR as a ring, with the proviso that when p=1, R, CO R. R", R and Rare not all hydrogens, and with the proviso that when p=1, R is not methyl; and O ii) a water-Soluble mer unit Selected from the group consisting of acrylic acid, methacrylic acid, (CHRCHRO-R' acrylamide, maleic anhydride, itaconic acid, Vinyl Sul 45 wherein p is an integer from 1-10; R and R are selected fonic acid, Styrene Sulfonate, N-tertbutylacrylamide, from the group consisting of hydrogen and C-C alkyl, R' butoxymethylacrylamide, N,N-dimethylacrylamide, is Selected from the group consisting of hydrogen, Sodium acrylamidomethyl propane Sulfonic acid, Vinyl phosphate, Sulfate and C-Cao alkyl; R and Rare selected alcohol, N-Vinyl pyrrollidone, maleic acid, and combi from the group consisting of hydrogen, carboxylate, C-C, nations thereof. 50 alkyl, and a cycloalkyl group of 1 to 6 carbon atoms formed The invention is also a method for preparing a ceramic by the linkage of R and R as a ring, with the proviso that material, which comprises the Steps of when p=1, R,R,R, R and Rare not all hydrogens, and A) mixing a ceramic powder with an aqueous Solution with the proviso that when p=1, R is not methyl; and containing a water-Soluble polymer to produce a slurry, Said B) a water-Soluble mer unit Selected from the group water-Soluble polymer having: 55 consisting of acrylic acid, methacrylic acid, acrylamide, maleic anhydride, itaconic acid, Vinyl Sulfonic acid, Styrene i) a mer unit of the formula Sulfonate, N-tertbutylacrylamide, butoxymethylacrylamide, II N,N-dimethylacrylamide, sodium acrylamidomethyl pro pane Sulfonic acid, Vinyl alcohol, N-Vinyl pyrrolidone, 60 maleic acid, and combinations thereof. CO Moreover the one or more ceramic materials may be Selected from the group consisting of alumina, aluminum O nitride, aluminum titanate, lead titanate, boron nitride, Silicon, Silicon carbide, Sialon, Zirconium nitride, Zirconium (CHRCHRO-R' 65 carbide, Zirconium boride, boron carbide, tungsten carbide, wherein p is an integer from 1-10; R and R are tungsten boride, tin oxide, ruthenium oxide, yttrium oxide, Selected from the group consisting of hydrogen and magnesium oxide, calcium oxide, and ferrites. 5,880,237 11 12 Furthermore, the invention is also an aqueous dispersion ii) a water-Soluble mer unit Selected from the group of ceramic material prepared according to the method above. consisting of acrylic acid, methacrylic acid, The invention is also a binder for ceramic materials that acrylamide, maleic anhydride, itaconic acid, Vinyl Sul comprises a water Soluble polymer having: fonic acid, Styrene Sulfonate, N-tertbutylacrylamide, A) a mer unit of the formula butoxymethylacrylamide, N,N-dimethylacrylamide, Sodium acrylamidomethyl propane Sulfonic acid, Vinyl R5 R6 III alcohol, N-Vinyl pyrrollidone, maleic acid, and combi nations thereof. The invention is also a method for preparing a ceramic CH2 material, which comprises the Steps of O A) mixing a ceramic powder with an aqueous Solution containing a water-Soluble polymer to produce a slurry, Said (CHRCHRO-R' water-Soluble polymer having: wherein p is an integer from 1-10; R and R are selected i) a mer unit of the formula from the group consisting of hydrogen and C-C alkyl, R' 15 is Selected from the group consisting of hydrogen, R5 R6 III phosphate, Sulfate and C-Cao alkyl; R and Rare selected from the group consisting of hydrogen, carboxylate, C-C, alkyl, and a cycloalkyl group of 1 to 6 carbon atoms formed --CH by the linkage of R and R as a ring, with the proviso that CH2 when p=1, R. R. R", Rand Rare not all hydrogens and O with the proviso that when p=1, R is not methyl and with the proviso that when p=1, R is not methyl; and (CHRCHROR B) a water-Soluble mer unit Selected from the group wherein p is an integer from 1-10; R and R are consisting of acrylic acid, methacrylic acid, acrylamide, 25 Selected from the group consisting of hydrogen and maleic anhydride, itaconic acid, Vinyl Sulfonic acid, Styrene Sulfonate, N-tertbutylacrylamide, butoxymethylacrylamide, C-C alkyl; R is selected from the group consisting N,N-dimethylacrylamide, Sodium acrylamidomethyl pro of hydrogen, phosphate, Sulfate and C-Cao alkyl, R pane Sulfonic acid, vinyl alcohol, N-Vinyl pyrrolidone, and R are selected from the group consisting of maleic acid, and combinations thereof. hydrogen, carboxylate, C-C alkyl, and a cycloalkyl AS used herein, the monomerS described above may be in group of 1 to 6 carbon atoms formed by the linkage of either their salt or acid forms. RandR as a ring, with the proviso that when p=1, R, The invention is also an unfired, ceramic precursor mate R. R", R and Rare not all hydrogens and with the rial comprising a mixture of proviso that when p=1, R is not methyl and with the A. a ceramic powder Selected from the group consisting proviso that when p=1, R is not methyl; and of aluminum oxide, Silicon nitride, aluminum nitride, Silicon 35 ii) a water-Soluble mer unit Selected from the group carbide, Silicon oxide, magnesium oxide, lead oxide, Zirco consisting of acrylic acid, methacrylic acid, nium oxide, titanium oxide, Steatite, barium titanate, lead acrylamide, maleic anhydride, itaconic acid, Vinyl Sul fonic acid, Styrene Sulfonate, N-tertbutylacrylamide, Zirconate titanate, clays, ferrite, yttrium oxide, Zinc oxide, butoxymethylacrylamide, N,N-dimethylacrylamide, tungsten carbide, Sialon, neodymium oxide and combina 40 tions thereof and Sodium acrylamidomethyl propane Sulfonic acid, Vinyl B. a water Soluble polymer having: alcohol, N-Vinyl pyrrollidone, maleic acid, and combi nations thereof; i) a mer unit of the formula B) drying the slurry by a process Selected from the group R5 R6 III consisting of fluidized bed spray drying, and Spray drying to 45 produce particles which include Said copolymer; C) compacting the particles by a process selected from the CH2 group consisting of dry pressing, roll compaction and isos tatic pressing to produce an aggregate Structure; and O D) heating the aggregate structure to produce a fired 50 ceramic material. (CHRCHRO-R' Moreover, for the practice of this invention, the particles wherein p is an integer from 1-10; R and R are may be produced by granulation and the Step of compacting Selected from the group consisting of hydrogen and the particles to produce an aggregate Structure may be C-C alkyl; R is selected from the group consisting Selected from the group consisting of dry pressing and of hydrogen, phosphate, Sulfate and C-Cao alkyl; R 55 isostatic pressing. and R are selected from the group consisting of Alternatively, other methods of making ceramics which hydrogen, carboxylate, C-C alkyl, and a cycloalkyl are Suitable for the purposes of this invention include group of 1 to 6 carbon atoms formed by the linkage of extrusion, jiggering, tape casting and slip casting. RandR as a ring, with the proviso that when p=1, R, The invention is also a method for dispersing one or more R. R", R and Rare not all hydrogens and with the 60 ceramic materials in an aqueous medium, comprising uti proviso that when p=1, R is not methyl and with the lizing an effective dispersing amount of a polymeric dis proviso that when p=1, R is not methyl; and persant comprising a water Soluble polymer having: 5,880,237 13 14 A) a mer unit of the formula Additionally, the binder may be of a structure wherein p=3; R, R, and R' are hydrogen; R is methyl in formula R5 R6 III IV of Step A, and the mer units of Step B are acrylic acid and acrylamide. CH2 Moreover, for the practice of this invention, mer units of general Structure IV with polyoxy N-pendant groups may O also be effective, as well as the alkyloxy groups described (CHRCHRO-R' above. For example multihydroxy N-pendant groupS. Such as wherein p is an integer from 1-10; R and R are selected those alkyl derivatives having dihydroxy and trihydroxy, as from the group consisting of hydrogen and C-C alkyl, R' well as alkyl derivatives containing diether and triether is Selected from the group consisting of hydrogen, moieties may also be effective. phosphate, Sulfate and C-Cao alkyl; R and Rare selected from the group consisting of hydrogen, carboxylate, C-C, The invention is also an unfired, ceramic precursor mate alkyl, and a cycloalkyl group of 1 to 6 carbon atoms formed 15 rial comprising a mixture of by the linkage of R and R as a ring, with the proviso that when p=1, R. R. R", Rand Rare not all hydrogens and A) a ceramic powder Selected from the group consisting with the proviso that when p=1, R is not methyl and with of aluminum oxide, Silicon nitride, aluminum nitride, Silicon the proviso that when p=1, R is not methyl; and carbide, Silicon oxide, magnesium oxide, lead oxide, Zirco B) a water-Soluble mer unit Selected from the group nium oxide, titanium oxide, Steatite, barium titanate, lead consisting of acrylic acid, methacrylic acid, acrylamide, Zirconate titanate, clays, ferrite, yttrium oxide, Zinc oxide, maleic anhydride, itaconic acid, Vinyl Sulfonic acid, Styrene tungsten carbide, Sialon, neodymium oxide and combina Sulfonate, N-tertbutylacrylamide, butoxymethylacrylamide, tions thereof and N,N-dimethylacrylamide, Sodium acrylamidomethyl pro pane Sulfonic acid, vinyl alcohol, N-Vinyl pyrrolidone, 25 B) a water-soluble polymer having: maleic acid, and combinations thereof. i) a mer unit of the formula Furthermore, the one or more ceramic materials may be Selected from the group consisting of alumina, aluminum R5 R6 IV nitride, aluminum titanate, lead titanate, boron nitride, Silicon, Silicon carbide, Sialon, Zirconium nitride, Zirconium carbide, Zirconium boride, boron carbide, tungsten carbide, tungsten boride, tin oxide, ruthenium oxide, yttrium oxide, (=o magnesium oxide, calcium oxide, and ferrites. R The invention is also an aqueous dispersion of ceramic material prepared according to the method described above. 35 (t), The invention is also a binder for ceramic materials that OR4 comprises a water-Soluble polymer having: wherein R is selected from the group consisting of A) a mer unit of the formula hydrogen, and C-C alkyl, p is an integer from 1-10; R" is selected from the group consisting of hydrogen, R5 R6 IV 40 phosphate, Sulfate and C-Co alkyl; R and R are Selected from the group consisting of hydrogen, carboxylate, C-C alkyl, and a cycloalkyl group of 1 (=o to 6 carbon atoms formed by the linkage of R and R' R 45 as a ring; and (t), ii) a mer unit Selected from the group consisting of acrylic OR4 acid, methacrylic acid, acrylamide, maleic anhydride, wherein R is selected from the group consisting of itaconic acid, Vinyl Sulfonic acid, Styrene Sulfonate, hydrogen, and C-C alkyl; p is an integer from 1-10; R is 50 N-tertbutylacrylamide, butoxymethylacrylamide, N,N- Selected from the group consisting of hydrogen, phosphate, dimethylacrylamide, Sodium acrylamidomethyl pro sulfate and C-Co alkyl; R and R are selected from the pane Sulfonic acid, Vinyl alcohol, Vinyl acetate, N-Vinyl group consisting of hydrogen, carboxylate, C-C alkyl, and pyrrollidone, maleic acid, and combinations thereof. a cycloalkyl group of 1 to 6 carbon atoms formed by the Preferably, the water-soluble polymer of the method linkage of R and R as a ring; and 55 described above has a structure wherein p=2; R', R", R, and B) amer unit Selected from the group consisting of acrylic Rare hydrogen for formula IV of step i; and the mer units acid, methacrylic acid, acrylamide, maleic anhydride, ita of Step ii are acrylic acid and acrylamide. conic acid, Vinyl Sulfonic acid, Styrene Sulfonate, N-tertbutylacrylamide, butoxymethylacrylamide, N,N- Alternatively, the water-soluble polymer of the method dimethylacrylamide, Sodium acrylamidomethyl propane Sul 60 described above has a structure wherein p=3; R, R, and R' fonic acid, Vinyl alcohol, Vinyl acetate, N-Vinyl pyrrolidone, are hydrogen; R" is methyl for formula IV of step i and the maleic acid, and combinations thereof. mer units of Step ii are acrylic acid and acrylamide. AS used herein, the monomerS described above may be in The invention is also a method for preparing a ceramic either their salt or acid forms. material, which comprises the Steps of Preferably, the binder is of a structure wherein p=2; R', 65 A) mixing a ceramic powder with an aqueous Solution R", R, and Rare hydrogen in formula IV of step A; and the containing a water-Soluble polymer to produce a slurry, Said mer units of Step B are acrylic acid and acrylamide. water-Soluble polymer having: 5,880,237 15 16 i) a mer unit of the formula Selected from the group consisting of hydrogen, phosphate, sulfate and C-C alkyl; R and R are selected from the R5 R6 IV group consisting of hydrogen, carboxylate, C-C alkyl, and a cycloalkyl group of 1 to 6 carbon atoms formed by the linkage of R and R as a ring; and B) a mer unit Selected from the group consisting of acrylic (=o acid, methacrylic acid, acrylamide, maleic anhydride, ita R conic acid, Vinyl Sulfonic acid, Styrene Sulfonate, N-tertbutylacrylamide, butoxymethylacrylamide, N,N- (t), dimethylacrylamide, Sodium acrylamidomethyl propane Sul OR4 fonic acid, Vinyl alcohol, Vinyl acetate, N-Vinyl pyrrolidone, wherein R' is selected from the group consisting of maleic acid, and combinations thereof. hydrogen, and C-C alkyl, p is an integer from 1-10; Preferably, the water-soluble polymer of the method R" is selected from the group consisting of hydrogen, described above has a structure wherein p=2; R', R", R, and phosphate, Sulfate and C-Co alkyl; R and R are 15 Rare hydrogen for formula IV of step A; and the mer units Selected from the group consisting of hydrogen, of Step B are acrylic acid and acrylamide. carboxylate, C-C alkyl, and a cycloalkyl group of 1 Alternatively, the water-soluble polymer of the method to 6 carbon atoms formed by the linkage of R and R' described above has a structure wherein p=3; R, R, and R' as a ring; and are hydrogen; R is methyl for formula IV of step A; and the ii) a mer unit Selected from the group consisting of acrylic mer units of Step B are acrylic acid and acrylamide. acid, methacrylic acid, acrylamide, maleic anhydride, For the practice of this invention, the one or more ceramic itaconic acid, vinyl Sulfonic acid, Styrene Sulfonate, materials may be selected from the group consisting of N-tertbutylacrylamide, butoxymethylacrylamide, N,N- alumina, aluminum nitride, aluminum titanate, lead titanate, dimethylacrylamide, Sodium acrylamidomethyl pro boron nitride, Silicon, Silicon carbide, Sialon, Zirconium pane Sulfonic acid, Vinyl alcohol, Vinyl acetate, N-Vinyl 25 nitride, Zirconium carbide, Zirconium boride, boron carbide, pyrrollidone, maleic acid, and combinations thereof; tungsten carbide, tungsten boride, tin oxide, ruthenium B) drying the Slurry by a process Selected from the group oxide, yttrium oxide, magnesium oxide, calcium oxide, and consisting of fluidized bed spray drying, and Spray drying to ferrites. produce particles which include Said copolymer; Moreover, the method may include an aqueous dispersion C) compacting the particles by a process selected from the of ceramic material. group consisting of dry pressing, roll compaction and isoS The following examples are presented to describe pre tatic pressing to produce an aggregate Structure; and ferred embodiments and utilities of the invention and are not D) heating the aggregate structure to produce a fired meant to limit the invention unless otherwise Stated in the ceramic material. claims appended hereto. Preferably, the water-soluble polymer of the method 35 described above has a structure wherein p=2; R', R", R, and EXAMPLE 1. Rare hydrogen for formula IV of step I and the mer units The synthesis of an ammonium acrylate/N- of Step ii are acrylic acid and acrylamide. (hydroxyethoxy)ethyl acrylamide copolymer was effected Alternatively, the water-soluble polymer of the method with the following reactants in the following amounts: described above has a structure wherein p=3; R, R, and 40 R" are hydrogen; R is methyl for formula IV of step i and the mer units of Step ii are acrylic acid and acrylamide. Reactant Amount (g) Furthermore, in the method described above, the particles Poly(AA), 25.6 weight % in water 1OO.OO may be produced by granulation and the Step of compacting Aminoethoxyethanol 11.92 the particles to produce an aggregate Structure may be 45 Ammonium Hydroxide, 29 weight % 2.51 Selected from the group consisting of dry pressing and isostatic pressing. Alternatively, other methods of making ceramics which To prepare the polymer, poly(AA) (25.6 weight percent are Suitable for the purposes of this invention include poly(acrylic acid) solution, pH=3.8, 16,000 MW) was extrusion, jiggering, tape casting and slip casting. 50 placed in a beaker, which was cooled using an ice bath. The invention is also a method for dispersing one or more Aminoethoxyethanol (available from Huntsman Petro ceramic materials in an aqueous medium, comprising uti chemical Co., in Houston,Tex.) was added dropwise into the lizing an effective dispersing amount of a polymeric dis poly(acrylic acid)/water Solution with vigorous stirring. persant comprising a water-Soluble polymer having: Afterwards, the Solution was stirred for another 15 minutes. A) a mer unit of the formula 55 The pH of the reaction mixture was measured using water wet pH Strips. Aqueous caustic was added to adjust the pH IV to about 5. Next, the reaction mixture was transferred into a 300 mL Parr reactor with a pressure rating of at least 800 psi. The reactor then was assembled and purged with nitrogen 60 for 60 minutes. The Parr reactor was then slowly heated to (=o 160° C. (or less, as the case may be) and held at that R temperature for 8 hours (or more, as the case may be). (t), Afterwards, the reactor was cooled to room temperature and OR4 the preSSure released. The product was then transferred to 65 Storage. wherein R is selected from the group consisting of 'C NMR confirmed product formation. The content of hydrogen, and C-C alkyl; p is an integer from 1-10; R is N-(hydroxyethoxy)ethyl acrylamide was 21 mole %, based 5,880,237 17 18 on the total moles of mer units on the polymer, which heated to 138 C. and held at that temperature for 12 hours. represents both Secondary amide and imide mer units. The Afterwards, the reactor was cooled to room temperature and polymer’s molecular weight was 24,000. the preSSure released. The product was then transferred to Storage. EXAMPLE 2 'C NMR confirmed product formation. The content of The Synthesis of an ammonium acrylate/acrylamide/N- N-(hydroxyethoxy)ethyl acrylamide was 33 mole %, based (hydroxyethoxy)ethyl acrylamide terpolymer was effected on the total moles of mer units on the polymer. The mole in the following manner with the reactants in the amounts ratio was 42/22/33 of acrylic acid/acrylamide(including 3% listed below: imide mer units)/N-(hydroxyethoxy)ethyl acrylamide (including imide mer units). The product polymer had a molecular weight of 12,000. Reactant Amount (g) EXAMPLE 4 Poly(NHAA/ACAm), 50/50 mol % 3OO.OO solution polymer, 38.2 weight % The synthesis of a sodium acrylate/acrylamide/N- Aminoethoxyethanol 114.OO 15 Methoxypropyl acrylamide terpolymer was effected in the following manner with the reactants in the amounts listed To prepare the polymer, Poly(NHAA/ACAm) (50/50 mol below: % ammonium acrylate/acrylamide copolymer, 38.2 weight percent, pH=5.5, 33,000 MW) was placed in a beaker, which was cooled using an ice bath. Aminoethoxyethanol Reactant Amount(g) (available from Huntsman Petrochemical Co., in Houston, Poly(NaAA/ACAm), 50/50 mol % 1OO.OO solution polymer, 32.0 weight % Tex.) was added dropwise into the above water solution with Methoxypropylamine 23.32 vigorous stirring (pH=10.1). Afterwards, the Solution was Sulfuric Acid (95%) 11.23 stirred for another 15 minutes. The pH of the reaction 25 mixture was measured using water-wet pH Strips. Next, the reaction mixture was transferred into a 600 mL Parr reactor To prepare the polymer, Poly(NaAA/AcAm) (50/50 mol with a pressure rating of at least 800 psi. The reactor then %, 32.0 weight %, pH=5.2, 11,000 MW) was placed in a was assembled and purged with nitrogen for 60 minutes. The beaker, which was cooled using an ice bath. Methoxypro Parr reactor was then slowly heated to 138 C. and held at pylamine (available from Aldrich Chem. Co., in Milwaukee, that temperature for 14 hours. Afterwards, the reactor was Wis.) was added dropwise into the above water solution with cooled to room temperature and the pressure released. The Vigorous stirring. Afterwards, the Solution was stirred for product was then transferred to storage. another 15 minutes. The pH of the reaction mixture was 'C NMR confirmed product formation. The content of measured using water-wet pH Strips. Sulfuric acid was N-(hydroxyethoxy)ethyl acrylamide was 33.3 mole %, 35 added to adjust the pH to about 5.6. Next, the reaction based on the total moles of mer units on the polymer. The mixture was transferred into a 300 mL Parr reactor with a polymer had a molecular weight of 35,000, and a mole ratio preSSure rating of at least 800 psi. The reactor then was of N-(hydroxyethoxy)ethyl acrylamide/acrylic acid/ assembled and purged with nitrogen for 60 minutes. The acrylamide of 33/41/26. Parr reactor was then slowly heated to 138 C. and held at 40 that temperature for 12 hours. Afterwards, the reactor was EXAMPLE 3 cooled to room temperature and the pressure released. The product was then transferred to Storage. The synthesis of a sodium acrylate/acrylamide/N- 'C NMR confirmed product formation. The content of (hydroxyethoxy)ethyl acrylamide terpolymer was effected methoxypropyl acrylamide was 34.2 mole %, based on the in the following manner with the reactants in the amounts 45 total moles of mer units on the polymer. The mole ratio of listed below: the product was 41/17/34 which represents acrylic acid/ acrylamide (including 6% imide mer units)/methoxypropyl Reactant Amount (g) acrylamide (including imide mer units). The product’s molecular weight was 11,000. Poly(NaAA/ACAm), 50/50 mol % 1OO.OO 50 solution polymer, 32.0 weight % EXAMPLE 5 Aminoethoxyethanol 32.OO Sulfuric Acid (95%) 11.5 The synthesis of a sodium acrylate/acrylamide/N-hydroxy (ethylamino)ethyl acrylamide terpolymer was effected in the To prepare the polymer, Poly(NaAA/AcAm) (50/50 mol 55 following manner with the reactants in the amounts listed % Sodium acrylate/acrylamide copolymer, 32.0 weight %, below: pH=5.2, 11,000 MW) was placed in a beaker, which was cooled using an ice bath. Aminoethoxyethanol (available from Huntsman Petrochemical Co., in Houston, Tex.) was Reactant Amount(g) added dropwise into the above water Solution with Vigorous 60 Poly(NaAA/ACAm), 50/50 mol % 8O.OO stirring. Afterwards, the solution was stirred for another 15 solution polymer, 24.0 weight % minutes. The pH of the reaction mixture was measured using (Aminoethylamine)ethanol 19.02 water-wet pH strips. Sulfuric acid was added to adjust the Sulfuric Acid (95%) 12.23 pH to about 5.6. Next, the reaction mixture was transferred into a 300 mL Parr reactor with a pressure rating of at least 65 To prepare the polymer, Poly(NaAA/AcAm) (50/50 mol 800 psi. The reactor then was assembled and purged with %, 24.0 weight %, pH=3.5, 15,000 MW) was placed in a nitrogen for 60 minutes. The Parr reactor was then slowly beaker, which was cooled using an ice bath. 5,880,237 19 20 (Aminoethylamino)ethanol (available from Aldrich Chem. N-(hydroxyethyl) acrylamide/AA/AcAm. The weight aver Co., in Milwaukee, Wis.) was added dropwise into the above age molecular weight of the product was 128,000, indicating water Solution with Vigorous stirring. Afterwards, the Solu the polymer was lightly crosslinked. To the stirred half tion was stirred for another 15 minutes. The pH of the amount of the product was added dropwise 50% NaOH reaction mixture was measured using water-wet pH Strips. Sulfuric acid was added to adjust the pH to about 5.6. Next, solution (19.24 g) at pH-11.39. The solution was further the reaction mixture was transferred into a 300 mL Parr stirred for 3.5 hours at room temperature. The pH was reactor with a pressure rating of at least 800 psi. The reactor adjusted to about 7 with 36% hydrochloric acid. The weight then was assembled and purged with nitrogen for 60 min average molecular weight was 42,600. NMR analysis results utes. The Parr reactor was then slowly heated to 138 C. and showed this product was a terpolymer of 33/50/17 held at that temperature for 14 hours. Afterwards, the reactor N-(hydroxyethyl)acrylamide/AA/Am. was cooled to room temperature and the preSSure released. The product was then transferred to Storage. EXAMPLE 8 'C NMR confirmed product formation. The content of hydroxy(ethylamino) ethyl acrylamide was 46 mole %, 15 The synthesis of a 35/51/14 mole percent based on the total moles of mer units on the polymer, N-(hydroxyethyl) acrylamide/acrylic acid/acrylamide ter representing both Secondary amide and imide mer units. The polymer was effected in the following manner. To 100 g of polymer also contained 51% of acrylic acid units. The a 52/48 AA/Am copolymer (42.7% polymer actives, weight product polymer’s molecular weight was 15,000. average molecular weight 34,100) in a Parr reactor was EXAMPLE 6 added 25.3 g of ethanolamine. The pH was adjusted with The synthesis of an acrylic acid/acrylamide/N- 18.8 g of 36% hydrochloric acid to about 5.3. The solution (hydroxyethoxy)ethyl acrylamide terpolymer was effected was purged with nitrogen for 1.0 hour and heated at in the following manner with the reactants in the amounts 136°-138° C. for about 7 hours. 37.0 g of 50% NaOH was listed below: 25 added dropwise to the stirred solution at pH-12 and at room temperature. After the solution was stirred for further 5 hours, the pH was adjusted with 36% hydrochloric acid to Reactant Amount(g) 8.5. NMR analysis results indicated the terpolymer compo Poly(AcAm), 50 weight % SO.OO sition was 35/51/14 N-(hydroxyethyl) acrylamide/AA/Am. Aminoethoxyethanol 12.9 The weight average molecular weight of the terpolymer was Deionized water SO.O 31,000. Sulfuric Acid (95%) 6.1 EXAMPLE 9 To prepare the polymer, Poly(AcAm) (50 wt %, available 35 from Aldrich Chemical Co., 10,000 MW) was placed in a To determine the disperSancy of the polymers, the fol beaker, which was cooled using an ice bath. Aminoethoxy lowing experimental procedure was followed. 1500 g Slips ethanol (available from Huntsman Petrochemical Co., in were prepared to 80 weight percent alumina powder (99.5% Houston, Tex.) was added dropwise into the above water calcinated alpha alumina oxide available from Alcan, C90 Solution with Vigorous Stirring. Afterwards, the Solution was 40 LSB Alumina) in water using 0.25 weight percent (polymer/ stirred for another 15 minutes. The pH of the reaction powder) of the polymer to be tested. mixture was measured using water-wet pH Strips. Sulfuric acid was added to adjust the pH to about 5.6. Next, the Each Slip was milled 3 hours in a 1-liter jar mill using reaction mixture was transferred into a 300 mL Parr reactor 1500 g milling media. Then, resulting slips were filtered with a pressure rating of at least 800 psi. The reactor then 45 through a 60 mesh Screen, and Brookfield Viscosity was was assembled and purged with nitrogen for 60 minutes. The measured using an LVT type Viscometer using a #2 Spindle. Parr reactor was then slowly heated to 138 C. and held at For comparison purposes, a commercially available, com that temperature for 14 hr. Afterwards, the reactor was mon alumina additive polymer was utilized. Polymer B is an cooled to room temperature and the pressure released. The ammonium poly(methacrylate) available from R. T. Vander product was then transferred to Storage. 50 bilt Co., Norwalk, Conn. Polymer A is a polymer synthe 'C NMR confirmed product formation. The content of sized according to the procedure of Example 2. N-(hydroxyethoxy) ethyl acrylamide was 19.6 mole %, The viscosity of a slurry must be suitable for necessary based on the total moles of mer units on the polymer. The handling and Spray drying. Although spray dry equipment product’s mole ratio was 32/44/20 which represents acrylic and running conditions may be adjusted to handle a variety acid/acrylamide/N-(hydroxyethoxy) ethyl acrylamide. 55 of Viscosities, larger particles will result from higher vis EXAMPLE 7 cosity slurries. The resultant large particles may lead to The synthesis of a 33/50/17 mole percent acrylic acid/ larger interstices between particles and hence a lower acrylamide/N-(hydroxyethyl) acrylamide terpolymer was strength. The binder may contribute to viscosity of the effected in the following manner. To 100 g of a 52/48 mole 60 continuous phase of the Slurry by virtue of its molecular ratio AA/ACAm copolymer (42.7% polymer actives, weight weight, Solubility, conformation in Solution, and possible average molecular weight=34,100) in a Parr reactor was incompatibility with the combination of powder and dis added 17.4 g of ethanolamine. The pH was adjusted with persant. Since a lower Viscosity is more desirable for 8.32 g of 36% hydrochloric acid to between 5.0 to 5.5. The ceramic applications, the results of Table I Show that a Solution was purged with nitrogen for 1.0 hour and heated at 65 polymer of this invention, prepared in accordance with the 138-142° C. for about 8 hours. NMR analysis results procedure of Example 2, works better than the common indicated the terpolymer composition was 38/52/10 treatment. 5,880,237 21 22 pressing force. The pellets were approximately 28.7 milli TABLE I meters in diameter and 5 to 6 millimeters in height. The dimensions and weights of the pellets were measured and Dispersancy in Alumina the pellets were crushed to determine the force required to Brookfield Viscosity (CP break them. Diametral compression strength (DCS) for each of the pellets was determined from the breaking force and Polymer 6 rpm 12 rpm 30 rpm 60 rpm the pellet dimensions. The average diametral compression A. 1OO 88 70 65 Strength in megapascals for each Set of three pellets is B 3OO 225 160 105 presented below in Table III. Green body diametral compressional Strength is important in ceramics applications for the following reasons. The EXAMPLE 10 principal function of the binder is to hold the compacted form together after pressing. The method utilized for deter The polymers were also tested in order to determine the mination of Suitable “green Strength” is the diametral com effects of Slip Viscosity as a function of binder type, accord 15 pression Strength or DCS of a cylindrical Section acroSS its ing to the following procedure. Deflocculated slips were diameter. DCS is actually a measure of tensile strength. The prepared as in the procedure of Example 9. To each slip So unit of measurement of preSSure tolerance is the megapascal prepared, the polymeric treatment to be tested was added, to (Mpa). Typical values for DCS of “green” parts are in the be a total of 4.0 weight percent (polymer/powder) level. range of 0.3-3.0 Mpa. Polymer A is a polymer prepared Next, each binder-containing Slip was propeller mixed at according to the procedure in Example 2. Polymer C is the 800 rpm for one hour. For any necessary dilution, deionized conventional additive described in Example 10. Therefore, water was added to attain the tabulated powder Solids level. since a higher DCS value indicates a more efficient binder, Finally, the slip Viscosity was measured using the method Table III shows that the polymers of the instant invention are described in Example 9. more efficient than a conventional treatment. D is another The results of Table II illustrate that even though the 25 additive that is often used in conjunction with these poly binder composition was varied, the polymers of this inven meric treatments for ceramic applications. tion caused lower Viscosity of the slip than the current Since a greater density is more desirable, the results of commercially available polymer treatment. In Table II, Poly Table III illustrate that the polymers of the instant invention mer C is a poly(Vinyl alcohol) which has a molecular weight are more advantageous in this respect also, as indicated by of 30,000 to 50,000 and is 88% hydrolyzed. It is available from Air Products of Allentown, Pa. Polymer A is a polymer the higher numbers obtained than in the case of the conven Synthesized according to the procedure in Example 2. For tional treatment. each polymer tested, 4 weight percent was utilized, and the The Springback characteristic is another important mea viscosity was measured at 3.14 sec'. Sure of the efficiency of a polymer for ceramicS applications 35 for the following reasons. Upon filling a die, the resulting compacted part must be Smoothly ejected, be as dense as TABLE II possible, and not Suffer Significant dimensional change from Slip Viscosity as a Function of Binder Type that of the die. Chemical additives have a major effect on the desired lubricity. The compressed powder will undergo Slip Powder Solids Polymer C Polymer A 40 StreSS relaxation in the form of expansion on release from the Weight Percent Slip BFV (cP) Slip BFV (cP) die. This phenomenon is referred to as “springback and is 76.4 >10,000 440 undesirable from the Standpoint of dimensional accuracy as 74.8 8,200 170 72 840 2O well as density and Strength. For this example, D was used 70 360 as a plasticizer. Maintenance of net shape is important, as the 45 occurrence of a larger amount of Springback can cause "Brookfield viscosity lamination defects, or undesirable density gradients. Therefore, the lower values for springback obtained for the EXAMPLE 11 polymers of this invention in Table III demonstrate that such polymers are more efficient than the conventional treatment. A copolymer Synthesized by the procedure described in 50 The pressure required for die ejection was also measured. Example 2 above, was tested as a binder for alumina The same test equipment was utilized as described above, particles of the type that are commonly used for producing except that after the pellet is pressed, a plunger on the ceramic materials. bottom of the apparatus is utilized to apply force to the die. The slip preparation described in Example 10 was utilized A lower pressure is more desirable, and was obtained by the in this Example to further examine the characteristics of the 55 use of polymers of the instant invention over polymers binders. conventionally utilized for ceramic purposes. The milled slurry was spray dried in a Yamato DL-41 laboratory Spray dryer. Dryer operating conditions were: TABLE III 250 C. air inlet temperature, atomizing air setting of 1.2, Slurry feed pump Setting of 5, and drying air feed rate of 0.7 60 Comparison of Green Body Properties cubic meters per minute. A dry powder was produced which was recovered, Screened and Stored overnight in a 20 percent Polymeric Treatment relative humidity chamber. Pressure (PS) A. C A + D C + D' A + D C + D? The Screened powder was pressed into nine pellets in a Green Body Diametrial Compressional Strength (MPa) Carver laboratory press, three at 5,000 pounds per Square 65 inch pressing force, three at 15,000 pounds per Square inch 5,000 O.64 O.2O 0.55 O.45 O.45 O.38 pressing force, and three at 25,000 pounds per Square inch 5,880,237 23 24 A) a mer unit of the formula TABLE III-continued R5 R6 I Comparison of Green Body Properties --i- Polymeric Treatment 5 =o Pressure (PS) A. C A + D C + D' A + D C + D? R 15,000 1.76 O.98 1.24 1.01 1.04 0.79 25,000 2.42 1.19 1.79 1.30 1.31 O.91 (CHR2CHR3Het! (- CHR2CHR3Het2 , R4 Pellet Green Density (g/cc) 1O wherein R is selected from the group consisting of 5,000 2.28 2.09 2.30 2.23 2.33 2.34 hydrogen, and C-C alkyl, p and q are integers from 15,000 2.52 2.38 2.51 2.43 2.54 2.50 1-10; R and Rare selected from the group consisting 25,000 2.60 2.43 2.61 2.51 2.60 2.57 of hydrogen and C-C alkyl, Het and Het selected Percent Springback in Green Bodies from the group consisting of O and NH, with the 15 5,000 O.O6 O.22 -0.02 O.19 O.11 O.12 proviso that Het' and Het are not both oxygen; R is 15,000 O.11 O.22 O.12 O.19 O.14 O.18 Selected from the group consisting of hydrogen, 25,000 O.16 O.23 O.14 O.19 O.15 O.18 phosphate, sulfate and C-Co alkyl; R and Rare Pressure Required for Die Ejection (PSI) Selected from the group consisting of hydrogen, 5,000 O.OO 7.93 O.96 29.16 7.46 22.47 carboxylate, C-C alkyl, and a cycloalkyl group of 1 15,000 1986 49.37 26.57 73.94 39.08 64.57 to 6 carbon atoms formed by the linkage of R and R' 25,000 41.30 77.87 42.12 101.14 59.48 92.OO as a ring; and B) a mer unit Selected from the group consisting of acrylic D'= poly(ethylene oxide/propylene oxide) ether linked to (1,2- ethandiyldintrilo) tetrakis propanol, 0.8 weight percent acid, methacrylic acid, acrylamide, maleic anhydride, D°= as D" above, 3.0 weight percent itaconic acid, Vinyl Sulfonic acid, Styrene Sulfonate, 25 N-tertbutylacrylamide, butoxymethylacrylamide, N,N- dimethylacrylamide, Sodium acrylamidomethyl pro pane Sulfonic acid, Vinyl alcohol, Vinyl acetate, N-Vinyl pyrrollidone, maleic acid, and combinations thereof. EXAMPLE 12 2. An unfired, ceramic precursor material comprising a mixture of: A. a ceramic powder Selected from the group consisting of aluminum oxide, Silicon nitride, aluminum nitride, The procedures utilized in Example 11 were utilized to Silicon carbide, Silicon oxide, magnesium oxide, lead obtain the results of Table IV. Rather than utilize a range of Oxide, Zirconium oxide, titanium oxide, Steatite, barium preSSures as in the previous example, the characteristics titanate, lead Zirconate titanate, clays, ferrite, yttrium were evaluated at a single density. The pressure which was 35 Oxide, Zinc oxide, tungsten carbide, Sialon, neodymium required to produce that density was recorded in the table. Oxide and combinations thereof and The polymers A, C and D are as defined in Example 11 B. a water Soluble polymer having: above. Even when measured at pellets pressed to a constant i) a mer unit of the formula density, the polymers of the instant invention provide Supe rior performance over the conventional polymeric treatment. 40 I

TABLE IV Comparative Green Body Properties at Green Density 2.4 g/mL. (=o 45 Polymeric Press Pressure DCS Ejection Force R Treatment Required PSI (MPa) % Springback (psi) (CHR2CHR3Het! (- CHR2CHR3Het2 , R4 A. 10,000 1.22 O.08 1O wherein R' is selected from the group consisting of C 19,200 1.1 O.23 63 hydrogen, and C-C alkyl, p and q are integers from A + D' 9,700 O.94 O.04 13 50 C + D' 13,300 O.88 O.19 67 1-10; R and R are selected from the group con A + D? 8,200 O.65 O.12 18 sisting of hydrogen and C-C alkyl; Het' and Hetf A + D? 8,800 O.56 O.14 39 selected from the group consisting of O and NH with D'= poly(ethylene oxide?propylene oxide) ether linked to (1,2- the proviso that Het' and Het’ are not both oxygen; ethandiyldintrilo) tetrakis propanol, 0.8 weight percent R" is selected from the group consisting of hydrogen, D°= as D" above, 3.0 weight percent 55 phosphate, Sulfate and C-Co alkyl; R and Rare Selected from the group consisting of hydrogen, carboxylate, C-C alkyl, and a cycloalkyl group of 1 to 6 carbon atoms formed by the linkage of R and Changes can be made in the composition, operation and R as a ring; and arrangement of the method of the present invention 60 ii) a mer unit Selected from the group consisting of described herein without departing from the concept and acrylic acid, methacrylic acid, acrylamide, maleic Scope of the invention as defined in the following claims: anhydride, itaconic acid, Vinyl Sulfonic acid, Styrene Sulfonate, N-tert butyl acrylamide, butoxymethylacrylamide, N,N-dimethylacrylamide, We claim: 65 Sodium acrylamidomethyl propane Sulfonic acid, 1. A binder for ceramic materials that comprises a water Vinyl alcohol, Vinyl acetate, N-Vinyl pyrrollidone, Soluble polymer having: maleic acid, and combinations thereof. 5,880,237 25 26 3. A method for preparing a ceramic material, which ii) a mer unit Selected from the group consisting of comprises the Steps of: acrylic acid, methacrylic acid, acrylamide, maleic A) mixing a ceramic powder with an aqueous solution anhydride, itaconic acid, Vinyl Sulfonic acid, Styrene containing a water-soluble polymer to produce a slurry, Sulfonate N-tert butyl acrylamide Said water-Soluble polymer having: 5 butoxymethylacrylamide,s N,N-dimethylacrylamide,s i) a mer unit of the formula Sodium acrylamidomethyl propane Sulfonic acid, R5 R6 I Vinyl alcohol, Vinyl acetate, N-Vinyl pyrrollidone, maleic acid, and combinations thereof; -C-CH 1O B) drying the slurry by a process Selected from the group (=o consisting of fluidized bed spray drying, and Spray NR1 drying to produce particles which include Said copoly mer, (CHRCHRHet' (-CHR-CHRHet? R' C) compacting the particles by a process selected from the wherein R is selected from the group consisting of 15 group consisting of dry pressing, roll compaction and hydrogen, and iC3 alkyl, p and q are integers from isostatic pressing to produce an aggregate Structure; 1-10; R and R are selected from the group con- and sisting of hydrogen and C-C alkyl; Het and Hetf selected from the group consisting of O and NH with D) heating the aggregate structure to produce a fired the proviso that Het' and Het are not both oxygen; CCC a terial. R" is selected from the group consisting of hydrogen, 20 4. The method of claim 3 wherein the particles are phosphate, sulfate and C-Co alkyl; R and Rare produced by granulation and the Step of compacting the Selected from the group consisting of hydrogen, particles to produce an aggregate Structure is Selected from carboxylate, C-C alkyl, and a cycloalkyl group of the group consisting of dry pressing and isostatic pressing. 1 to 6 carbon atoms formed by the linkage of Rand R as a ring; and k . . . .