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WO 2U11/112647 Al (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date Χ i 15 September 2011 (15.09.2011) WO 2U1 1/1 12647 Al (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every C06C 5/00 (2006.01) C06C 5/06 (2006.01) kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, (21) International Application Number: CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO, PCT/US201 1/027639 DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (22) International Filing Date: HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, ' March 201 1 (09.03.201 1) KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, (25) Filing Language: English NO, NZ, OM, PE, PG, PH, PL, PT, RO, RS, RU, SC, SD, (26) Publication Langi English SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (30) Priority Data: 61/3 11,857 ' March 2010 (09.03.2010) US (84) Designated States (unless otherwise indicated, for every kind of regional protection available): ARIPO (BW, GH, (71) Applicant (for all designated States except US): DYNO GM, KE, LR, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, NOBEL INC. [US/US]; 2795 East Cottonwood Parkway, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, Suite 500, Salt Lake City, Utah 84121 (US). TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, (72) Inventors; and LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, (75) Inventors/ Applicants (for US only): PLITT, Tyson J. SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, [US/US]; 17 Goose Green Rd., Barkhamsted, Connecticut GW, ML, MR, NE, SN, TD, TG). 06063 (US). TWAROG, Jr., Joseph W. [US/US]; 4 1 Horseshoe Circle, Barkhamsted, Connecticut 06063 (US). Declarations under Rule 4.17 : DORMAN, Mark [US/US]; 19 Heather Lane, North — as to applicant's entitlement to apply for and be granted Granby, Connecticut 06060 (US). OVERSTROM, Ray¬ a patent (Rule 4.1 7(H)) mond T. [US/US]; 110 Lexington Rd., Glastonbury, Con necticut 06033 (US). CHILDS, John [US/US]; 11 Tim — as to the applicant's entitlement to claim the priority of ber Lane, Shelburne, Vermont 05482 (US). the earlier application (Rule 4.17(Hi)) (74) Agent: LIBERT, Victor E.; Cantor Colburn LLP, 20 Published: Church St., 22nd Floor, Hartford, Connecticut — with international search report (Art. 21(3)) 06103-3207 (US). (54) Title: SEALER ELEMENTS, DETONATORS CONTAINING THE SAME, AND METHODS OF MAKING (57) Abstract: A gas-impermeable sealer element (24, 124) for a detonator or other explosive initiation device includes a non-re active sleeve (26, 126) having a channel (28, 128) formed therein. A reactive material strip (30, 130) is sealed within the channel for transmission of an explosive's initiation signal through the sealer element (24, 124), either alone or in cooperation with transfer o charges located at the input and/or output end of the non-reactive sleeve (26, 126). The reactive material strip (30, 130) comprises a reactive metal wire or other substrate (34) having on one or both sides thereof a layer of reactive material (30, 130, 36), either reactive metal foils which react exothermically when ignited, or a deposited fuel-oxidizer reactive material. The reactive materials, o upon being energized, react exothermically in the absence of atmospheric oxygen or other extraneous oxidizer and so may be en capsulated, sealed or otherwise isolated from the atmosphere in use. SEALER ELEMENTS, DETONATORS CONTAINING THE SAME, AND METHODS OF MAKING BACKGROUND OF THE INVENTION CROSS-REFERENCE TO RELATED APPLICATION [0001] This application claims the benefit of priority of provisional patent application Se¬ rial No. 61/31 1,857, filed on March 9, 2010, entitled "SEALER ELEMENTS, DETONATORS CONTAINING THE SAME, AND METHODS OF MAKING". Field of the Invention [0002] The present invention relates to gas-impermeable sealer elements for pyrotechnic delay detonators and to methods of making such sealer elements. The sealer elements of the pre¬ sent invention comprise encapsulated reactive materials such as multilayer metal foils or wires or oxidation/reduction reaction pairs deposited on suitable substrates, or the like. Description of Related Art [0003] It is known that reactive metal foils may be utilized in a multilayered foil structure which, upon appropriate excitation, undergoes an exothermic chemical reaction to generate a significant amount of heat. U.S. Patent 6,736,942, issued May 18, 2004 to T.E. Weihs et al., dis¬ closes (column 1, lines 34-44) that such multilayer foils may be used primarily as sources of highly localized (column 2, line 26 et seq.) heat for various purposes including ignition in virtu¬ ally any environment including air, vacuum, water, etc. Other examples of such reactive multi¬ layer foils are described in U.S. Patent 6,863,992, issued March 8, 2005 to Weihs et al. The en¬ tire disclosures of the two Weihs et al. patents are incorporated by reference herein. [0004] Such reactive multilayer foils are fabricated by depositing onto a substrate multi¬ ple alternating thin layers of dissimilar materials, e.g., metals, by any suitable process. The dis¬ similar metals, e.g., nickel and aluminum, may be comprised of any materials which undergo self-sustaining exothermic reactions such as alloying of the metals, or other exothermic changes in chemical bonding, in response to being heated to an elevated (initiation) temperature. Atmos¬ pheric oxygen or other extraneous oxidizers are not required for such reactions, which are there- fore referred to herein as "self-sustaining" reactions. Metallic multilayered foil laminates com¬ prising hundreds of alternating, extremely thin layers of such dissimilar metals are commercially available from Reactive Nanotechnologies, Inc. of Hunt Valley, Maryland. [0005] A product sold under the trademark PYROFUZE ® is a wire manufactured by Sigmund Cohen Corp. of Mount Vernon, New York, and consisting of at least two metallic ele¬ ments in intimate contact with each other, including arrangements of one metal as a sheath en¬ casing the other metal, thereby providing a laminated reactive multilayer wire. A plurality of thin sheaths of alternating different reactive metals may overlie each other. As is the case with the multilayer foils, when the two metallic elements of the wire are brought to their initiation temperature, they alloy rapidly, resulting in an exothermic, rapid reaction without necessity of atmospheric oxygen or other extraneous oxidizer. [0006] U.S. patent application publication US 2006/0236887 A l of John Childs et al. for "Delay Units and Method of Making the Same" was published October 26, 2006, and matured into U.S. Patent 7,650,840 ("the '840 Patent"). The '840 Patent discloses a delay unit for detona¬ tors comprised of a timing strip 14 (Figure 1) deposited on a substrate 12 and comprised of a re¬ active material which emits energy upon being heated to its initiation temperature. The energetic material, which may comprise explosive, pyrotechnic or other energy-emitting material such as a fuel and an oxidizer, may be applied to the substrate by ink compositions containing particles of the energetic material dispersed in a continuous liquid phase, and some or all of the energetic material particles may be nanosize particles. See the Abstract and col. 2, lines 43-55. The ink dries or cures to form a solid, agglomerated mass, i.e., a mass without loose particulate materials. [0007] U.S. Patent Application 1/674,300, filed on February 13, 2007, in the name of Tyson J. Plitt et al. and entitled "Delay Elements, Detonators Containing the Same and Methods of Making" ("the Plitt et al. Application"), now abandoned, discloses a delay element suitable for use in otherwise conventional detonators. The delay element comprises a substrate upon which is disposed a reactive material which may be a reactive multilayer laminate of at least two differ¬ ent materials, e.g., aluminum and nickel. [0008] While the reactive materials of the '840 Patent and the Plitt et al. Application may be similar or identical to those utilized in the present invention, both the '840 Patent and the Plitt et al. Application require that the reactive material must be configured into a zig-zag, serpentine or coiled path, and/or multiple paths connected in series, in order to increase the effective travel path of the reaction and commensurately increase the time delay provided by the delay element. See, e.g., Figure 1 of the '840 Patent and Figures 9 and 11 of the Plitt et al. Application. [0009] In blasting systems, signal transmission lines, such as electrical wires, detonating cord, shock tube and the like serve as energy sources to transmit an electric or non-electric ener¬ getic initiation signal to detonators or other devices. As is well known in the art, it is often nec¬ essary to attain precisely controlled delays between receipt of the initiation signal by the detona¬ tor and initiation of the output charge of the detonator in order to effectuate the desired timing of sequential detonations in a given shot, which may contain hundreds of detonators. Typical delay periods range from 9 to 9,600 milliseconds or more, for example, 9, 25, 350, 500 and 1,000 mil¬ liseconds. In order to attain such delays, conventional pyrotechnic delay elements are disposed within the detonator between the energy source, i.e., the signal transmission line, and the output charge.
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