IP Library › Granted Patent US 12,215,236
Granted Patent B2
US 12,215,236 · App. 17/691,006 · Granted Feb 4, 2025

Multifunctional reactive inks, methods of use and manufacture thereof

Inventors: Kyle Sullivan (Pleasanton, CA); John M. Densmore (Livermore, CA); Eric Duoss (Dublin, CA); Alexander E. Gash (Brentwood, CA); Joshua Kuntz (Livermore, CA); John Vericella (Oakland, CA)
Assignee: Lawrence Livermore National Security, LLC
C09D11/02B29C64/118C09D11/03Y10T428/24893
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 12,215,236
App. No.
17/691,006
Granted
Feb 4, 2025
Kind
B2
Abstract

In one embodiment, a method includes dispersing a plurality of particles in a solution to form a dispersion; and adding a stabilizing agent to the dispersion in an amount sufficient to cause the dispersion to exhibit one or more predetermined rheological properties, wherein the particles are characterized by a core-shell configuration, wherein the core-shell configuration includes a core formed from a first material and a shell formed from a second material, wherein the first material and the second material form a combustible composition and/or a reactive binary composition that is configured to complete a self-propagating reaction and/or a self-sustaining reaction upon initiation thereof. Corresponding materials, and methods of using such materials, are also disclosed.

Claims (40)

1. A composition of matter, comprising:

a plurality of particles in a dispersion;

wherein the particles are characterized by a core-shell configuration;

wherein the core-shell configuration includes a core formed from a first material and a shell formed from a second material;

wherein the first material and the second material form a combustible composition and/or a reactive binary composition that is configured to complete a self-propagating reaction and/or a self-sustaining reaction upon initiation thereof; and

wherein the composition of matter exhibits one or more predetermined rheological properties that include being structurally self-supporting during deposition of the composition of matter onto a substrate and prior to initiation of the self-propagating reaction and/or the self-sustaining reaction.

2. The composition of matter as recited in claim 1 , wherein the particles are characterized by an average diameter in a range from about 0.01 microns to about 100 microns.

3. The composition of matter as recited in claim 1 , wherein the dispersion further comprises one or more stabilizing agents, and wherein the one or more stabilizing agents include one or more components selected from the group consisting of: at least one polymer, at least one surfactant, at least one acid, at least one base, at least one electrolyte and/or at least one polyelectrolyte, and at least one salt.

4. The composition of matter as recited in claim 1 , wherein the dispersion further comprises one or more stabilizing agents, wherein the one or more stabilizing agents include at least one polymer, and wherein the at least one polymer is selected from the group consisting of: polyvinylpyrrolidone (PVP), polyacrylic acid, polyethyleneimine, and ammonium polymethacrylate.

5. The composition of matter as recited in claim 1 , further comprising at least one additional component selected from the group consisting of: a humectant, a graded volatility solvent system, a brazing agent, and a gelation agent.

6. The composition of matter as recited in claim 1 , wherein either:

the first material comprises one or more constituents selected from the group consisting of: aluminum, boron, barium, beryllium, bismuth, carbon, calcium, cerium, chromium, copper, iron, germanium, hafnium, lanthanum, lithium, magnesium, manganese, molybdenum, sodium, niobium, palladium, plutonium, sulfur, silicon, tantalum, thorium, uranium, yttrium, zinc, and zirconium, and combinations thereof, and the second material comprises one or more constituents selected from the group consisting of silver oxides, boron, boron oxides, bismuth, bismuth oxides, carbon, calcium, cerium, cobalt, cobalt oxides, chromium, chromium oxides, copper, copper oxides, iron, iron oxides, hafnium, mercury oxides, iodine oxides, potassium, lanthanum, lithium, magnesium, manganese, manganese oxides, molybdenum, molybdenum oxides, sodium, niobium, niobium oxides, nickel, nickel oxides, lead, lead oxides, palladium, palladium oxides, praseodymium, platinum, plutonium, sulfur, antimony, selenium, silicon, silicon oxides, samarium, tin, tin oxides, strontium, tantalum, tantalum oxides, tellurium, thorium, titanium, titanium oxides, uranium, uranium oxides vanadium, vanadium oxides, tungsten, tungsten oxides, yttrium, zinc, zirconium, and combinations thereof; or

the first material comprises one or more constituents selected from the group consisting of: silver oxides, boron, boron oxides, bismuth, bismuth oxides, carbon, calcium, cerium, cobalt, cobalt oxides, chromium, chromium oxides, copper, copper oxides, iron, iron oxides, hafnium, mercury oxides, iodine oxides, potassium, lanthanum, lithium, magnesium, manganese, manganese oxides, molybdenum, molybdenum oxides, sodium, niobium, niobium oxides, nickel, nickel oxides, lead, lead oxides, palladium, palladium oxides, praseodymium, platinum, plutonium, sulfur, antimony, selenium, silicon, silicon oxides, samarium, tin, tin oxides, strontium, tantalum, tantalum oxides, tellurium, thorium, titanium, titanium oxides, uranium, uranium oxides vanadium, vanadium oxides, tungsten, tungsten oxides, yttrium, zinc, zirconium, and combinations thereof; and the second material comprises one or more constituents selected from the group consisting of: aluminum, boron, barium, beryllium, bismuth, carbon, calcium, cerium, chromium, copper, iron, germanium, hafnium, lanthanum, lithium, magnesium, manganese, molybdenum, sodium, niobium, palladium, plutonium, sulfur, silicon, tantalum, thorium, uranium, yttrium, zinc, and zirconium, and combinations thereof; and

wherein the first material and the second material collectively exclude combinations of:

aluminum and iron oxides;

aluminum and silicon oxides;

aluminum and chromium oxides;

aluminum and bismuth oxides;

aluminum and manganese oxides; and

aluminum and bismuth oxides.

7. A method for forming a composition of matter as recited in claim 1 , the method comprising:

dispersing the plurality of particles in a solution to form the dispersion.

8. The method as recited in claim 7 , wherein the particles comprise from about 30 vol % to about 80 vol % of the dispersion.

9. The method as recited in claim 7 , wherein the dispersion comprises the particles dispersed throughout a liquid metal matrix.

10. The method as recited in claim 7 , wherein the particles are characterized by an average diameter in a range from about 0.01 microns to about 100 microns.

11. The method as recited in claim 7 , wherein the solution comprises a stabilizing agent including one or more components selected from the group consisting of: at least one polymer, at least one surfactant, at least one acid, at least one base, at least one electrolyte and/or at least one polyelectrolyte, and at least one salt.

12. The method as recited in claim 7 , wherein the solution comprises a stabilizing agent including at least one polymer, and wherein the at least one polymer is selected from the group consisting of: polyvinylpyrrolidone (PVP), polyacrylic acid, polyethyleneimine, and ammonium polymethacrylate.

13. The method as recited in claim 7 , further comprising adding at least one additional component to the dispersion, wherein the at least one additional component is selected from the group consisting of: a humectant, a graded volatility solvent system, a brazing agent, and a gelation agent.

14. A method of utilizing the composition of matter as recited in claim 1 , the method comprising:

depositing the composition of matter on a substrate.

15. The method as recited in claim 14 , wherein the self-propagating reaction and/or the self-sustaining reaction renders at least surface(s) of the substrate onto which the composition of matter is deposited conductive.

16. The method as recited in claim 14 , wherein the self-propagating reaction and/or the self-sustaining reaction comprises a thermite reaction and/or an intermetallic reaction.

17. The method as recited in claim 14 , further comprising initiating the self-propagating reaction and/or the self-sustaining reaction.

18. The method as recited in claim 14 , wherein the composition of matter is deposited as a first layer, the method further comprising: depositing one or more additional layers of the composition of matter above the first layer.

19. The method as recited in claim 18 , further comprising initiating the self-propagating reaction and/or the self-sustaining reaction in each of the one or more additional layers subsequent to depositing the one or more additional layers and prior to depositing a subsequent second one of the one or more additional layers of the composition of matter.

20. The method as recited in claim 14 , further comprising:

depositing one or more additional layers of the composition of matter and one or more layers of a second composition of matter to form a structure comprising alternating layers of the composition of matter and the second composition of matter, wherein the second composition of matter comprises a non-energetic material; and

initiating the self-propagating reaction and/or the self-sustaining reaction in each layer of the composition of matter;

wherein each self-propagating and/or self-sustaining reaction generates heat; and

wherein the heat generated by each self-propagating reaction and/or each self-sustaining reaction at least partially melts at least one adjacent layer comprising the second composition of matter.

Assignments (2)
CONFIRMATORY LICENSE (SEE DOCUMENT FOR DETAILS) Recorded May 13, 2022
From: LAWRENCE LIVERMORE NATIONAL SECURITY, LLC
To: U.S. DEPARTMENT OF ENERGY
Reel/Frame 060064/0181 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 25, 2022
From: SULLIVAN, KYLE; DENSMORE, JOHN M.; DUOSS, ERIC; GASH, ALEXANDER E.; KUNTZ, JOSHUA; VERICELLA, JOHN
To: LAWRENCE LIVERMORE NATIONAL SECURITY, LLC
Reel/Frame 059399/0361 →
Continuity (3)
Continuation 16452301 · Jun 25, 2019
Division 14049141 · Oct 8, 2013
Related Publication 20220195220A1 · Jun 23, 2022
References Cited (70)
US 3325316A · MacDonald · 1967 [cited by applicant]
US 3600163A · Badia et al. · 1971 [cited by applicant]
US 3753810A · Leneveu et al. · 1973 [cited by applicant]
US 3794535A · Bertrand et al. · 1974 [cited by applicant]
US 5980785A · Xi et al. · 1999 [cited by applicant]
US 6030755A · Matsumoto et al. · 2000 [cited by applicant]
US 6051242A · Patel et al. · 2000 [cited by applicant]
US 6156130A · Hegner et al. · 2000 [cited by applicant]
US 8048242B1 · Tappan et al. · 2011 [cited by applicant]
US 8460451B2 · Xu et al. · 2013 [cited by applicant]
US 10377090B2 · Sullivan et al. · 2019 [cited by applicant]
US 11370927B2 · Sullivan et al. · 2022 [cited by applicant]
US 20030230335A1 · Tsukahara · 2003 [cited by applicant]
US 20040247931A1 · Weihs et al. · 2004 [cited by applicant]
US 20050189520A1 · Okada et al. · 2005 [cited by applicant]
US 20070224441A1 · Bunyan · 2007 [cited by applicant]
US 20080000382A1 · Li et al. · 2008 [cited by applicant]
US 20090108229A1 · Silverman et al. · 2009 [cited by applicant]
US 20090148680A1 · Toyoda · 2009 [cited by applicant]
US 20090186195A1 · Spraker et al. · 2009 [cited by applicant]
US 20110127314A1 · Heinrich · 2011 [cited by examiner]
US 20120061454A1 · Rudd et al. · 2012 [cited by applicant]
US 20120141747A1 · Deeter et al. · 2012 [cited by applicant]
US 20120231159A1 · Weihs et al. · 2012 [cited by applicant]
US 20120231232A1 · Xu et al. · 2012 [cited by applicant]
US 20150099102A1 · Sullivan et al. · 2015 [cited by applicant]
US 20200023571A1 · Sullivan et al. · 2020 [cited by applicant]
US 20220275222A1 · Sullivan et al. · 2022 [cited by applicant]
EP 0970776A1 · 2000 [cited by applicant]
EP 0988919A1 · 2000 [cited by applicant]
WO 2008013806A2 · 2008 [cited by applicant]
US 6,875,521 B2, 04/2005, Weihs (withdrawn) [cited by applicant]
Yen et al., “Reactive Metals in Explosives,” Propellants, Explosives, Pyrotechnics, vol. 37, No. 3, 2012, pp. 143-155 (abstract only). [cited by applicant]
International Search Report and Written Opinion from International Application No. PCT/US2014/059735, dated Jan. 26, 2015. [cited by applicant]
Sullivan et al., U.S. Appl. No. 14/049,141, filed Oct. 8, 2013. [cited by applicant]
Restriction Requirement from U.S. Appl. No. 14/049,141, dated Jan. 23, 2015. [cited by applicant]
Non-Final Office Action from U.S. Appl. No. 14/049,141, dated May 6, 2015. [cited by applicant]
Final Office Action from U.S. Appl. No. 14/049,141, dated Oct. 22, 2015. [cited by applicant]
Advisory Action from U.S. Appl. No. 14/049,141, dated Apr. 6, 2016. [cited by applicant]
Anon, “Field Welding Alternatives,” Modern Railroads, vol. 42, No. 8, Aug. 1987, pp. 39-40. [cited by applicant]
Fischer et al., “A Survey of Combustible Metals, Thermites, and Intermetallics for Pyrotechnic Applications,” 32nd AIAA/ASME/SAE/ASEE Joint Propulsion Conference, Jul. 1-3, 1996, pp. 1-15. [cited by applicant]
Grieseler et al., “Bonding of low temperature co-fired ceramics to copper and to ceramic blocks by reactive aluminum/nicke multilayers,” 2011 Wiley-VCH Verlag Gmbh & Co., Physica Status Solidi A, vol. 209, No. 3, 2012, … [cited by applicant]
Krylov et al. “Possibilities of Producing Thermite Mixtures Based on B4C-Metal and SiC-Metal Composites,” Poroshkovaya Metallurgiya, vol. 12, No. 156, Dec. 1975, pp. 57-60,. [cited by applicant]
Matsuura et al., “Development of Freeform Fabrication of Intermetallic Compounds,” 2001 Acta Metallurgica Inc., Scripta Materialia, vol. 44, No. 3, 2001, pp. 539-544. [cited by applicant]
Matsuura et al., “In-situ Joining of Nickel Monoaluminide to Iron by Reactive Sintering,” ISIJ International, vol. 38, No. 3, 1998, pp. 310-315. [cited by applicant]
Matsuura et al., “Joining and Coating of Intermetallic Compounds to Metallic Materials by Reactive Casting,” International Journal of Self-Propagating High-Temperature Synthesis, vol. 12, No. 3, 2003, pp. 223-237. [cited by applicant]
Matsuura et al., “Joining of NiAl to Iron-Based Alloys by Reactive Casting,” Metallurgical and Materials Transactions A, vol. 33A, Jul. 2002, pp. 2073-2080. [cited by applicant]
Matsuura et al., “Padding, Welding and Freeform Fabrication of Nickel Aluminide Intermetallic Compound by Reactive Rapid Prototyping Process,” The Japan Institute of Light Metals, Materials Transactions, vol. 43, No. 5,… [cited by applicant]
Matsuura et al., “Use of SHS Reaction Between Powder and Droplets for Coating, Welding and Freeform Fabrication of Intermetallics,” Materials Science Forum, vol. 426-432, 2003, pp. 4271-4276. [cited by applicant]
Orling et al., “Self-Propagating High-Temperature Synthesis as a Process for Joining Materials,” Welding Research Supplement, Mar. 1996, pp. 93-100. [cited by applicant]
Pascal et al., “Joining of nickel monoaluminide to a superalloy substrate by high pressure self-propagating high-temperature synthesis,” Journal of Alloys and Compounds, vol. 337, 2002, pp. 221-225. [cited by applicant]
Walker et al., “Reactive Silver Inks for Patterning High-Conductivity Features at Mild Temperatures,” Journal of the American Chemical Society, vol. 134, 2012, pp. 1419-1421. [cited by applicant]
Zhang et al., “A1/Ni Multilayer Used as a Local Heat Source for Mounting Microelectronic Components,” International Conference on Electronic Packaging Technology & High Density Packaging (ICEPT-HDP), 2009, pp. 838-842. [cited by applicant]
Sullivan et al., “Electrophoretic Deposition of Thermites onto Micro-Engineered Electrodes Prepared by Direct-Ink Writing,” Journal of Physical Chemistry B, vol. 117, No. 6, Aug. 16, 2012, pp. 1686-1693. [cited by applicant]
Cao et al., “Joining of TiAl intermetallic by self-propagating high-temperature synthesis,” Journal of Materials Science, vol. 41, No. 15, May 2006, pp. 4720-4724. [cited by applicant]
Eluri et al., “Silver nanoparticie-assisted diffusion brazing of 3003 Al alloy for microchannel applications,” Materials and Design, vol. 36, Apr. 2012, pp. 13-23. [cited by applicant]
Examiner's Answer to Appeal Brief from U.S. Appl. No. 14/049,141, dated Aug. 5, 2016. [cited by applicant]
Patent Board Decision on Appeal from U.S. Appl. No. 14/049,141, dated Dec. 20, 2018. [cited by applicant]
Ex Parte Quayle from U.S. Appl. No. 14/049,141, dated Jan. 3, 2022. [cited by applicant]
Notice of Allowance from U.S. Appl. No. 14/049,141, dated Apr. 2, 2019. [cited by applicant]
Sullivan et al., U.S. Appl. No. 16/452,301, filed Jun. 25, 2019. [cited by applicant]
Restriction Requirement from U.S. Appl. No. 16/452,301 dated May 26, 2021. [cited by applicant]
Non-Final Office Action from U.S. Appl. No. 16/452,301, dated Aug. 16, 2021. [cited by applicant]
Notice of Allowance from U.S. Appl. No. 16/452,301 dated Feb. 18, 2022. [cited by applicant]
Corrected Notice of Allowance from U.S. Appl. No. 16/452,301 dated Apr. 4, 2022. [cited by applicant]
Restriction Requirement from U.S. Appl. No. 17/749,920 , dated Dec. 5, 2023. [cited by applicant]
Sullivan et al., U.S. Appl. No. 17/749,920, filed May 20, 2022. [cited by applicant]
Non-Final Office Action from U.S. Appl. No. 17/749,920, dated May 7, 2024. [cited by applicant]
Notice of Allowance from U.S. Appl. No. 17/749,920, dated Sep. 9, 2024. [cited by applicant]
Corrected Notice of Allowance from U.S. Appl. No. 17/749,920, dated Oct. 29, 2024. [cited by applicant]