US20210323891A1 - Material and method of manufacture for engineered reactive matrix compositions - Google Patents
Material and method of manufacture for engineered reactive matrix compositions Download PDFInfo
- Publication number
- US20210323891A1 US20210323891A1 US17/359,765 US202117359765A US2021323891A1 US 20210323891 A1 US20210323891 A1 US 20210323891A1 US 202117359765 A US202117359765 A US 202117359765A US 2021323891 A1 US2021323891 A1 US 2021323891A1
- Authority
- US
- United States
- Prior art keywords
- reactive
- matrix composite
- microns
- binder
- primary core
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000011159 matrix material Substances 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title abstract description 38
- 239000000203 mixture Substances 0.000 title description 13
- 238000004519 manufacturing process Methods 0.000 title description 12
- 239000002131 composite material Substances 0.000 claims abstract description 64
- 239000011230 binding agent Substances 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000000919 ceramic Substances 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims description 91
- 238000000576 coating method Methods 0.000 claims description 60
- 239000011248 coating agent Substances 0.000 claims description 48
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 38
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 30
- 239000011777 magnesium Substances 0.000 claims description 27
- 229910052749 magnesium Inorganic materials 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 229910052725 zinc Inorganic materials 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 15
- 229910002804 graphite Inorganic materials 0.000 claims description 14
- 239000010439 graphite Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 4
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 4
- 239000012267 brine Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 229920002313 fluoropolymer Polymers 0.000 claims description 3
- 239000007769 metal material Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 3
- UJXVAJQDLVNWPS-UHFFFAOYSA-N [Al].[Al].[Al].[Fe] Chemical compound [Al].[Al].[Al].[Fe] UJXVAJQDLVNWPS-UHFFFAOYSA-N 0.000 claims description 2
- 229910021326 iron aluminide Inorganic materials 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 5
- 229910052735 hafnium Inorganic materials 0.000 claims 5
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims 5
- 229910052750 molybdenum Inorganic materials 0.000 claims 5
- 239000011733 molybdenum Substances 0.000 claims 5
- 229910052721 tungsten Inorganic materials 0.000 claims 5
- 239000010937 tungsten Substances 0.000 claims 5
- 229910052726 zirconium Inorganic materials 0.000 claims 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 3
- QDMRQDKMCNPQQH-UHFFFAOYSA-N boranylidynetitanium Chemical compound [B].[Ti] QDMRQDKMCNPQQH-UHFFFAOYSA-N 0.000 claims 3
- 229910052791 calcium Inorganic materials 0.000 claims 3
- 239000011575 calcium Substances 0.000 claims 3
- 229910052732 germanium Inorganic materials 0.000 claims 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 2
- RWDBMHZWXLUGIB-UHFFFAOYSA-N [C].[Mg] Chemical compound [C].[Mg] RWDBMHZWXLUGIB-UHFFFAOYSA-N 0.000 claims 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims 2
- 239000004917 carbon fiber Substances 0.000 claims 2
- HPNSNYBUADCFDR-UHFFFAOYSA-N chromafenozide Chemical compound CC1=CC(C)=CC(C(=O)N(NC(=O)C=2C(=C3CCCOC3=CC=2)C)C(C)(C)C)=C1 HPNSNYBUADCFDR-UHFFFAOYSA-N 0.000 claims 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims 2
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims 2
- MHKWSJBPFXBFMX-UHFFFAOYSA-N iron magnesium Chemical compound [Mg].[Fe] MHKWSJBPFXBFMX-UHFFFAOYSA-N 0.000 claims 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims 2
- 229910052759 nickel Inorganic materials 0.000 claims 2
- 229910052758 niobium Inorganic materials 0.000 claims 2
- 239000010955 niobium Substances 0.000 claims 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims 2
- 229920000642 polymer Polymers 0.000 claims 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 claims 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 claims 1
- CYUOWZRAOZFACA-UHFFFAOYSA-N aluminum iron Chemical compound [Al].[Fe] CYUOWZRAOZFACA-UHFFFAOYSA-N 0.000 claims 1
- RAWGYCTZEBNSTP-UHFFFAOYSA-N aluminum potassium Chemical compound [Al].[K] RAWGYCTZEBNSTP-UHFFFAOYSA-N 0.000 claims 1
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 1
- 229910010293 ceramic material Inorganic materials 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 239000000446 fuel Substances 0.000 claims 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 229910000765 intermetallic Inorganic materials 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 235000010333 potassium nitrate Nutrition 0.000 claims 1
- 239000004323 potassium nitrate Substances 0.000 claims 1
- NDQAIVHSPRMJBW-UHFFFAOYSA-N potassium silver dinitrate Chemical compound [N+](=O)([O-])[O-].[K+].[Ag+].[N+](=O)([O-])[O-] NDQAIVHSPRMJBW-UHFFFAOYSA-N 0.000 claims 1
- 229910001961 silver nitrate Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 229910001220 stainless steel Inorganic materials 0.000 claims 1
- 239000010935 stainless steel Substances 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000007771 core particle Substances 0.000 abstract description 22
- 230000008569 process Effects 0.000 abstract description 18
- 239000011162 core material Substances 0.000 abstract description 16
- 230000009257 reactivity Effects 0.000 abstract description 16
- 239000011246 composite particle Substances 0.000 abstract description 8
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000005065 mining Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 230000000638 stimulation Effects 0.000 abstract 1
- 239000011164 primary particle Substances 0.000 description 27
- 239000000843 powder Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000010410 layer Substances 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000007596 consolidation process Methods 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 238000005755 formation reaction Methods 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- 229910000861 Mg alloy Inorganic materials 0.000 description 6
- 229910001092 metal group alloy Inorganic materials 0.000 description 6
- 238000004663 powder metallurgy Methods 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 238000005253 cladding Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910010272 inorganic material Inorganic materials 0.000 description 5
- 239000011147 inorganic material Substances 0.000 description 5
- 239000013528 metallic particle Substances 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 239000012190 activator Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000005242 forging Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000002490 spark plasma sintering Methods 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 230000004075 alteration Effects 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011156 metal matrix composite Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- FVFLHJZAFUCZAK-UHFFFAOYSA-N [C].[Mg].[Fe] Chemical compound [C].[Mg].[Fe] FVFLHJZAFUCZAK-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012072 active phase Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000004200 deflagration Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000010338 mechanical breakdown Methods 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000009704 powder extrusion Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000009716 squeeze casting Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/18—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component
- C06B45/30—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an inorganic explosive or an inorganic thermic component
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B27/00—Compositions containing a metal, boron, silicon, selenium or tellurium or mixtures, intercompounds or hydrides thereof, and hydrocarbons or halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B43/00—Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/18—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component
- C06B45/30—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an inorganic explosive or an inorganic thermic component
- C06B45/32—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an inorganic explosive or an inorganic thermic component the coating containing an organic compound
- C06B45/34—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an inorganic explosive or an inorganic thermic component the coating containing an organic compound the compound being an organic explosive or an organic thermic component
Definitions
- the present invention is a divisional of U.S. patent application Ser. No. 16/137,934, filed Sep. 21, 2018, which in turn is a divisional of U.S. patent application Ser. No. 14/432,875, filed Apr. 1, 2015, which in turn is a 371 filing of PCT/US2013/073988, filed Dec. 10, 2013, which in turn claims priority to U.S. Provisional Patent Application Ser. No. 61/735,246, filed Dec. 10, 2012, which is incorporated herein by reference.
- the present invention relates to the formation of multi-grain compacts or particles fabricated by a sintering process, which particles can be modified with one or more coatings applied to their surfaces to control the reactivity and/or mechanical properties of the compact.
- the present invention also relates to the production of a reactive composite having controlled reaction kinetics catalyzed by an external stimulus.
- the invention also relates to individual particles or agglomerates which have applied to their surface a second, discreet phase material of different composition from the particle which provides for at least partial control over the reaction with the core particle or the environment during exposure and/or which may be tailored by controlling the relative particle sizes and/or amounts to provide a controlled reactivity rate.
- Sintered products of inorganic non-metallic or metallic powders have been used in structural parts, wear parts, semiconductor substrates, printed circuit boards, electrically insulating parts, high hardness and high precision machining materials (e.g., cutting tools, dies, bearings, etc.), functional materials such as grain boundary capacitors, humidity sensors, and precision sinter molding materials, among other applications.
- high hardness and high precision machining materials e.g., cutting tools, dies, bearings, etc.
- functional materials such as grain boundary capacitors, humidity sensors, and precision sinter molding materials, among other applications.
- the starting particles are often blended with additives for such purposes as lowering the sintering/consolidation temperature and/or pressure, or modifying/improving the physical or mechanical properties of the resultant compact.
- the current state of the art in metals and ceramics processing is to mill or blend additives and modifiers using a ball mill or attrition milling technology. More recent inventions utilize coprecipitation, atomization, or self-assembly to improve distribution and reaction controllability of these composite materials.
- Applicant has proposed in a prior application a method for coating fine particles with coatings of ceramic and metallic materials. This is a process for applying coatings to particles in a continuous (or discontinuous, depending on application), pore-free manner.
- the current invention relates to the design and/or composition of matter for metal and/or ceramic particles to which have been applied a surface modifying layer or layers.
- the core and claddings posses highly different properties, including electronegativity, free energy of formation, or oxidizing potential
- the combination can be made to react in a controlled fashion in response to the imposition of an external stimulus, such as shear (e.g., impact), thermal (high temperature ignition), or catalysis or activation (addition of an electrolyte such as salt water or acid).
- Umeya (U.S. Pat. No. 5,489,449) discloses the use of ultrafine sintering aids dispersed/coated onto the surface of ceramic particles using precipitation techniques. Umeya further describes a process for forming ultrafine ceramic particles through gas-phase nucleation which are then deposited onto the surfaces of ceramic particles. This process has inherent limitations in that it does not provide for a continuous, uninterrupted coating on the ceramic surface, and does not address reaction/interaction of the sintering aid with the particle itself. Umeya uses chemical reduction of copper oxide and other precursors, and the techniques described are not applicable to reactive systems due to temperature and chemical environments, and the reactivity of magnesium, aluminum, and other reactive metals.
- Beane U.S. Pat. Nos. 5,614,320 and 5,453,293 disclose a related process for controlling the end thermal (CTE, thermal conductivity) properties of a material by forming a coated particle having two materials that have distinctly different intrinsic properties. Such process allows for the production of a material with a property controlled by rules of mixture relationships between the limits set by the two materials consisting of the coating material and the core particle material.
- Lee et al. (U.S. Pat. No 4,063,907) discloses a process for producing smeared metal coatings on diamond particles to produce a chemically bonded coating on the diamond particles to improve adhesion in a matrix material.
- Kuo et al. (U.S. Pat. No 5,008,132) discloses a process for applying a titanium nitride coating to silicon carbide particles using a diffusion barrier interlayer to improve the wettability and to inhibit the reaction of the silicon carbide particles in a titanium metal matrix.
- Gabor et al. (U.S. Pat. No 5,405,720) discloses the use of refractory carbide and nitride coatings on abrasive particles.
- Yajima et al. (U.S. Pat. No 4,134,759) discloses the use of certain coatings on continuous SiC ceramic fibers that have an exterior carbon coating that increases the wettability in aluminum and aluminum alloys.
- Wheeler et al. (U.S. Pat. No 5,171,419) discloses the use of CoW and NiW interlayers on ceramic fibers for this purpose.
- Chance et al. (U.S. Pat. No 5,292,477) discloses an atomizing process for producing uniform distributions of grain growth control additives throughout the bulk of a particle.
- the present invention relates to the formation of multi-grain compacts or particles fabricated by a sintering process, which particles can be modified with one or more coatings applied to their surfaces to control the reactivity and/or the mechanical properties of the compact.
- the present invention also relates to the production of a reactive composite having controlled reaction kinetics catalyzed by an external stimulus, such as, but not limited to, an ignition source and/or environmental change (e.g., an electrolyte addition, etc.).
- an external stimulus such as, but not limited to, an ignition source and/or environmental change (e.g., an electrolyte addition, etc.).
- the present invention creates particles so that the reaction kinetics can be at least partially controlled through the use of engineered building block repeating units combined with a solid and/or semi-solid state consolidation.
- the use of engineered particles or building block repeating units leads to more controllable, predictable, and/or lower cost fabrication of reactive composite parts using powder metallurgy techniques.
- the invention also relates to individual particles or agglomerates which have applied to their surface a second, discreet phase material of different composition from the particle which provides for at least partial control over the reaction with the core particle or the environment during exposure and/or which may be tailored by controlling the relative particle sizes and/or amounts (e.g., with third phase additions, etc.) to provide a controlled reactivity rate while simultaneously controlling mechanical and/or physical properties.
- the combination can be made to react in a controlled fashion in response to the imposition of an external stimulus, such as shear (e.g., impact, etc.), thermal (e.g., high temperature ignition, etc.), and/or catalysis or activation (e.g., addition of an electrolyte such as salt water or acid, etc.).
- shear e.g., impact, etc.
- thermal e.g., high temperature ignition, etc.
- catalysis or activation e.g., addition of an electrolyte such as salt water or acid, etc.
- an engineered reactive matrix composite which includes a core material and a reactive binder matrix.
- the engineered reactive matrix composite includes a) a repeating metal or ceramic particle core material of about 30%-90% (e.g., 30%, 30.1%, 30.2%, 50%, 72%, . . . 89.98%, 89.99%, 90%) by volume and any value or range therebetween, and b) a reactive binder/matrix of about 10%-70% (e.g., 10%, 10.01%, 10.02%, . . . 69.98%, 69.99%, 70%) by volume and any value or range therebetween.
- the reactive/matrix binder can be distributed relatively homogenously around the core particles; however, other controlled arrangements are possible.
- the reactivity of the reactive binder/matrix can be engineered by controlling the relative interfacial surface area of the reactive components, through the selection of catalytic agents or accelerants, or through other techniques.
- a method of manufacturing reactive composites which method includes the preparation of a plurality of engineered, reactive composite building blocks, and then consolidating these building blocks below the liquidus of the binder material using a combination of heat (e.g., 100° F.-1500° F., etc.) and pressure (e.g., 1.1-10 Atm, etc.), either simultaneously or in two separate steps.
- heat e.g., 100° F.-1500° F., etc.
- pressure e.g., 1.1-10 Atm, etc.
- the techniques for consolidating the materials include, but are not limited to, powder forging or field-assisted sintering (e.g., spark plasma sintering, etc.), direct powder extrusion, or press and sinter techniques.
- powder forging or field-assisted sintering e.g., spark plasma sintering, etc.
- direct powder extrusion e.g., direct powder extrusion
- press and sinter techniques e.g., direct powder extrusion
- a porous perform can be fabricated with controlled density/particle loading to be further processed using infiltration (squeeze casting, pressureless infiltration, etc.) of a reactive metal matrix such as magnesium or aluminum.
- a powder structure of a metallic or inorganic non-metallic particle to which has been applied one or more coatings of a reactive inorganic material is generally a non-reactive particle or a particle that is less reactive than the reactive inorganic material; however, this is not required.
- the metallic or inorganic non-metallic particle is generally not reactive with the reactive inorganic material; however, however, this is not required. Generally, 50% to 100% (e.g., 50%, 50.01%, 50.02% . . .
- any valve or range therebetween of the outer surface of the metallic or inorganic non-metallic particle is coated with the reactive inorganic material.
- a continuous, uniform coating of a reactive inorganic material is coated onto the complete outer surface of the metallic or inorganic non-metallic particle.
- Such coating can be of a uniform or non-uniform thickness.
- the core is a high stiffness, relatively inert material
- the binder is a reactive material such as, but not limited to, an electropositive and/or easily oxidizable metal (e.g., magnesium, zinc, etc.).
- a non-limiting object of the present invention is the provision of a multi-grain compacts and a process and method for forming the multi-grain compacts.
- Another and/or alternative non-limiting object of the present invention is the provision of multi-grain compacts or particles fabricated by a sintering process, which particles can be modified with one or more coatings applied to their surfaces to control the reactivity and/or the mechanical properties of the compact.
- Still another and/or alternative non-limiting object of the present invention is the provision of multi-grain compacts and a process and method for forming the multi-grain compacts having controlled reaction kinetics catalyzed by an external stimulus, such as, but not limited to, an ignition source and/or environmental change.
- an external stimulus such as, but not limited to, an ignition source and/or environmental change.
- Yet another and/or alternative non-limiting object of the present invention is the provision of particles and the formation of particles wherein the reaction kinetics can be at least partially controlled through the use of engineered building block repeating units combined with a solid and/or semi-solid state consolidation.
- Still yet another and/or alternative non-limiting object of the present invention is the provision of engineered particles or building block repeating units that have more controllable, predictable, and/or lower cost fabrication of reactive composite parts using powder metallurgy techniques.
- Another and/or alternative non-limiting object of the present invention is the provision of individual particles or agglomerates which have applied to their surface a second, discreet phase material of different composition from the particle which provides for at least partial control over the reaction with the core particle or the environment during exposure and/or which may be tailored by controlling the relative particle sizes and/or amounts to provide a controlled reactivity rate.
- Still another and/or alternative non-limiting object of the present invention is the provision of a method and process for coating fine particles with ceramic and metallic materials.
- Yet another and/or alternative non-limiting object of the present invention is the provision of a method and process that involves the applying of coatings to particles in a continuous (or discontinuous, depending on application), pore-free manner.
- Still yet another and/or alternative non-limiting object of the present invention is the provision of the design and/or composition of matter for metal and/or ceramic particles to which have been applied a surface modifying layer or layers.
- Another and/or alternative non-limiting object of the present invention is the provision of coated particles wherein in the coating and particle have different properties, the combination of which can be made to react in a controlled fashion in response to the imposition of an external stimulus.
- Still another and/or alternative non-limiting object of the present invention is the provision of an engineered reactive matrix composite which include a core material, and a reactive binder matrix, which engineered reactive matrix is a repeating metal or ceramic particle core material and a reactive binder/matrix.
- Yet another and/or alternative non-limiting object of the present invention is the provision of an engineered reactive matrix composite which include a core material, and a reactive binder matrix, and the reactivity of the reactive binder/matrix can be engineered by controlling the relative interfacial surface area of the reactive components.
- Still yet another and/or alternative non-limiting object of the present invention is the provision of a method of manufacturing reactive composites, which method includes the preparation of a plurality of engineered, reactive composite building blocks, and then consolidating these building blocks below the liquidus of the binder or core material.
- Another and/or alternative non-limiting object of the present invention is the provision of adding an additive/modifier onto the surface of a powder to form an integral unit to achieve simplified handling of powder materials, simplified production of a compact with increased homogeneity and/or improved and more repeatable performance/properties.
- FIGS. 1-2 are a cross-sectional illustration of composite particles in accordance with the present invention wherein the black core represents the primary particle which can be a metal, metal alloy, and/or a ceramic particle, and the surrounding white section represents the additive/modifier which has been added to the surface of the primary particle in accordance with the present invention;
- FIGS. 3A-3C illustrate magnesium-coated graphite, a consolidated magnesium-graphite part in its microstructure respectively, in accordance with the present invention
- FIG. 4 illustrates a magnesium-iron-graphite reactive composite microstructure in accordance with the present invention.
- FIG. 5 is a schematic diagram showing carbon particles embedded in a matrix of magnesium alloy with an iron interface, along with an actual composite structure, wherein the carbon particles (black) are first coated with a wetting and reaction accelerator (iron) and then with an activator (slightly darker shade), and these composite powders are then embedded in a matrix of magnesium alloy using powder metallurgy techniques.
- a metal, metal alloy, and/or ceramic particle typically used for powder metallurgy fabrication, is provided which is made from a primary particle which has a thin, continuous or non-continuous coating of a reactive matrix and/or binder used to improve the consolidation behavior, properties of the resultant powder metallurgy compact, and/or to provide controlled response to external stimuli.
- the coated particle is comprised of a metal, metal alloy, and/or a ceramic particle, to which has been applied a surface coating of at least about 1% of the primary particle diameter, typically no more than about 50% of the primary particle diameter (e.g., 1%, 1.01%, 1.02% . . .
- FIGS. 1-2 are illustrations of non-limiting coated particles 10 in accordance with the present invention.
- the primary or core particle 20 is designed in black and the coating of a reactive matrix and/or binder 30 is illustrated as the white layer about the primary or core particle.
- the relative interfacial area between the core and the coating is controlled to provide for a controlled reaction rate. This rate may be further augmented by the production of a dual-phase matrix/binder having a much higher interfacial area than the coarser core particles; however, this is not required.
- the starting material is a metal, metal alloy, and/or ceramic particle having an average particle diameter size of at least about 0.1 microns, typically no more than about 500 microns (e.g., 0.1 microns, 0.1001 microns, 0.1002 microns . . . 499.9998 microns, 499.9999 microns, 500 microns) and including any value or range therebetween, more typically about 0.1 to 400 microns, and still more typically about 10 to 50 microns.
- the primary particles may be prepared through any number of synthesis routes including, but not limited to, gas and/or vacuum atomization, mechanical breakdown, gas precipitation and/or liquid precipitation, and/or other suitable techniques.
- the starting primary particles are typically heat treated and/or etched to remove any adsorbed gases and/or surface oxide layers; however, this is not required.
- the primary particles are then coated with a metal, metal alloy, ceramic and/or composite layer.
- This layer serves to modify the mechanical properties and reactivity of the compact (i.e., particle plus coating), for example, by providing for an intermetallic or galvanic reaction with the primary particle and/or with interaction with secondary particles added during consolidation.
- the particle coating may prevent reoxidation of the primary particle, limit reaction of the particle with a metal matrix, and/or modify the diffusional properties (i.e., grain growth, grain boundary strength, etc.) of the particle when consolidated.
- the formation of the coated particles may be accomplished by applying either a single layer of a metal, metal alloy, ceramic and/or composite coating, and/or a multilayer or composite coating system. Additional particles of a finer size (i.e., small average diameter size) than the primary particle or the coated particles may further be added during consolidation to reduce cost, and/or modify the mechanical or reactive functions of the reactive matrix (i.e., primary particle plus coating or primary particle plus coating plus finer additional particles).
- the coating can have a thickness that is neither too thin nor too thick. A thicker coating facilitates wetting of the particles during consolidation.
- the coating is at least about 1% of the primary particle diameter, typically no more than about 50% primary particle diameter (e.g., 1%, 1.01%, 1.02% . . . 49.98%, 49.99%, 50%) and any value or range therebetween, and typically about 1 to 30% of the primary particle diameter. Also or alternatively, the coating is at least about 0.01 microns thick, typically no more than about 10 microns thick (e.g., 0.01 microns, 0.01001 microns, 0.01002 microns . . .
- the primary or core particle can be deformable during consolidation to promote the formation of a space-filling array of repeating engineered particle units; however, this is not required.
- the particles include aluminum particles having an average particle diameter size of about 5 to 50 microns (e.g., 5 microns, 5.01 microns, 5.02 microns . . . 49.98 microns, 49.99 microns, 50 microns) and any value or range therebetween, that are degassed and/or deoxidized, and then coated with about 0.3 to 2 microns coating thickness (e.g., 0.3 microns, 0.301 microns, 0.302 microns . . . 1.998 microns, 1.999 microns, 2 microns) and any value or range therebetween, of silicon, silver, and/or zinc.
- smaller or larger particles can be coated with thicker or thinner coatings.
- multilayer coatings can be applied to one or more of the primary or core particles.
- the primary or core particles include iron and/or carbon particles having an average particle diameter size of about 5 to 50 microns (e.g., 5 microns, 5.01 microns, 5.02 microns . . . 49.98 microns, 49.99 microns, 50 microns) and any value or range therebetween, that are coated with about 0.3 to 3 microns coating thickness (e.g., 0.3 microns, 0.301 microns, 0.302 microns . . . 2.998 microns, 2.999 microns, 3 microns) and any value or range therebetween, of a matrix of magnesium and/or zinc.
- the primary or core particles include iron and/or carbon particles having an average particle diameter size of about 5 to 50 microns (e.g., 5 microns, 5.01 microns, 5.02 microns . . . 49.98 microns, 49.99 microns, 50 microns) and any value or range therebetween, that are coated with about 0.3 to 3 micron
- the consolidated compact reacts when activated by an electrolyte, with the reactive binder dissolving at a controlled rate. Having a high surface area of the cathode (iron and/or graphite) and a small area of the reactive binder can speed the reaction rate.
- a tungsten powder having an average particle diameter size of about 5 to 100 microns e.g., 5 microns, 5.01 microns, 5.02 microns . . . 99.98 microns, 99.99 microns, 100 microns
- about 0.3 to 3 microns coating thickness e.g., 0.3 microns, 0.301 microns, 0.302 microns . . . 2.998 microns, 2.999 microns, 3 microns
- This high density composite can be activated by vaporizing the zinc and/or magnesium upon high velocity impact, wherein the magnesium and/or zinc vapor reacts with the air that can produce a secondary explosion or deflagration thermal event.
- a high density reactive material such as silicon, boron, and/or tantalum having an average particle diameter size of about 5 to 100 microns (e.g., 5 microns, 5.01 microns, 5.02 microns . . . 99.98 microns, 99.99 microns, 100 microns) and any value or range therebetween, is coated with about 0.3 to 3 microns coating thickness (e.g., 0.3 microns, 0.301 microns, 0.302 microns . . .
- a reactive composite binder e.g., aluminum, magnesium, etc.
- an oxidizer e.g., fluorinated polymer, etc.
- a coating thickness of about 0.01 to 3 microns coating thickness (e.g., 0.01 microns, 0.01001 microns, 0.01002 microns . . . 2.998 microns, 2.999 microns, 3 microns) and any value or range therebetween.
- the reactive composite binder can optionally be designed to rapidly ignite upon a thermal stimulus (e.g., a fuse, via high velocity impact, etc.), dispersing and igniting the core particles which produce a secondary reaction.
- a thermal stimulus e.g., a fuse, via high velocity impact, etc.
- the core particles are normally not ignitable without the preheating and dispersion created by the reactive composite coating; however, this is not required.
- the reactivity of an electrolytically activated reactive composite of magnesium and/or zinc and iron is controlled to produce a dissolution rate from about 1 to 10 mm/day and any value or range therebetween, by controlling the relative phase amounts and interfacial surface area of the two galvanically active phases.
- a mechanical mixture of iron and/or graphite and/or and zinc and/or magnesium is prepared and applied to the surface of about 30 to 200 micron and any value or range therebetween of iron and/or graphite particles, followed by consolidation using spark plasma sintering or powder forging at a temperature below the magnesium and/or zinc melting point.
- the resultant structure has an accelerated rate of reaction due to the high exposed surface area of the iron and/or graphite cathode phase, but low relative area of the anodic (zinc and/or magnesium) reactive binder.
- FIGS. 3A-3C and 4 illustrate a representative microstructure for a magnesium-graphite composite and a magnesium-iron-graphite composite.
- FIG. 3A is a magnified picture of magnesium-coated graphite.
- FIG. 3B is consolidated magnesium-graphite part.
- FIG. 3C is a magnified view of the microstructure of the magnesium-graphite part of FIG. 3B .
- FIG. 4 is a magnified view of a magnesium-iron-graphite reactive composite microstructure.
- FIG. 5 is a schematic diagram showing a composite particle 10 formed of primary or core particles, such as, but not limited to, carbon particles, embedded in a matrix of coating of, but not limited to, a magnesium alloy with an interface of, but not limited to, iron, along with an actual composite structure.
- the primary or core particles 20 are illustrated as the black colored core.
- the primary or core particles are first coated with a wetting and reaction accelerator (e.g., iron, etc.) 30 which is illustrated as the white colored coating layer about the primary or core particles.
- An activator 40 is subsequently coated onto the wetting and reaction accelerator layer, which activator layer is illustrated as the slightly darker shade or grey colored layer about the white colored wetting and reaction accelerator layer.
- the coating thicknesses of the wetting and reaction accelerator layer and the activator layer can be the same or different. All three layers of the composite particle are generally formed of a different material; however, two non-adjacently positioned layers can be formed of the same material.
- the composite particle can have the same shape and/or size; however, this is not required.
- a plurality of composite particles 10 are illustrated as being embedded in a matrix of material 50 such as, but not limited, to magnesium alloy to form a matrix composite material 60 .
- the process of embedding the composite particles in the matrix material to form the matrix composite material can be by use of powder metallurgy techniques.
- Iron powder having a particle size of about 20 to 40 microns is loaded into a fluidized bed reactor. Magnesium metal vapor is then introduced into the reactor and condenses to form a magnesium coating on the iron particles. About 8 to 12% by volume (e.g., 10% by volume) of magnesium is added to the iron powder. The resultant magnesium coated iron powder is then consolidated into a billet, and powder forged into a final shape at about 380 to 480° C. under about 30 to 100 tons/in 2 compaction pressure.
- the resultant compact has high mechanical properties, generally above 30 KSI strength, and when exposed to slightly acidic or salt solutions, is corroded at a rate of 0.1-15 mm/day depending on environment and temperature.
- Magnesium powder is dry-milled under inert atmosphere with about 10 to 60% by volume of 1 to 3 microns carbonyl iron powder (a composite of iron and carbon) and a small amount of catalyst (iron aluminide is one example) to produce a composite powder blend. Additionally, coarse iron powder (as in Example 1) is loaded into a fluidized bed reactor, and the milled magnesium-iron-carbon is then applied to the surface of the coarse graphite powder by spraying a solution of the magnesium powder, a binder, and a liquid carrier onto the surface of the powder in a fluidized bed. Thereafter is the addition of about 8 to 22% by volume magnesium composite powder.
- the resultant composite powder is consolidated using spark plasma sintering or powder forging with 20-40% upset to form a fully dense compact, which is machined into galvanically activated reactive composite parts having a dissolution rate of about 0.1 to 5 mm/hour in a brine solution.
- Silicon, titanium, or zirconium metal powder having a particle size of about 10 to 50 microns is loaded into a fluidized bed.
- a mixture of fine magnesium powder and polyvinylidene difluoride (PVDF) in a solvent is applied as a surface coating onto the silicon powder and the solvent is removed.
- PVDF polyvinylidene difluoride
- the resultant powder is warm-compacted to form a high density reactive metal matrix composite having a strength greater than 10 KSI, and which can be initiated to disperse, react, and produce a high energy blast effect using an external stimulus such as hard target penetration or electrically stimulated to generate heat and disintegrate rapidly.
- Tungsten powder having a particle size of about 10 to 20 microns is placed into a fluidized bed and coated with a mixture of titanium and boron powders with an atomic ratio of about 0.5-2:1.
- the resultant coated particles are cold-pressed, outgased, and powder forged or spark plasma sintered into a conical structure.
- This reactive cone is able to be explosively formed into a reactive slug which provides excellent penetration into tight formations to release oil and gas concentrations, self-heating itself to over 800 C and providing a high density slug with excellent penetration characteristics.
- a magnesium or zinc coating is applied using vapor deposition to an oxidizer core, which can be iron oxide, KClO4, AgNO3, or Bi2O3 or other oxidizer particle, having a size between 1 and 50 microns, and preferably between 10 and 25 microns.
- oxidizer core which can be iron oxide, KClO4, AgNO3, or Bi2O3 or other oxidizer particle, having a size between 1 and 50 microns, and preferably between 10 and 25 microns.
- a thermoplastic fluorinated polymeric material such as PVDF or PTFE.
- the resultant blended mixture is warm compacted or molded to form a fully dense (greater than 95% dense) compact having mechanical properties of greater than 5,000 PSIG flexure strength and a high energy density that can be triggered to give a large thermal or gas pressure response using an electrical or thermal signal.
- a magnesium or zinc coating is applied using vapor deposition to a 1-50 micron graphite, metal, or ceramic core particle to form a 0.1-3 micron thick Mg coating.
- the coated core particles are warm-compacted or pressed and sintered to form a porous perform having between 10 and 50% open porosity, but near-zero “touching” of the ceramic or metallic core particles.
- This controlled density perform is then melt-infiltrated with aluminum, magnesium alloy, aluminum-magnesium alloy, or zinc alloy to form a reactive metal matrix composite having a strength above 8000 psig, and meeting predetermined dissolution or reactive rates, where such reactivity is controlled by controlling the relative amounts of phases and the size and composition of the starting core particles.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
- The present invention is a divisional of U.S. patent application Ser. No. 16/137,934, filed Sep. 21, 2018, which in turn is a divisional of U.S. patent application Ser. No. 14/432,875, filed Apr. 1, 2015, which in turn is a 371 filing of PCT/US2013/073988, filed Dec. 10, 2013, which in turn claims priority to U.S. Provisional Patent Application Ser. No. 61/735,246, filed Dec. 10, 2012, which is incorporated herein by reference.
- The present invention relates to the formation of multi-grain compacts or particles fabricated by a sintering process, which particles can be modified with one or more coatings applied to their surfaces to control the reactivity and/or mechanical properties of the compact. The present invention also relates to the production of a reactive composite having controlled reaction kinetics catalyzed by an external stimulus. The invention also relates to individual particles or agglomerates which have applied to their surface a second, discreet phase material of different composition from the particle which provides for at least partial control over the reaction with the core particle or the environment during exposure and/or which may be tailored by controlling the relative particle sizes and/or amounts to provide a controlled reactivity rate.
- Sintered products of inorganic non-metallic or metallic powders have been used in structural parts, wear parts, semiconductor substrates, printed circuit boards, electrically insulating parts, high hardness and high precision machining materials (e.g., cutting tools, dies, bearings, etc.), functional materials such as grain boundary capacitors, humidity sensors, and precision sinter molding materials, among other applications.
- When inorganic non-metallic or metal powders are sintered to produce a product (often with the application of pressure), the starting particles are often blended with additives for such purposes as lowering the sintering/consolidation temperature and/or pressure, or modifying/improving the physical or mechanical properties of the resultant compact.
- The current state of the art in metals and ceramics processing is to mill or blend additives and modifiers using a ball mill or attrition milling technology. More recent inventions utilize coprecipitation, atomization, or self-assembly to improve distribution and reaction controllability of these composite materials.
- Applicant has proposed in a prior application a method for coating fine particles with coatings of ceramic and metallic materials. This is a process for applying coatings to particles in a continuous (or discontinuous, depending on application), pore-free manner. The current invention relates to the design and/or composition of matter for metal and/or ceramic particles to which have been applied a surface modifying layer or layers. When the core and claddings posses highly different properties, including electronegativity, free energy of formation, or oxidizing potential, the combination can be made to react in a controlled fashion in response to the imposition of an external stimulus, such as shear (e.g., impact), thermal (high temperature ignition), or catalysis or activation (addition of an electrolyte such as salt water or acid).
- Umeya (U.S. Pat. No. 5,489,449) discloses the use of ultrafine sintering aids dispersed/coated onto the surface of ceramic particles using precipitation techniques. Umeya further describes a process for forming ultrafine ceramic particles through gas-phase nucleation which are then deposited onto the surfaces of ceramic particles. This process has inherent limitations in that it does not provide for a continuous, uninterrupted coating on the ceramic surface, and does not address reaction/interaction of the sintering aid with the particle itself. Umeya uses chemical reduction of copper oxide and other precursors, and the techniques described are not applicable to reactive systems due to temperature and chemical environments, and the reactivity of magnesium, aluminum, and other reactive metals.
- Beane (U.S. Pat. Nos. 5,614,320 and 5,453,293) and others disclose a related process for controlling the end thermal (CTE, thermal conductivity) properties of a material by forming a coated particle having two materials that have distinctly different intrinsic properties. Such process allows for the production of a material with a property controlled by rules of mixture relationships between the limits set by the two materials consisting of the coating material and the core particle material.
- Lee et al. (U.S. Pat. No 4,063,907) discloses a process for producing smeared metal coatings on diamond particles to produce a chemically bonded coating on the diamond particles to improve adhesion in a matrix material.
- Kuo et al. (U.S. Pat. No 5,008,132) discloses a process for applying a titanium nitride coating to silicon carbide particles using a diffusion barrier interlayer to improve the wettability and to inhibit the reaction of the silicon carbide particles in a titanium metal matrix.
- Gabor et al. (U.S. Pat. No 5,405,720) discloses the use of refractory carbide and nitride coatings on abrasive particles.
- Yajima et al. (U.S. Pat. No 4,134,759) discloses the use of certain coatings on continuous SiC ceramic fibers that have an exterior carbon coating that increases the wettability in aluminum and aluminum alloys.
- Wheeler et al. (U.S. Pat. No 5,171,419) discloses the use of CoW and NiW interlayers on ceramic fibers for this purpose.
- Chance et al. (U.S. Pat. No 5,292,477) discloses an atomizing process for producing uniform distributions of grain growth control additives throughout the bulk of a particle.
- Quick et al. (U.S. Pat. No 5,184,662) disclose a related process for forming metal/ceramic composite particles that have a continuous cladding of the metal.
- In each of these prior art references, the disclosures do not include the controlling of particle reactivity.
- The present invention relates to the formation of multi-grain compacts or particles fabricated by a sintering process, which particles can be modified with one or more coatings applied to their surfaces to control the reactivity and/or the mechanical properties of the compact. The present invention also relates to the production of a reactive composite having controlled reaction kinetics catalyzed by an external stimulus, such as, but not limited to, an ignition source and/or environmental change (e.g., an electrolyte addition, etc.). The present invention creates particles so that the reaction kinetics can be at least partially controlled through the use of engineered building block repeating units combined with a solid and/or semi-solid state consolidation. The use of engineered particles or building block repeating units leads to more controllable, predictable, and/or lower cost fabrication of reactive composite parts using powder metallurgy techniques. The invention also relates to individual particles or agglomerates which have applied to their surface a second, discreet phase material of different composition from the particle which provides for at least partial control over the reaction with the core particle or the environment during exposure and/or which may be tailored by controlling the relative particle sizes and/or amounts (e.g., with third phase additions, etc.) to provide a controlled reactivity rate while simultaneously controlling mechanical and/or physical properties.
- When the core and claddings possesses highly different properties, including electronegativity, free energy of formation, and/or oxidizing potential, the combination can be made to react in a controlled fashion in response to the imposition of an external stimulus, such as shear (e.g., impact, etc.), thermal (e.g., high temperature ignition, etc.), and/or catalysis or activation (e.g., addition of an electrolyte such as salt water or acid, etc.).
- In one non-limiting aspect of the present invention, there is provided an engineered reactive matrix composite which includes a core material and a reactive binder matrix. In one non-limiting embodiment of the invention, the engineered reactive matrix composite includes a) a repeating metal or ceramic particle core material of about 30%-90% (e.g., 30%, 30.1%, 30.2%, 50%, 72%, . . . 89.98%, 89.99%, 90%) by volume and any value or range therebetween, and b) a reactive binder/matrix of about 10%-70% (e.g., 10%, 10.01%, 10.02%, . . . 69.98%, 69.99%, 70%) by volume and any value or range therebetween. The reactive/matrix binder can be distributed relatively homogenously around the core particles; however, other controlled arrangements are possible. The reactivity of the reactive binder/matrix can be engineered by controlling the relative interfacial surface area of the reactive components, through the selection of catalytic agents or accelerants, or through other techniques.
- In still another non-limiting aspect of the present invention, there is provided a method of manufacturing reactive composites, which method includes the preparation of a plurality of engineered, reactive composite building blocks, and then consolidating these building blocks below the liquidus of the binder material using a combination of heat (e.g., 100° F.-1500° F., etc.) and pressure (e.g., 1.1-10 Atm, etc.), either simultaneously or in two separate steps. Generally, the binder and/or core material are above approximately 40% of the solidus temperature and below the liquidus temperature at the time such components of the reactive composite are combined together, although for certain systems much lower relative temperatures above room temperature can be used with elevated pressures. The techniques for consolidating the materials include, but are not limited to, powder forging or field-assisted sintering (e.g., spark plasma sintering, etc.), direct powder extrusion, or press and sinter techniques. Using press and sinter techniques, a porous perform can be fabricated with controlled density/particle loading to be further processed using infiltration (squeeze casting, pressureless infiltration, etc.) of a reactive metal matrix such as magnesium or aluminum.
- It has been found that if the additive/modifier can be deposited as a thin, continuous coating onto the surface of the sintering powder to form an integral unit, the limitations of the prior art can be overcome, thus achieving simplified handling of powder materials, simplified production of a sintered compact with increased homogeneity, and improved and more repeatable performance/properties (particularly reactivity) can be achieved.
- It is still another non-limiting aspect of the present invention, there is provided a powder structure of a metallic or inorganic non-metallic particle to which has been applied one or more coatings of a reactive inorganic material. The metallic or inorganic non-metallic particle is generally a non-reactive particle or a particle that is less reactive than the reactive inorganic material; however, this is not required. The metallic or inorganic non-metallic particle is generally not reactive with the reactive inorganic material; however, however, this is not required. Generally, 50% to 100% (e.g., 50%, 50.01%, 50.02% . . . 99.98%, 99.99%, 100%) and any valve or range therebetween of the outer surface of the metallic or inorganic non-metallic particle is coated with the reactive inorganic material. In one non-limiting embodiment, a continuous, uniform coating of a reactive inorganic material is coated onto the complete outer surface of the metallic or inorganic non-metallic particle. Such coating can be of a uniform or non-uniform thickness. In another and/or alternative non-limiting embodiment of the invention, the core is a high stiffness, relatively inert material, while the binder is a reactive material such as, but not limited to, an electropositive and/or easily oxidizable metal (e.g., magnesium, zinc, etc.).
- A non-limiting object of the present invention is the provision of a multi-grain compacts and a process and method for forming the multi-grain compacts.
- Another and/or alternative non-limiting object of the present invention is the provision of multi-grain compacts or particles fabricated by a sintering process, which particles can be modified with one or more coatings applied to their surfaces to control the reactivity and/or the mechanical properties of the compact.
- Still another and/or alternative non-limiting object of the present invention is the provision of multi-grain compacts and a process and method for forming the multi-grain compacts having controlled reaction kinetics catalyzed by an external stimulus, such as, but not limited to, an ignition source and/or environmental change.
- Yet another and/or alternative non-limiting object of the present invention is the provision of particles and the formation of particles wherein the reaction kinetics can be at least partially controlled through the use of engineered building block repeating units combined with a solid and/or semi-solid state consolidation.
- Still yet another and/or alternative non-limiting object of the present invention is the provision of engineered particles or building block repeating units that have more controllable, predictable, and/or lower cost fabrication of reactive composite parts using powder metallurgy techniques.
- Another and/or alternative non-limiting object of the present invention is the provision of individual particles or agglomerates which have applied to their surface a second, discreet phase material of different composition from the particle which provides for at least partial control over the reaction with the core particle or the environment during exposure and/or which may be tailored by controlling the relative particle sizes and/or amounts to provide a controlled reactivity rate.
- Still another and/or alternative non-limiting object of the present invention is the provision of a method and process for coating fine particles with ceramic and metallic materials.
- Yet another and/or alternative non-limiting object of the present invention is the provision of a method and process that involves the applying of coatings to particles in a continuous (or discontinuous, depending on application), pore-free manner.
- Still yet another and/or alternative non-limiting object of the present invention is the provision of the design and/or composition of matter for metal and/or ceramic particles to which have been applied a surface modifying layer or layers.
- Another and/or alternative non-limiting object of the present invention is the provision of coated particles wherein in the coating and particle have different properties, the combination of which can be made to react in a controlled fashion in response to the imposition of an external stimulus.
- Still another and/or alternative non-limiting object of the present invention is the provision of an engineered reactive matrix composite which include a core material, and a reactive binder matrix, which engineered reactive matrix is a repeating metal or ceramic particle core material and a reactive binder/matrix.
- Yet another and/or alternative non-limiting object of the present invention is the provision of an engineered reactive matrix composite which include a core material, and a reactive binder matrix, and the reactivity of the reactive binder/matrix can be engineered by controlling the relative interfacial surface area of the reactive components.
- Still yet another and/or alternative non-limiting object of the present invention is the provision of a method of manufacturing reactive composites, which method includes the preparation of a plurality of engineered, reactive composite building blocks, and then consolidating these building blocks below the liquidus of the binder or core material.
- Another and/or alternative non-limiting object of the present invention is the provision of adding an additive/modifier onto the surface of a powder to form an integral unit to achieve simplified handling of powder materials, simplified production of a compact with increased homogeneity and/or improved and more repeatable performance/properties.
- These and other objects, features and advantages of the present invention will become apparent in light of the following detailed description of preferred embodiments thereof, as illustrated in the accompanying drawings.
-
FIGS. 1-2 are a cross-sectional illustration of composite particles in accordance with the present invention wherein the black core represents the primary particle which can be a metal, metal alloy, and/or a ceramic particle, and the surrounding white section represents the additive/modifier which has been added to the surface of the primary particle in accordance with the present invention; -
FIGS. 3A-3C illustrate magnesium-coated graphite, a consolidated magnesium-graphite part in its microstructure respectively, in accordance with the present invention; -
FIG. 4 illustrates a magnesium-iron-graphite reactive composite microstructure in accordance with the present invention; and, -
FIG. 5 is a schematic diagram showing carbon particles embedded in a matrix of magnesium alloy with an iron interface, along with an actual composite structure, wherein the carbon particles (black) are first coated with a wetting and reaction accelerator (iron) and then with an activator (slightly darker shade), and these composite powders are then embedded in a matrix of magnesium alloy using powder metallurgy techniques. - In accordance with the present invention, a metal, metal alloy, and/or ceramic particle, typically used for powder metallurgy fabrication, is provided which is made from a primary particle which has a thin, continuous or non-continuous coating of a reactive matrix and/or binder used to improve the consolidation behavior, properties of the resultant powder metallurgy compact, and/or to provide controlled response to external stimuli. The coated particle is comprised of a metal, metal alloy, and/or a ceramic particle, to which has been applied a surface coating of at least about 1% of the primary particle diameter, typically no more than about 50% of the primary particle diameter (e.g., 1%, 1.01%, 1.02% . . . 49.98%, 49.99%, 50%) and any valve or range therebetween, and still more typically about 1 to 40% of the primary particle diameter using any applicable technique such as, but not limited to CVD, plating, spray-cladding, solution precipitation, mechanochemical cladding, electrostatic agglomeration, etc.
FIGS. 1-2 are illustrations of non-limitingcoated particles 10 in accordance with the present invention. The primary orcore particle 20 is designed in black and the coating of a reactive matrix and/orbinder 30 is illustrated as the white layer about the primary or core particle. - The relative interfacial area between the core and the coating is controlled to provide for a controlled reaction rate. This rate may be further augmented by the production of a dual-phase matrix/binder having a much higher interfacial area than the coarser core particles; however, this is not required.
- The starting material is a metal, metal alloy, and/or ceramic particle having an average particle diameter size of at least about 0.1 microns, typically no more than about 500 microns (e.g., 0.1 microns, 0.1001 microns, 0.1002 microns . . . 499.9998 microns, 499.9999 microns, 500 microns) and including any value or range therebetween, more typically about 0.1 to 400 microns, and still more typically about 10 to 50 microns. The primary particles may be prepared through any number of synthesis routes including, but not limited to, gas and/or vacuum atomization, mechanical breakdown, gas precipitation and/or liquid precipitation, and/or other suitable techniques.
- The starting primary particles are typically heat treated and/or etched to remove any adsorbed gases and/or surface oxide layers; however, this is not required. The primary particles are then coated with a metal, metal alloy, ceramic and/or composite layer. This layer serves to modify the mechanical properties and reactivity of the compact (i.e., particle plus coating), for example, by providing for an intermetallic or galvanic reaction with the primary particle and/or with interaction with secondary particles added during consolidation. Also, in accordance with the present invention, the particle coating may prevent reoxidation of the primary particle, limit reaction of the particle with a metal matrix, and/or modify the diffusional properties (i.e., grain growth, grain boundary strength, etc.) of the particle when consolidated.
- In accordance with the present invention, the formation of the coated particles may be accomplished by applying either a single layer of a metal, metal alloy, ceramic and/or composite coating, and/or a multilayer or composite coating system. Additional particles of a finer size (i.e., small average diameter size) than the primary particle or the coated particles may further be added during consolidation to reduce cost, and/or modify the mechanical or reactive functions of the reactive matrix (i.e., primary particle plus coating or primary particle plus coating plus finer additional particles). The coating can have a thickness that is neither too thin nor too thick. A thicker coating facilitates wetting of the particles during consolidation. On the other hand, too thick a coating will reduce the concentration of the primary particles, reduce the dissolution rate of the matrix in a controlled electrolytic reaction, and/or may result in detrimental effects on the final compact properties. Typically, the coating is at least about 1% of the primary particle diameter, typically no more than about 50% primary particle diameter (e.g., 1%, 1.01%, 1.02% . . . 49.98%, 49.99%, 50%) and any value or range therebetween, and typically about 1 to 30% of the primary particle diameter. Also or alternatively, the coating is at least about 0.01 microns thick, typically no more than about 10 microns thick (e.g., 0.01 microns, 0.01001 microns, 0.01002 microns . . . 9.9998 microns, 9.9999 microns, 10 microns) and any value or range therebetween, and more typically about 0.1 to 5 microns thick. In one non-limiting embodiment of the invention, the primary or core particle can be deformable during consolidation to promote the formation of a space-filling array of repeating engineered particle units; however, this is not required.
- In one non-limiting embodiment of the invention, the particles include aluminum particles having an average particle diameter size of about 5 to 50 microns (e.g., 5 microns, 5.01 microns, 5.02 microns . . . 49.98 microns, 49.99 microns, 50 microns) and any value or range therebetween, that are degassed and/or deoxidized, and then coated with about 0.3 to 2 microns coating thickness (e.g., 0.3 microns, 0.301 microns, 0.302 microns . . . 1.998 microns, 1.999 microns, 2 microns) and any value or range therebetween, of silicon, silver, and/or zinc. In another non-limiting embodiment, smaller or larger particles can be coated with thicker or thinner coatings. As can be appreciated, multilayer coatings can be applied to one or more of the primary or core particles.
- In still another embodiment, the primary or core particles include iron and/or carbon particles having an average particle diameter size of about 5 to 50 microns (e.g., 5 microns, 5.01 microns, 5.02 microns . . . 49.98 microns, 49.99 microns, 50 microns) and any value or range therebetween, that are coated with about 0.3 to 3 microns coating thickness (e.g., 0.3 microns, 0.301 microns, 0.302 microns . . . 2.998 microns, 2.999 microns, 3 microns) and any value or range therebetween, of a matrix of magnesium and/or zinc. The consolidated compact reacts when activated by an electrolyte, with the reactive binder dissolving at a controlled rate. Having a high surface area of the cathode (iron and/or graphite) and a small area of the reactive binder can speed the reaction rate.
- In yet another embodiment, a tungsten powder having an average particle diameter size of about 5 to 100 microns (e.g., 5 microns, 5.01 microns, 5.02 microns . . . 99.98 microns, 99.99 microns, 100 microns) and any value or range therebetween, is coated with about 0.3 to 3 microns coating thickness (e.g., 0.3 microns, 0.301 microns, 0.302 microns . . . 2.998 microns, 2.999 microns, 3 microns) and any value or range therebetween, of zinc and/or magnesium, followed by powder forging or spark plasma sintering to form a high density reactive matrix composite. This high density composite can be activated by vaporizing the zinc and/or magnesium upon high velocity impact, wherein the magnesium and/or zinc vapor reacts with the air that can produce a secondary explosion or deflagration thermal event.
- In still yet another embodiment, a high density reactive material such as silicon, boron, and/or tantalum having an average particle diameter size of about 5 to 100 microns (e.g., 5 microns, 5.01 microns, 5.02 microns . . . 99.98 microns, 99.99 microns, 100 microns) and any value or range therebetween, is coated with about 0.3 to 3 microns coating thickness (e.g., 0.3 microns, 0.301 microns, 0.302 microns . . . 2.998 microns, 2.999 microns, 3 microns) and any value or range therebetween, of a reactive composite binder (e.g., aluminum, magnesium, etc.) and an oxidizer (e.g., fluorinated polymer, etc.) having a coating thickness of about 0.01 to 3 microns coating thickness (e.g., 0.01 microns, 0.01001 microns, 0.01002 microns . . . 2.998 microns, 2.999 microns, 3 microns) and any value or range therebetween. The reactive composite binder can optionally be designed to rapidly ignite upon a thermal stimulus (e.g., a fuse, via high velocity impact, etc.), dispersing and igniting the core particles which produce a secondary reaction. The core particles are normally not ignitable without the preheating and dispersion created by the reactive composite coating; however, this is not required.
- In still a further embodiment, the reactivity of an electrolytically activated reactive composite of magnesium and/or zinc and iron is controlled to produce a dissolution rate from about 1 to 10 mm/day and any value or range therebetween, by controlling the relative phase amounts and interfacial surface area of the two galvanically active phases. In one non-limiting example, a mechanical mixture of iron and/or graphite and/or and zinc and/or magnesium is prepared and applied to the surface of about 30 to 200 micron and any value or range therebetween of iron and/or graphite particles, followed by consolidation using spark plasma sintering or powder forging at a temperature below the magnesium and/or zinc melting point. The resultant structure has an accelerated rate of reaction due to the high exposed surface area of the iron and/or graphite cathode phase, but low relative area of the anodic (zinc and/or magnesium) reactive binder.
- These non-limiting examples of the invention lead to an excellent material for powder metallurgical processing.
FIGS. 3A-3C and 4 illustrate a representative microstructure for a magnesium-graphite composite and a magnesium-iron-graphite composite.FIG. 3A is a magnified picture of magnesium-coated graphite.FIG. 3B is consolidated magnesium-graphite part.FIG. 3C is a magnified view of the microstructure of the magnesium-graphite part ofFIG. 3B .FIG. 4 is a magnified view of a magnesium-iron-graphite reactive composite microstructure. -
FIG. 5 is a schematic diagram showing acomposite particle 10 formed of primary or core particles, such as, but not limited to, carbon particles, embedded in a matrix of coating of, but not limited to, a magnesium alloy with an interface of, but not limited to, iron, along with an actual composite structure. The primary orcore particles 20 are illustrated as the black colored core. The primary or core particles are first coated with a wetting and reaction accelerator (e.g., iron, etc.) 30 which is illustrated as the white colored coating layer about the primary or core particles. Anactivator 40 is subsequently coated onto the wetting and reaction accelerator layer, which activator layer is illustrated as the slightly darker shade or grey colored layer about the white colored wetting and reaction accelerator layer. The coating thicknesses of the wetting and reaction accelerator layer and the activator layer can be the same or different. All three layers of the composite particle are generally formed of a different material; however, two non-adjacently positioned layers can be formed of the same material. The composite particle can have the same shape and/or size; however, this is not required. A plurality ofcomposite particles 10 are illustrated as being embedded in a matrix ofmaterial 50 such as, but not limited, to magnesium alloy to form amatrix composite material 60. The process of embedding the composite particles in the matrix material to form the matrix composite material can be by use of powder metallurgy techniques. - Iron powder having a particle size of about 20 to 40 microns is loaded into a fluidized bed reactor. Magnesium metal vapor is then introduced into the reactor and condenses to form a magnesium coating on the iron particles. About 8 to 12% by volume (e.g., 10% by volume) of magnesium is added to the iron powder. The resultant magnesium coated iron powder is then consolidated into a billet, and powder forged into a final shape at about 380 to 480° C. under about 30 to 100 tons/in2 compaction pressure.
- The resultant compact has high mechanical properties, generally above 30 KSI strength, and when exposed to slightly acidic or salt solutions, is corroded at a rate of 0.1-15 mm/day depending on environment and temperature.
- Magnesium powder is dry-milled under inert atmosphere with about 10 to 60% by volume of 1 to 3 microns carbonyl iron powder (a composite of iron and carbon) and a small amount of catalyst (iron aluminide is one example) to produce a composite powder blend. Additionally, coarse iron powder (as in Example 1) is loaded into a fluidized bed reactor, and the milled magnesium-iron-carbon is then applied to the surface of the coarse graphite powder by spraying a solution of the magnesium powder, a binder, and a liquid carrier onto the surface of the powder in a fluidized bed. Thereafter is the addition of about 8 to 22% by volume magnesium composite powder. The resultant composite powder is consolidated using spark plasma sintering or powder forging with 20-40% upset to form a fully dense compact, which is machined into galvanically activated reactive composite parts having a dissolution rate of about 0.1 to 5 mm/hour in a brine solution.
- Silicon, titanium, or zirconium metal powder having a particle size of about 10 to 50 microns is loaded into a fluidized bed. A mixture of fine magnesium powder and polyvinylidene difluoride (PVDF) in a solvent is applied as a surface coating onto the silicon powder and the solvent is removed. The resultant powder is warm-compacted to form a high density reactive metal matrix composite having a strength greater than 10 KSI, and which can be initiated to disperse, react, and produce a high energy blast effect using an external stimulus such as hard target penetration or electrically stimulated to generate heat and disintegrate rapidly.
- Tungsten powder having a particle size of about 10 to 20 microns is placed into a fluidized bed and coated with a mixture of titanium and boron powders with an atomic ratio of about 0.5-2:1. The resultant coated particles are cold-pressed, outgased, and powder forged or spark plasma sintered into a conical structure. This reactive cone is able to be explosively formed into a reactive slug which provides excellent penetration into tight formations to release oil and gas concentrations, self-heating itself to over 800 C and providing a high density slug with excellent penetration characteristics.
- A magnesium or zinc coating is applied using vapor deposition to an oxidizer core, which can be iron oxide, KClO4, AgNO3, or Bi2O3 or other oxidizer particle, having a size between 1 and 50 microns, and preferably between 10 and 25 microns. These powders are then further blended with 5-30V% of a thermoplastic fluorinated polymeric material such as PVDF or PTFE. The resultant blended mixture is warm compacted or molded to form a fully dense (greater than 95% dense) compact having mechanical properties of greater than 5,000 PSIG flexure strength and a high energy density that can be triggered to give a large thermal or gas pressure response using an electrical or thermal signal.
- A magnesium or zinc coating is applied using vapor deposition to a 1-50 micron graphite, metal, or ceramic core particle to form a 0.1-3 micron thick Mg coating. The coated core particles are warm-compacted or pressed and sintered to form a porous perform having between 10 and 50% open porosity, but near-zero “touching” of the ceramic or metallic core particles. This controlled density perform is then melt-infiltrated with aluminum, magnesium alloy, aluminum-magnesium alloy, or zinc alloy to form a reactive metal matrix composite having a strength above 8000 psig, and meeting predetermined dissolution or reactive rates, where such reactivity is controlled by controlling the relative amounts of phases and the size and composition of the starting core particles.
- It will thus be seen that the objects set forth above, among those made apparent from the preceding description, are efficiently attained, and since certain changes may be made in the constructions set forth without departing from the spirit and scope of the invention, it is intended that all matter contained in the above description and shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense. The invention has been described with reference to preferred and alternate embodiments. Modifications and alterations will become apparent to those skilled in the art upon reading and understanding the detailed discussion of the invention provided herein. This invention is intended to include all such modifications and alterations insofar as they come within the scope of the present invention. It is also to be understood that the following claims are intended to cover all of the generic and specific features of the invention herein described and all statements of the scope of the invention, which, as a matter of language, might be said to fall there between. The invention has been described with reference to the preferred embodiments. These and other modifications of the preferred embodiments as well as other embodiments of the invention will be obvious from the disclosure herein, whereby the foregoing descriptive matter is to be interpreted merely as illustrative of the invention and not as a limitation. It is intended to include all such modifications and alterations insofar as they come within the scope of the appended claims.
Claims (18)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17/359,765 US20210323891A1 (en) | 2012-12-10 | 2021-06-28 | Material and method of manufacture for engineered reactive matrix compositions |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201261735246P | 2012-12-10 | 2012-12-10 | |
PCT/US2013/073988 WO2014093269A1 (en) | 2012-12-10 | 2013-12-10 | Engineered reactive matrix composites |
US201514432875A | 2015-04-01 | 2015-04-01 | |
US16/137,934 US11530170B2 (en) | 2012-12-10 | 2018-09-21 | Material and method of manufacture for engineered reactive matrix composites |
US17/359,765 US20210323891A1 (en) | 2012-12-10 | 2021-06-28 | Material and method of manufacture for engineered reactive matrix compositions |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/137,934 Division US11530170B2 (en) | 2012-12-10 | 2018-09-21 | Material and method of manufacture for engineered reactive matrix composites |
Publications (1)
Publication Number | Publication Date |
---|---|
US20210323891A1 true US20210323891A1 (en) | 2021-10-21 |
Family
ID=50934869
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/432,875 Active 2035-02-03 US10392314B2 (en) | 2012-12-10 | 2013-12-10 | Material and method of manufacture for engineered reactive matrix composites |
US16/137,934 Active 2035-12-18 US11530170B2 (en) | 2012-12-10 | 2018-09-21 | Material and method of manufacture for engineered reactive matrix composites |
US17/359,765 Abandoned US20210323891A1 (en) | 2012-12-10 | 2021-06-28 | Material and method of manufacture for engineered reactive matrix compositions |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/432,875 Active 2035-02-03 US10392314B2 (en) | 2012-12-10 | 2013-12-10 | Material and method of manufacture for engineered reactive matrix composites |
US16/137,934 Active 2035-12-18 US11530170B2 (en) | 2012-12-10 | 2018-09-21 | Material and method of manufacture for engineered reactive matrix composites |
Country Status (3)
Country | Link |
---|---|
US (3) | US10392314B2 (en) |
CA (1) | CA2888137C (en) |
WO (1) | WO2014093269A1 (en) |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10364631B2 (en) | 2016-12-20 | 2019-07-30 | Baker Hughes, A Ge Company, Llc | Downhole assembly including degradable-on-demand material and method to degrade downhole tool |
US10865617B2 (en) | 2016-12-20 | 2020-12-15 | Baker Hughes, A Ge Company, Llc | One-way energy retention device, method and system |
US10450840B2 (en) | 2016-12-20 | 2019-10-22 | Baker Hughes, A Ge Company, Llc | Multifunctional downhole tools |
US10364630B2 (en) | 2016-12-20 | 2019-07-30 | Baker Hughes, A Ge Company, Llc | Downhole assembly including degradable-on-demand material and method to degrade downhole tool |
US10364632B2 (en) | 2016-12-20 | 2019-07-30 | Baker Hughes, A Ge Company, Llc | Downhole assembly including degradable-on-demand material and method to degrade downhole tool |
US10221641B2 (en) | 2017-03-29 | 2019-03-05 | Baker Hughes, A Ge Company, Llc | Downhole tools having controlled degradation and method |
US10221642B2 (en) | 2017-03-29 | 2019-03-05 | Baker Hughes, A Ge Company, Llc | Downhole tools having controlled degradation and method |
US10167691B2 (en) | 2017-03-29 | 2019-01-01 | Baker Hughes, A Ge Company, Llc | Downhole tools having controlled disintegration |
US10221643B2 (en) | 2017-03-29 | 2019-03-05 | Baker Hughes, A Ge Company, Llc | Downhole tools having controlled degradation and method |
US10815748B1 (en) * | 2017-05-19 | 2020-10-27 | Jonathan Meeks | Dissolvable metal matrix composites |
US11015409B2 (en) | 2017-09-08 | 2021-05-25 | Baker Hughes, A Ge Company, Llc | System for degrading structure using mechanical impact and method |
WO2019126336A1 (en) | 2017-12-20 | 2019-06-27 | Terves Inc. | Material and method of controlled energy deposition |
US11426818B2 (en) | 2018-08-10 | 2022-08-30 | The Research Foundation for the State University | Additive manufacturing processes and additively manufactured products |
CN109082549B (en) * | 2018-10-26 | 2020-08-11 | 北京理工大学 | Preparation method of easy-reaction aluminum/tungsten active material |
DE102019205276A1 (en) * | 2019-04-11 | 2020-10-15 | Christof-Herbert Diener | Coating process of an energetic material and coating system for coating the energetic material by such a coating process |
CN110981670B (en) * | 2019-11-15 | 2021-12-07 | 上海航天化工应用研究所 | Solid propellant containing core-shell modified oxidant and preparation method thereof |
CN114890855B (en) * | 2022-04-24 | 2023-03-14 | 江苏理工学院 | Interlayer hybrid energy-containing structural material and preparation method thereof |
CN116283456B (en) * | 2023-01-05 | 2024-03-05 | 北京理工大学 | Heat-insensitive aluminum-containing mixed explosive and preparation method thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110067789A1 (en) * | 2008-05-16 | 2011-03-24 | Digital Solid State Propulsion, Llc | Family of Modifiable High Performance Electrically Controlled Propellants and Explosives |
US20110135953A1 (en) * | 2009-12-08 | 2011-06-09 | Zhiyue Xu | Coated metallic powder and method of making the same |
US20120006562A1 (en) * | 2010-07-12 | 2012-01-12 | Tracy Speer | Method and apparatus for a well employing the use of an activation ball |
US20120247765A1 (en) * | 2011-03-29 | 2012-10-04 | Baker Hughes Incorporated | High Permeability Frac Proppant |
US20130206425A1 (en) * | 2012-02-13 | 2013-08-15 | Baker Hughes Incorporated | Selectively Corrodible Downhole Article And Method Of Use |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4063907A (en) | 1975-07-28 | 1977-12-20 | General Electric Company | Modifying the surface of diamond particles |
JPS6041136B2 (en) | 1976-09-01 | 1985-09-14 | 財団法人特殊無機材料研究所 | Method for manufacturing silicon carbide fiber reinforced light metal composite material |
US5008132A (en) | 1989-06-06 | 1991-04-16 | Norton Company | Process for preparing titanium nitride coated silicon carbide materials |
US5171419A (en) | 1990-01-18 | 1992-12-15 | American Cyanamid Company | Metal-coated fiber compositions containing alloy barrier layer |
US5184662A (en) | 1990-01-22 | 1993-02-09 | Quick Nathaniel R | Method for clad-coating ceramic particles |
GB2242443B (en) | 1990-03-28 | 1994-04-06 | Nisshin Flour Milling Co | Coated particles of inorganic or metallic materials and processes of producing the same |
US5820721A (en) | 1991-07-17 | 1998-10-13 | Beane; Alan F. | Manufacturing particles and articles having engineered properties |
US5453293A (en) | 1991-07-17 | 1995-09-26 | Beane; Alan F. | Methods of manufacturing coated particles having desired values of intrinsic properties and methods of applying the coated particles to objects |
US5292477A (en) | 1992-10-22 | 1994-03-08 | International Business Machines Corporation | Supersaturation method for producing metal powder with a uniform distribution of dispersants method of uses thereof and structures fabricated therewith |
US20110027547A1 (en) * | 2000-05-02 | 2011-02-03 | Reactive Nanotechnologies, Inc. | Methods of making reactive composite materials and resulting products |
WO2006093519A2 (en) | 2004-07-01 | 2006-09-08 | Advanced Ceramics Research, Inc. | Compositions for preparing materials having controlled reactivity |
EA201290595A1 (en) * | 2009-12-31 | 2012-12-28 | Оксан Материалз, Инк. | CERAMIC PARTICLES WITH ADJUSTABLE TIMES AND / OR LOCATION AND / OR MICROSPHERE SIZE AND METHOD OF THEIR MANUFACTURE |
US8231748B1 (en) | 2011-08-18 | 2012-07-31 | The United States Of America As Represented By The Secretary Of The Navy | Scalable low-energy modified ball mill preparation of nanoenergetic composites |
US8857513B2 (en) * | 2012-01-20 | 2014-10-14 | Baker Hughes Incorporated | Refracturing method for plug and perforate wells |
AU2012376793B2 (en) * | 2012-04-10 | 2015-02-12 | Halliburton Energy Services, Inc. | Method and apparatus for generating seismic pulses to map subterranean fractures |
US9429005B2 (en) * | 2012-11-28 | 2016-08-30 | Halliburton Energy Services, Inc. | Methods for hindering the settling of proppant in a subterranean formation |
US20140144620A1 (en) * | 2012-11-28 | 2014-05-29 | General Plastics & Composites, L.P. | Electrostatically coated composites |
-
2013
- 2013-12-10 WO PCT/US2013/073988 patent/WO2014093269A1/en active Application Filing
- 2013-12-10 US US14/432,875 patent/US10392314B2/en active Active
- 2013-12-10 CA CA2888137A patent/CA2888137C/en not_active Expired - Fee Related
-
2018
- 2018-09-21 US US16/137,934 patent/US11530170B2/en active Active
-
2021
- 2021-06-28 US US17/359,765 patent/US20210323891A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110067789A1 (en) * | 2008-05-16 | 2011-03-24 | Digital Solid State Propulsion, Llc | Family of Modifiable High Performance Electrically Controlled Propellants and Explosives |
US20110135953A1 (en) * | 2009-12-08 | 2011-06-09 | Zhiyue Xu | Coated metallic powder and method of making the same |
US20120006562A1 (en) * | 2010-07-12 | 2012-01-12 | Tracy Speer | Method and apparatus for a well employing the use of an activation ball |
US20120247765A1 (en) * | 2011-03-29 | 2012-10-04 | Baker Hughes Incorporated | High Permeability Frac Proppant |
US20130206425A1 (en) * | 2012-02-13 | 2013-08-15 | Baker Hughes Incorporated | Selectively Corrodible Downhole Article And Method Of Use |
Also Published As
Publication number | Publication date |
---|---|
US11530170B2 (en) | 2022-12-20 |
US20190023630A1 (en) | 2019-01-24 |
US20150259263A1 (en) | 2015-09-17 |
US10392314B2 (en) | 2019-08-27 |
CA2888137C (en) | 2021-01-26 |
WO2014093269A1 (en) | 2014-06-19 |
CA2888137A1 (en) | 2014-06-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20210323891A1 (en) | Material and method of manufacture for engineered reactive matrix compositions | |
EP2509734B1 (en) | Method of making a nanomatrix powder metal compact | |
CA2783547C (en) | Coated metallic powder and method of making the same | |
AU2010328281B2 (en) | Nanomatrix powder metal compact | |
EP2509732B1 (en) | Engineered powder compact composite material | |
US10737321B2 (en) | Magnesium alloy powder metal compact | |
EP2750819B1 (en) | Nanostructured powder metal compact | |
CN102256740A (en) | Novel wear-resistant films and a method for the production and for the use thereof | |
Dobrzański et al. | Overview of conventional technologies using the powders of metals, their alloys and ceramics in Industry 4.0 stage | |
US7297310B1 (en) | Manufacturing method for aluminum matrix nanocomposite | |
CN106282718B (en) | A kind of gradient distribution hard alloy and preparation method thereof | |
Lemboub et al. | Complex TiC-Ni-based composites joined to steel support by thermal explosion under load: Synthesis, microstructure and tribological behavior |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: POWDERMET, INC., OHIO Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SHERMAN, ANDREW J.;DOUD, BRIAN P.;REEL/FRAME:056682/0892 Effective date: 20150410 |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |