EP2555891A1 - Composite system - Google Patents
Composite systemInfo
- Publication number
- EP2555891A1 EP2555891A1 EP10850356A EP10850356A EP2555891A1 EP 2555891 A1 EP2555891 A1 EP 2555891A1 EP 10850356 A EP10850356 A EP 10850356A EP 10850356 A EP10850356 A EP 10850356A EP 2555891 A1 EP2555891 A1 EP 2555891A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- powder
- titanium
- composite system
- mixture
- aluminum
- 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.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 160
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 130
- 239000000203 mixture Substances 0.000 claims abstract description 87
- 239000010936 titanium Substances 0.000 claims abstract description 69
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 69
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000000463 material Substances 0.000 claims abstract description 54
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 51
- 239000000956 alloy Substances 0.000 claims abstract description 51
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 37
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 30
- 239000000919 ceramic Substances 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 155
- 238000000034 method Methods 0.000 claims description 95
- 239000000758 substrate Substances 0.000 claims description 41
- 239000008187 granular material Substances 0.000 claims description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 238000005245 sintering Methods 0.000 claims description 22
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 15
- 229910000838 Al alloy Inorganic materials 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 229910010293 ceramic material Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 239000010955 niobium Substances 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 229910014813 CaC2 Inorganic materials 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 239000011573 trace mineral Substances 0.000 claims description 6
- 235000013619 trace mineral Nutrition 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005275 alloying Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 150000004678 hydrides Chemical class 0.000 claims 5
- 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 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 29
- 239000011159 matrix material Substances 0.000 abstract description 18
- 239000012071 phase Substances 0.000 description 38
- 239000010410 layer Substances 0.000 description 37
- 208000010392 Bone Fractures Diseases 0.000 description 19
- 206010017076 Fracture Diseases 0.000 description 19
- 238000001878 scanning electron micrograph Methods 0.000 description 15
- 238000005336 cracking Methods 0.000 description 11
- 239000004615 ingredient Substances 0.000 description 10
- 235000012431 wafers Nutrition 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 102100031831 Adipogenesis regulatory factor Human genes 0.000 description 3
- 229910052580 B4C Inorganic materials 0.000 description 3
- 101000775473 Homo sapiens Adipogenesis regulatory factor Proteins 0.000 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 description 3
- -1 and optionally Chemical compound 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 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 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001513 hot isostatic pressing Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910001000 nickel titanium Inorganic materials 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DMJXRYSGXCLCFP-LBPRGKRZSA-N (3s)-n-tert-butyl-1,2,3,4-tetrahydroisoquinoline-3-carboxamide Chemical compound C1=CC=C2CN[C@H](C(=O)NC(C)(C)C)CC2=C1 DMJXRYSGXCLCFP-LBPRGKRZSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000005997 Calcium carbide Substances 0.000 description 1
- 229910000760 Hardened steel Inorganic materials 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- CAVCGVPGBKGDTG-UHFFFAOYSA-N alumanylidynemethyl(alumanylidynemethylalumanylidenemethylidene)alumane Chemical compound [Al]#C[Al]=C=[Al]C#[Al] CAVCGVPGBKGDTG-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000005495 investment casting Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000010120 permanent mold casting Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000008733 trauma Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
Definitions
- This invention relates to alloy systems containing hard particles, such as particles of TiC.
- TiC alloys have been formed by "cementing" very hard TiC powder (Vickers 3200) using binders made of nickel, molybdenum, niobium, and tungsten, with the binding elements typically constituting about 40 to 50% of the total weight of such an alloy.
- these TiC alloys are formed using powder metallurgy techniques from very fine particles, in particular, materials having a particle size under 20 microns, with a substantial portion being under 6 microns.
- the metals historically used for binding in TiC alloys have relatively high densities, in particular, nickel at 8.9 g/cc, molybdenum at 10.22 g/cc, niobium at 8.57 g/cc, and tungsten at 19.3g/cc. As a result, such composite TiC alloys have had a density of about 6 g/cc or higher. Materials of that high density are
- a new composite system described herein has superior properties, being not only hard, but also being much lighter in weight than 6 grams/cc and having better toughness characteristics than previously reported TiC alloys.
- the composite systems described herein are formed from a hard powder as described herein, such as a TiC powder, combined with a green binder system of titanium sponge granules and/or other titanium powders and a binder system comprising titanium, nickel, and aluminum provided either as a master alloy or as elemental powders, which then are compressed and sintered. It is observed that the nickel forms lower melting point eutectoid-like structures when combined with the titanium of the green binder system.
- Bodies of TiC composite systems described herein can bind with bodies of titanium or other materials, allowing for the production of layered composite armor structures.
- Such layered composite structures can have advantageous attachment configurations, and favorable weight, ductility, and ballistics properties.
- FIG. 1 is a schedule showing calculated chemical compositions of various TiC composite systems.
- FIG. 2a includes SEM micrographs showing backscattered electron images and energy dispersive x-ray spectra acquired from the fracture surface of a prior art material that is believed to be an alloy that contains titanium carbide as the principal ingredient and nickel-molybdenum as a binder material.
- FIG. 2b includes SEM micrographs showing backscattered electron images and energy dispersive x-ray spectra acquired from the fracture surface of a TiC composite system described herein, the images showing TiC particles in the aggregate phase that are larger than any of the grains in the materials of FIG. 2a and FIG. 2c.
- FIG. 2c includes SEM micrographs showing backscattered electron images and energy dispersive x-ray spectra acquired from the fracture surface of a prior art ceramic material believed to be used for making armor tiles.
- FIG. 3a is a photograph of a tile made of a TiC composite system described herein bonded to a substrate layer of titanium, the tile having defeated a high velocity impact by a 5.56 mm, 62 grain, full metal jacket bullet shot by a 16 inch barrel AR-15 rifle in a ballistics test.
- FIG. 3b is a photograph of the standard APM2 armor-piercing hardened steel penetrator (upper portion) that was defeated and broken by impact with the tile of the TiC composite system described herein in a ballistics test and a photograph of an unbroken APM2 penetrator (lower portion) shown for comparison.
- FIG. 3c includes SEM micrographs of the defeated APM2 penetrator of FIG. 3b showing cracking, a blunted tip, axial gouges and scoring, and deposition of a lower density material (darker areas).
- FIG. 4a includes SEM micrographs that show secondary electron and backscattered electron images of the TiC composite system layer fracture surface of the tile of FIG. 3a and that identify structure and cracking patterns that result when the tile is impacted and account for the enhanced energy absorption and superior ballistics performance of the tile of FIG. 3a.
- the three secondary electron images indicate a mixed ductile/brittle fracture. Comparison of the backscattered electron and secondary electron images indicates brittle faceted fracture of a low density aggregate phase and ductile fracture of a higher density matrix phase.
- FIG. 4b includes an SEM micrograph that shows a backscattered electron image and energy dispersive x-ray spectra acquired from ductile and brittle areas of the TiC composite fracture surface of the tile of FIG. 3a.
- the results suggest a two phase matrix consisting of a lower nickel, nickel-titanium alloy and a higher nickel, nickel-titanium alloy. Ductile fracture appears to be confined to the lower nickel matrix phase.
- FIG. 4c includes SEM micrographs that show backscattered electron images of a metallo graphic section through secondary cracking through the TiC composite layer of the tile of FIG. 3a.
- the TiC composite includes a low density aggregate phase (titanium carbide) and a two phase (white and light grey) matrix.
- the crack tip (lower micrograph) terminated at an area of discontinuous cracking in the titanium carbide phase only.
- FIG. 4d is an SEM micrograph that shows a backscattered electron image of a polished metallographic section through the primary fracture through the TiC composite layer of the tile of FIG. 3a. Cracking extended through all three phases. Cracking was not confined to a single phase or to the boundaries between the phases.
- FIG. 4e is an SEM micrograph that shows a backscattered electron image of a polished metallographic section through a secondary crack through the TiC composite layer of the tile of FIG. 3a.
- Cracking within the carbide phase is highly branched. Many of the cracks appear to terminate at the carbide to matrix boundary. The creating of multiple branched cracks and crack termination at phase boundaries would predictably absorb energy.
- the apparent fracture mechanism (crack branching in the carbide phase and crack termination at the phase boundaries) may account for reported good ballistic properties.
- FIG. 4f is an SEM micrograph that shows a backscattered electron image of a metallographic section through the primary fracture through the TiC composite layer of the tile of FIG. 3a. Branched cracking within the titanium carbide phase and crack termination at the carbide to matrix phase boundary is apparent.
- FIG. 5a includes an SEM micrograph that shows a backscattered electron image and an energy dispersive x-ray spectra acquired from the failed interface on the TiC composite system layer of the tile of FIG. 3a, the two-phase structure and presence of nickel indicating failure within the TiC composite system layer rather than at the titanium to TiC composite system interface.
- FIG. 5b includes SEM micrographs that show backscattered electron images and an energy dispersive x-ray spectra acquired from the fracture in the titanium layer of the tile of FIG. 3a, fracture having occurred in a ductile manner.
- FIG. 5c is an SEM micrograph that shows a backscattered electron image of a polished metallographic section through the titanium layer at the separation between the titanium and TiC composite system layers of the tile of FIG. 3a, separation having occurred in the TiC composite system layer as evidenced by the adhering TiC composite system material to the titanium layer.
- FIG. 5d is an SEM micrograph of a metallographic section through the interface of a tile comprising a layer of a TiC composite system described herein bonded to a substrate layer of alumina ceramic showing microhardness test locations and Vickers (HV) hardness data obtained.
- HV Vickers
- FIG. 5e includes SEM micrographs that show increasing magnification backscattered electron images of a metallographic section through the interface of the tile of FIG. 5d, with three distinct interface layers apparent between the ceramic (black band at the bottom) and the TiC composite system (multi-phase areas at the tops of the micrographs).
- a composite system that is a multiphase alloy is produced by binding very hard particles of various sizes using master alloys or a blend of elemental materials and titanium powders.
- the composite system has characteristics that make the composite system particularly well suited for energy absorption.
- the composite system has an aggregate phase of hard particles and a matrix phase that binds the hard particles together.
- FIGS. 2b and 4a-4f illustrate an example of such a composite system in which the hard particles are TiC (referred to as TiC composite systems or TiCC). Testing of examples of such TiC composite systems indicates that the matrix phase, which comprises amounts of nickel, titanium, and aluminum, has at least two phases as shown in FIG. 4b. The phases of nickel, titanium, aluminum matrix phase have varying degrees of hardness and ductility.
- the slightly ductile matrix phase is believed to be responsible for an observed tortuous crack propagation pattern, as shown in FIGS. 4a-4f, that forms when a body of the TiC composite system is subjected to ballistics trauma such as by impact with a high velocity ballistic projectile. Crack propagation progresses in very random directions and redirections, which is believed to enhance rapid absorption of a projectile's energy.
- the TiC composite system thereby exhibits a greater toughness than prior materials that are brittle and rapidly shatter in straight line crack patterns.
- the bonding of the matrix phase with the aggregate phase also serves to reduce cracking of the relatively brittle hard particles which constitute the aggregate phase.
- the composite system has hard particles that are relatively large such that there is more space between the hard particles to be occupied by the more ductile matrix phases than in prior composites. Because of their size, such large hard particles have a relatively large mass to better absorb energy and resist cracking.
- the composite system may be formed from a mixture comprising (1) titanium powder, such as titanium sponge granules (TSGs), (2) a master alloy containing nickel, titanium, aluminum, and optionally, iron (NiTiAl master alloy), and (3) hard powder.
- titanium powder such as titanium sponge granules (TSGs)
- TSGs titanium sponge granules
- master alloy containing nickel, titanium, aluminum, and optionally, iron
- hard powder e.g., a mixture of the following amounts:
- titanium powder from 20 wt.% to 54 wt.%
- NiTiAl master alloy from 12.5 wt.% to 25 wt.%
- hard powder from 32 wt.% to 55% wt.%.
- Such a mixture of NiTiAl master alloy and titanium powder has a melting point below their respective melting points and well below the melting point of the hard powder. As a result, melting and then cooling the NiTiAl master alloy and titanium powder in such a mixture produces a composite system having a lamellar microstructure.
- a master alloy is a composition made for the purpose of melting and/or bonding with other metals to form composite systems or other alloys. Master alloys are used to overcome the problems of alloying metals of widely differing melting points, or to facilitate closer control over the final composition. Such a master alloy is made by melting or exothermic reaction of the metals making up the composition; and the resulting mixture which is very friable is reduced to the desired particle size by mechanical methods before blending with other components of the product alloy. Non-melted titanium sponge granules (TSGs) are believed to be best titanium powders to use for the green binder for forming the composite systems described herein.
- TSGs Non-melted titanium sponge granules
- TSGs are defined as irregular shaped particles of sponge fines from titanium metal reduction processes using sodium, magnesium or calcium as the reducing agent to extract the titanium and where the titanium sponge granules have not been melted.
- TSGs have a low apparent density, below 1.50 g/cc and a low tap density, specifically a tap density of less than 1.90 g/cc.
- titanium powder made from melted powders such as those made by the hydride- dehydride process using previously melted titanium material, or by using spherical titanium powders that may be made by the rotating electrode process, commonly known as REP method.
- Spherical powders are also made by a plasma process such as that used by TEKNA Plasma Systems, where titanium sponge particles or particles made by other methods such as HDH are fed through a induction plasma on controlled basis and fully or partially melted to form spherical type titanium powders.
- the green binder also can be a mixture of such titanium powders with or without TSGs.
- Hard powder as referred to herein includes powders, particles and/or granules that are so hard that a volume of hard powder will not stick together when compacted in a die to form a compact for subsequent processing by the application of heat and/or pressure such as sintering, hot pressing, and hot isostatic pressing, without contamination of the base material or subsequently formed alloy.
- Hard powders include many different types of carbides and nitrides. Hard powders of particular utility are aluminum carbide, AI 4 C 3 , boron carbide, B 4 C, silicon carbide, SiC, calcium carbide, CaC 2 , titanium carbide, TiC, titanium nitride, TiN, and boron nitride, BN.
- Another suitable hard powder is A1 2 0 3 . Mixtures of such materials can be used as the hard powder component for forming the composite system. Low density hard particles, having a specific gravity of not more than 6.0, are particularly useful in forming ballistic armor for portable uses, such as in body armor.
- the starting materials and alloys described in this disclosure typically will contain small amounts of other elements, sometimes referred to herein as "trace elements," including residuals, impurities, dopants, and the like.
- Commercially available component materials typically contain small amounts of one or more of O, H, N, Na, CI, Co, Cr, Cu, Mg, Mn, Mo, Nb, Pd, Sb, Sn, Ta, V, W, Zr, and S.
- the exact amounts of such elements in starting materials typically is not known because commercially available component materials are not routinely assayed for all possible included elements. Therefore the main elements, i.e. titanium and nickel, are normally established by subtracting the elements analyzed for from 100%.
- the titanium powder serves to bind together the hard powders and the hard
- Titanium sponge granules thus should be present in an amount sufficient to impart green strength to a green compact formed from the mixture of ingredient materials.
- NiTiAl master alloy is combined with TiC and TSGs to form a TiC composite system.
- the master alloy comprises:
- balance nickel and trace elements.
- This master alloy is friable and can be milled to fine powder of various sizes.
- the mixture is compacted at forces ranging from 275 MPa to 827 MPa to form a green compact.
- the pressed green compact is sintered in a vacuum furnace at temperatures from 900°C to 1400°C depending on the ratios of nickel, TiC, and TSG in the mixture.
- the compact may also be processed by hot isostatic pressing (HIP) either before or after vacuum sintering.
- HIP hot isostatic pressing
- the majority of the hard powder material input weight will comprise particles of various sizes in the range of 50-150 microns. A small fraction may be smaller in size, as small as 5 microns.
- at least 60 wt.% of the hard powder material input weight will comprise particles of at least 45 microns to achieve the desired aggregate mixture and spacing.
- the use of such relatively large particles is a departure from prior material systems.
- the majority of particles in the ingredient mixture are below 10 microns and most below 6 microns.
- TiC particles in prior material systems are relatively small in size as shown in FIG. 2a and 2c.
- composite systems can be formed from a powder mixture wherein 90 wt.% of the hard powder is less than 45 microns.
- the size of the particles of each ingredient powder used can be varied to produce different green compacts and sintered structures depending on desired properties, pressing, and sintering parameters.
- composition of the resulting composite system will vary within ranges depending on the variations in the input materials and the allowable variations in the elements in the master alloy.
- composition will fall within the following ranges where the ingredient materials are adjusted to produce a final composition that is equal to 100% within the limitations shown below:
- the density of the composite system will vary depending on the ratios of the input materials and can be as high as 5.0 grams/cc. Measured densities of experimental TiC composite systems have ranged from 3.63 grams/cc to 4.42 grams/cc.
- the composite system has an average hardness as measured by Vickers indenters of not less than 1000, with the lowest reading not less than 660 Vickers.
- Ductility and fracture toughness of the composite system are characterized by the formation of multiple ductile and brittle, branched, tortuous, energy absorbing crack paths with measurable deformation upon impact by a ballistic projectile and by ductility of at least 0.5% elongation.
- Useful composite systems can, however, also be made by melting an ingredient mixture sufficiently to at least partially liquefy the NiTiAl master alloy and titanium components.
- the liquefied mixture may be poured into a solid mold configured to form an ingot or into a mold shaped to produce a specific final or preform configuration in the manner of investment casting or permanent mold casting technology.
- Favorable results are achieved when the ingredient mixture contains 32 wt% to 55 wt% hard powder.
- Elemental powders may be substituted for all or a portion of the NiTiAl master alloy in the procedures discussed above, but use of the master alloy typically is most efficient.
- composition of the resulting TiC composite system will vary depending on the ratios of the input materials. By the calculations shown in FIG. 1, the composition will fall within the following ranges where the ingredient materials are adjusted to equal 100% which produces a final composition that is equal to 100% within the limitations shown below:
- Table I is a summary of results of tests made on exemplary TiC composite systems as described herein.
- Table I Titanium Carbide Composite System
- a body of the composite system material may be used by itself depending on the application.
- the composite system also may be used along with a body of another material, particularly a body of titanium, a titanium alloy, aluminum, an aluminum alloy, or a ceramic, to form a multi-component composite structure.
- the term “substrate” is used to refer to a material other than a composite system as described herein.
- body refers to a structure that can hold a shape, as opposed to a loose mixture of powders that cannot hold a shape unless confined within a vessel.
- a “green body” or “green compact” is a mixture of powders that have been pressed together to form a compact that can hold a shape, but that has not been sintered.
- Substrate precursor powder refers to a material or mixture of materials in powdered form that can be sintered or can be melted and cast to form a solid body of substrate material.
- “Composite system precursor powder” refers to a mixture of powders that can be sintered to form a solid body of composite system material.
- one or more layers of the composite system and one or more layers of titanium, a titanium alloy, aluminum, an aluminum alloy, and/or a ceramic can be combined to form a layered composite structure.
- Such layered composite structures can be produced with single or multiple layers of various different thicknesses and combinations that will have different densities and properties.
- Example layered composite structures are illustrated in FIG. 3a and 5a-5e.
- Layered composite structures can be made, for example, by placing a volume of substrate precursor powder, such as loose commercially pure (CP) titanium powder, and a volume of composite system precursor powder mixture into a die in layers of desired thickness ratios, followed by pressing to form a compact and sintering as described herein. Powders of a titanium alloy, aluminum, an aluminum alloy, or a mixture of such powders also can be used with the composite system to form such composite structures to meet special application needs.
- substrate precursor powder such as loose commercially pure (CP) titanium powder
- CP commercially pure
- Layered composite structures also can be made from a volume of a powder and a preformed solid body that serves as a substrate.
- a preformed wafer of the composite system material can be placed into physical contact with a volume of a powder of titanium, a titanium alloy, aluminum, or an aluminum alloy, or a mixture of such powders in a closed die. The wafer and the powder then are compressed within the die to cause the powder to form a layered compact that can be sintered to bond the powder to the wafer.
- Preformed bodies such as wafers, of one or each of the layer components can be used to form the composite structure.
- a body of titanium, a titanium alloy, aluminum, an aluminum alloy, or a ceramic can be placed into physical contact with a body of the composite system and the bodies heated to a sufficient temperature to cause the bodies to adhere upon cooling.
- a volume of composite system precursor powder is placed in a die and compressed to form a green compact.
- the green compact and a solid substrate body are placed in physical contact, with the substrate covering all or part of a surface of the green compact.
- the combined green compact and substrate then are heated to sinter the green compact and to bond the sintered green compact to the substrate.
- Sintering in a separate furnace typically is most efficient for any of these methods where materials are compressed within a die.
- the compressed layered structure can be heated in the die under pressure, by the procedure sometimes referred to as hot pressing, to bond the layers together.
- various heating methods and temperatures can be used to bond different materials together, to allow for variations among materials that will behave differently at different temperatures, before and after heating.
- Adjacent layers of a layered composite structure can be larger or smaller than one another in any dimension.
- a layer may be in the form of one or more wires or whiskers that can be included a layered composite structure to provide reinforcement or an attachment mechanism.
- Example titanium alloys are described in Materials Property Handbook - Titanium Alloys (ed. R. Boyer, E.W. Collings, and G. Welsch; published 2009 by Titanium Information Group, Rotherham, UK.
- Other examples of suitable alloys can be found in ASTM B265 - 09ael Standard Specification for Titanium and Titanium Alloy Strip, Sheet, and Plate (Active Standard ASTM B265, developed by Subcommittee B10.01, Book of Standards Volume 02.04, 2009).
- titanium powder combined with other powders can create new alloys and materials with desirable properties for substrate layers.
- the selection of such materials that may be used substrate layers will be driven by characteristics including but not limited to compatibility for bonding with a composite system layer, to reduce the weight of the layered composite system, to increase the ductility and crack absorption properties, to reduce the transfer of impact energy, and exterior or interior layers that are harder, or more ductile than the TiC composite system.
- substrates consist essentially of titanium and aluminum, with the aluminum being present in an amount of from 2 wt.% to 12 wt.%.
- Such an alloy can be produced from a powder that is a mixture consisting essentially of 88 wt.% to 98 wt.% titanium powder and 2 wt.% to 12 wt.% aluminum powder.
- TiAl 10 titanium- aluminum alloy
- substrate precursor powder mixture of 90 wt.% titanium sponge granules and 10 wt.% aluminum powder.
- the substrate precursor powder mixture was placed in a die and a volume of TiC composite system precursor powder was placed on top of the substrate precursor powder mixture.
- the powders then were compacted to form a green compact, which subsequently was sintered within the parameters described herein. A good metallurgical bond was observed similar to that shown in FIG 3a.
- a body of titanium sponge granules that had been previously pressed and sintered to create a solid wafer was placed on a pressed, but not sintered, green compact of TiC composite system precursor powder, the combined body was subjected to sintering conditions within the parameters described herein.
- the green compact was sintered and good metallurgical bond between the layers, similar to that shown in FIG 3a, was observed.
- Layered composite structures have been made using standard wrought titanium materials such as Ti 6 Al 4 V including reinforcing wires, and titanium alloys made with mixtures of elemental powders, such as 90 wt.% titanium powder with 10 wt.% aluminum powder as described above.
- a wrought CP titanium wire .095 inch diameter and a wrought Ti 6 Al 4 V wire .080 inch diameter were placed on a volume of TiC composite system precursor powder in a die, pressed to imbed the wires and sintered as described herein.
- a good bond was observed between the wrought Ti 6 Al 4 V wire and the TiC composite material, which when broken apart showed a ductile fracture within the Ti 6 Al 4 V wire.
- the small diameter CP titanium wire was fully alloyed with and became a part of the matrix of the TiC composite system consistent with the observations that the TiC composite system forms a phase that will bond
- FIG. 3a illustrates a potential application of a TiC composite system for armor tile.
- a wafer about 0.2 inch thick of the S-3 TiC composite system described in Table I was pressed and sintered onto an about 0.1 inch thick substrate layer of titanium sponge granules.
- the resulting two-layer wafer was shot with an AR-15, 16 inch barrel, full metal jacket, standard NATO round.
- the TiC composite system portion of the composite was cracked and broken loose from the substrate but the bullet did not penetrate the substrate as shown in the photo of the back side of the two-layer wafer.
- the same type of bullet fully penetrated a mild steel target, about .25 inch thick, a ceramic armor tile about .24 inch thick and a TiC tile about .25 inch thick.
- the tile shown in FIG. 3a was found to have the following properties.
- the tortuous crack path and frequent changes in direction as the crack propagated through interfaces suggests substantial energy absorption and substantial resistance to cracking relative to other hard materials such as ceramics.
- Armor tiles may also be made by adhering a body of the TiC composite system to another substrate material such a ceramic, including those made from alumina, boron carbide and/or silicon carbide by sintering the TiC composite system onto the ceramic material to produce the composite material shown in FIG. 5d.
- a wafer of the TiC composite system was sintered in an alumina ceramic boat,
- FIG. 5d Vickers micro hardness data appears in FIG. 5d for the TiC composite system/ceramic composite shown in FIG. 5e.
- a method for forming a reduced density TiC composite system wherein titanium, aluminum, or a mixture thereof is substituted for at least a portion of one or more of the heavy elements nickel, molybdenum, niobium and tungsten of a known alloy system for cementing carbide powder, such as TiC powder, with the titanium, aluminum, or mixture thereof being substituted in an amount sufficient to reduce the density of the resulting alloy system containing cemented carbide to not more than 5.0 g/cc.
- Also more generally described herein is a method for forming an composite system suitable for bonding to a substrate wherein titanium, aluminum, or a mixture thereof is substituted for at least a portion of one or more of the heavy elements nickel, molybdenum, niobium and tungsten of a known alloy system for cementing hard powder, such as TiC powder, with the titanium, aluminum, or mixture thereof being substituted in an amount sufficient that components of the resulting alloy system containing TiC can bond to titanium structures and ceramic structures by sintering.
- a known alloy system for cementing hard powder such as TiC powder
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JPH03150331A (en) * | 1989-11-08 | 1991-06-26 | Toshiba Corp | Erosion-resistant alloy |
JPH042742A (en) * | 1990-04-19 | 1992-01-07 | Fuso Off Service:Kk | Composite titanium alloy, multilayered titanium material, titanium cutter and their manufacture |
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US2753261A (en) * | 1952-09-30 | 1956-07-03 | Sintercast Corp America | Sintering process for forming a die |
DE69128692T2 (en) * | 1990-11-09 | 1998-06-18 | Toyoda Chuo Kenkyusho Kk | Titanium alloy made of sintered powder and process for its production |
US5736658A (en) * | 1994-09-30 | 1998-04-07 | Valenite Inc. | Low density, nonmagnetic and corrosion resistant cemented carbides |
US6911063B2 (en) * | 2003-01-13 | 2005-06-28 | Genius Metal, Inc. | Compositions and fabrication methods for hardmetals |
US7192464B2 (en) * | 2003-09-03 | 2007-03-20 | Apex Advanced Technologies, Llc | Composition for powder metallurgy |
US7687023B1 (en) * | 2006-03-31 | 2010-03-30 | Lee Robert G | Titanium carbide alloy |
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JPH03150331A (en) * | 1989-11-08 | 1991-06-26 | Toshiba Corp | Erosion-resistant alloy |
JPH042742A (en) * | 1990-04-19 | 1992-01-07 | Fuso Off Service:Kk | Composite titanium alloy, multilayered titanium material, titanium cutter and their manufacture |
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