CA2104288A1 - Methods for alloying a metal containing material into a densified ceramic or cermet body and alloyed bodies produced thereby - Google Patents
Methods for alloying a metal containing material into a densified ceramic or cermet body and alloyed bodies produced therebyInfo
- Publication number
- CA2104288A1 CA2104288A1 CA 2104288 CA2104288A CA2104288A1 CA 2104288 A1 CA2104288 A1 CA 2104288A1 CA 2104288 CA2104288 CA 2104288 CA 2104288 A CA2104288 A CA 2104288A CA 2104288 A1 CA2104288 A1 CA 2104288A1
- Authority
- CA
- Canada
- Prior art keywords
- metal
- alloying metal
- alloying
- inorganic compound
- exterior surface
- 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
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 159
- 239000002184 metal Substances 0.000 title claims abstract description 159
- 238000005275 alloying Methods 0.000 title claims abstract description 101
- 239000000919 ceramic Substances 0.000 title claims abstract description 86
- 239000011195 cermet Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims description 49
- 239000000463 material Substances 0.000 title claims description 32
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 40
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 40
- 238000002844 melting Methods 0.000 claims abstract description 19
- 230000008018 melting Effects 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000011159 matrix material Substances 0.000 claims description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 229910052802 copper Inorganic materials 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 15
- 229910052580 B4C Inorganic materials 0.000 claims description 14
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000011888 foil Substances 0.000 claims description 11
- 239000011777 magnesium Substances 0.000 claims description 11
- 150000002739 metals Chemical class 0.000 claims description 11
- 238000009792 diffusion process Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 230000008595 infiltration Effects 0.000 claims description 4
- 238000001764 infiltration Methods 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000005496 eutectics Effects 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 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 description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims 16
- 239000000843 powder Substances 0.000 description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000006023 eutectic alloy Substances 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 4
- 238000007569 slipcasting Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- 229910019878 Cr3Si Inorganic materials 0.000 description 2
- 229910018563 CuAl2 Inorganic materials 0.000 description 2
- 101100156763 Schizosaccharomyces pombe (strain 972 / ATCC 24843) wos2 gene Proteins 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910016384 Al4C3 Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910003322 NiCu Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 235000018734 Sambucus australis Nutrition 0.000 description 1
- 244000180577 Sambucus australis Species 0.000 description 1
- 229910003682 SiB6 Inorganic materials 0.000 description 1
- 229910033181 TiB2 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229940075894 denatured ethanol Drugs 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- -1 oxides Chemical class 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 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
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
-
- 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
- C22C29/062—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 based on B4C
-
- 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
-
- 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
- C22C32/0057—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 based on B4C
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
- C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
- F16D69/00—Friction linings; Attachment thereof; Selection of coacting friction substances or surfaces
- F16D69/02—Composition of linings ; Methods of manufacturing
- F16D69/027—Compositions based on metals or inorganic oxides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Ceramic Products (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Place an alloying metal or an inorganic compound containing an alloying metal in contact with at least a portion of the exterior surface of a densified cermet or ceramic body and then heat the cermet body or the ceramic body to a temperature that allows alloying to occur. The temperature for the cermet body is close enough to the melting temperature of the metal portion of the cermet to allow alloying to occur. The temperature for the ceramic body is close enough for the body's glassy-phase component to soften and allow alloying to occur. The resultant alloyed bodies have a composition gradient that extends into the body perpendicular to the exterior surface portion if alloying stops prior to completion.
Description
WOg2~1~70 7 1 o ~ PCT/US92J01928 MET~ODS FOR ALLOYING A METAL-CONTAINING MATERIAL INTO A
DENSIFIED CERAMIC OR CERMET BODY AND ALLOYED BODIES
PRODUCED THEREBY
This in~e~tion relates to processes for alloying metal, or an inorganic compound containing such a metal, into a ceramic or ceramic-metal (cermet) body that has a de~sity greater than or equal to 95% of the body's theoretical de~sity.
It is well known that metal alloys often have more desirable propertiec than pure metals. It would follow that alloyed cermets and ceramics may have more desirable properties than non-alloyed cermets and ceramics. It would thereore be desirable to have methods ~or making such alloyed cermets and ceramics. -It would also be desirable to be able to alter the properties of a ceramic or cermet body by alloying without significa~tly changing the shape or density of the body. It would further be desirable to be able to make a cermet or ceramic body tha~ has different properties such as improved oxidative resistance or wear ,' resistance at separate locations on the body.
.:
' :` .
- : ~
:
WO 92/16670 Pcr/uss2to1s2s One aspect of the presen~ invention is a process for alloying a ~etal or a metal-containing material into a densified cermet body comprising:
(a) placing an alloying metal or an inorganic compount containing an alloying metal in contact with at least a portion of an exterior surface of a cermet body that has a densi~y of at least 95% of the theoretical full density and is formed of a ceramic that has a ~atrix metal di persed therein, the matrix ~etal 0 extending fro~ the exterior surface portion at least partially into the cermet body; and (b) heating ~he cermet body, while it is in contact with the alloying metal or the inorganic 1~ compound containing the alloying metal~ to a temperature that is greater than or equal to 50C belo~ the lesser of the ~atrix metal's melting point and the temperature at which the matrix metal and the alloying metal form an eutectic, to diffuse the alloying metal into the cermet body and form an alloy between the alloying metal and the matrix metal.
A second aspect of the invention includes a method for alloying a metal or a metal-containing material into a densified ceramic body comprising:
(a) placing an alloying metal or an inorganic compound containing an alloying metal in contact with at least a portion of an exterior surface of a ceramic body that has a density of at least 95% of the theoretical full density and is formed of a glassy-phase component ~, and a non-glassy-phase component, the glassy-phase component extending from the exterior surface portion at least partially into the ceramic body; and ~ ' . - I ' ':
.
"'' ~ -. . ..
WO 92~T6670 2 1 a ~ 2 X ~ PCT/US92/01928 (b) heating the ceramic body to a temperature ~t least nea~ that at which the glassy-phase component softens while the alloying me~al or the inorganic compound containing an alloying metal is in contact with the ceramic body to diffuse the alloying metal into the ceramic body and form an alloy between the alloyi~g metal and the glassy-phase component.
Bodies prepared by the methods described immediately above are also disclosed.
The first aspect of the invention concerns a method for alloying a metal, or a material containlng a metal, into a densified cermet body. The term 'Imetal--containing maeerial" collectivel~ refers to alloying metals and inorganic compounds co~taining an alloying metal. The metal-containing material is ~uitably selected fro~ pure metals, alloys of two or more metals, and inorganic compounds containing at lea~t one metal.
A "metal" is an element from the Periodic Table of the Elements that forms positive ions when its compounds are in solution and whose oxides form hydroxides rather than acids with water. De~irable metals include nickel, chromium, copper, vanadium, titanium, silicon, magnesium, hafnium, tungsten, molybdenum, manganese, iron, copper or tantalum. Satisfactory inorganic compounds relea~e or give up metal under conditions of the present invention to form a metal alloy with the matrix metal of the cermet. Inorganic compounds that 3 are stable, in that they do not release metal to form an alloy under conditions of the present invention, are not suitable. Illustrative inorganic compounds include nitrides, oxides, carbides, borides or silicides of the WO92/l~70 PCT/US~2/0192B
~ ' -4-metals. Carbides, nitrides and oxides are preferred inorganic compound~.
The metal component of the metal-containing -;
material is preferably different from the matrix metal of the cermet body~ The metal-containing material may be either solid or molten when it is initially placed in contact with the cermet body. When the metal-containing material is solid, it may be in any form including powder or foil. When the metal-containi~g material is in the form of a foil, the foil is desirably less than 0.75 mm thick, more desirably~ less than 0.5 mm thick, and, preferably, less than 0.1 mm thick.
Examples of cermet/alloying metal combinations suitable for this invention include those provided in Table 1.
Table 1 Cermet Possible AlloYinq Metals B4C/Al Ni, Cr, Cu, V, Ti, Si, Mg, ~f, W
SiC/Al Ni, Cr, Cu, Mn, V, Ti, Mg, Si, Hf, W
Tis2/Al Ni, Cr, Cu, Mn, Ti TiB2/Cu Al, Ti, Si, Ta, Fe, Co Si3N4/Al Cr, Mn, Ti Si3N4/Ni Ti, Fe, Co, Mn SiB6/Al Ni, Cr, Cu, Mn, Tl, Si The cermet body, prior to contact with the metal-contai?ning material, has a ceramic component and a matrix metal component. The cermet body desirably cont~ins from 15 to 99 weight percent ceramic component ?
and from 85 to 1 weight percent matrix metal component.
The cermet body preferably contains from 60 to 80 weight :~ t~
WO92/1~70 ~1 a i 2 .~ ~ PCT/U~92/0i928 percent ceramic component and from 40 to 20 weight percent matrix metal component. The weight percen~ages total lO0 percent. The ceramic component is desirably boron carbide, silicon carbide, titanium boride, alumina, or silicon nitride. The matrix me~al component is desirably aluminumt titanium, copper or nickel. In order for the metal-containing material to d;ffuse into the cermet body, two conditions must exist. First, the matrix metal must be in physical contact with the metal--containing material at least at an exterior surface portion of the cermet body. Second, the matrix metal must extend at least partially i~to the cermet body from that surface portion. The matrix ~etal may be continuous throughout the bulk of the cermet body with the ceramic being the discontinuous phase.
The non-alloyed cermet body may be prepared by any conventional method. For example, the cer~et body may be prepared by densifying a mixture of ceramic and matrix metal powders into a desired shape. The densification may be accomplished by conventional processes such as cold pressing or slip casting. If desired, these processes may be follo~ed by sintering to further densify the cermet body.
Another method of preparing a non-alloyed cermet body includes a first step of forming a porous ceramic body. Conventional procedures, such as slip casting a ceramic dispers~on or cold pressing ceramic pcwder, produce porous bodies with a desired shape.
Molten matrix metal is then placed in contact ~ith the porous ceramic body. The molten metal infiltrates into the porous ceramic body by capillary actisn. Such WO92~l~7~ PCT/US92/0!928 ~ ?,~3 -6-methods are di~closed in U.S. Patent Nos. 4,702,770, 4,718,941, and 4,834,938.
U.S~-A 4,702,770 describes, at column 6, lines 5-25, a four ~tep method for producing low density boron carbide-aluminum ~omposites. The first three ~teps yield a satisfactory cermet body. In step one, a colloidal consolidation technique is u~ed to form a porous boron carbide compact from a homogeneous dispersion of boron carbide. In step two, the compact in enriched with carbon by heat treating or sintering the boron carbide in the pre~ence of graphite. In step three, aluminum is infiltrated into the enriched compact.
U.S.-A 4,718,941 discloses the infiltration of molten reactive metals into chemically pretreated boron carbide, boron or boride starting material~. The chemical pretreatment procedure is described in detail at column 7, line 8 through column 8, line 12. The starting materials are immersed in a chemical substance that reacts with B203, BH303, or both, for as long as necessary to change the surface chemistry by forming boron-carbon-hydrogen-oxygen complexes that pyrolyze upon heating, either prior to, or during, infiltration.
Suitable chemical substances include various alcohols, such as methanol, isopropyl alcohol and denatured ethanol.
U.S.-A 4~834,938 outlines a process for making a composite article having an internal surface or cavity. A porous compact is formed about an insert body that has an external surface corresponding to the internal surface of the composite. The article is heated to the wetting temperature of the insert body to ~ . . .
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wos2/l667o PCT/US92/0192~
~:la~ ,f.~) melt the insert and cause it to infiltrate into the porous compact.
The non-alloyed cermet body required for purposes of the present invention has a density o at least 95% of theoretical density. The density is more preferably at least 99% of theoretical de~sity.
Alloying, or the diffu~ion of an alloying metal into a matrix metal, is desirably initiated by heating the cermet body to a temperature greater than or equal to that at which the matrix metal melt~. If an eutectic alloy is formed between the matrix metal and the alloying metal, the eutectic alloy typically ha~ a melting point lower than that of the matrix metal. If an eutectic alloy i9 formed, the temperature may be decreased to equal or exceed the melting point of the eutectic alloy. If no eutectic alloy is formed, the temperature is preferably maintained at or above the melting temperaturc of the matrix metal until alloying reaches a desired level.
Temperature plays an important role in determining the rate at which alloys between the matrix metal and the alloying metal form. Diffusion occurs so slowly at room temperature that it is not readily detected over a period of several days. As the temperature approaches the melting temperature of the matrix metal, diffusion becomes more discernible. At the melting temperature, diffusion is rapid enough to yield a readily detectable amount of alloy. At temperatures in excess of the melting temperature, diffusion occurs very rapidly. The temperature must not, however, be 30 high that the ceramic portion of the cermet begin~ to decompose or dissociate. The term "at . :
: , `: :
W092/1~70 PC~/~JS92/01928 A a~ ;s~ -8-least near" means greater than or equal to a temperature that is 50C below the melting temperature of the matrix metal. The temperature preferably equals or exceed~ the melting temperature of the matrix metal, but is less than the di~sociation temperature of the ceramic portion 5 of the cermet.
During the alloying process, the metal--containing material ~ay or may not become molten, depending on its melting po;nt. A satisfactory degree 0 of alloying is attainable if only the matrix metal becomes liquefied. When foils are used and the metal--containing material is to become molten during the alloying process, thin foils are preferred as they melt 15 faster and result in more uniform diffusion across the contacted susface of the cermet body. The matrix metal preferably has a melting point that is less than or equal to the melting point of the metal-containing material.
The second aspect of the invention is a method for alloying a metal-containing material into a densified ceramic body. The ceramic body contains a glassy-phase compone~t and a ~on-glassy-phase component.
25 The ceramic body desirably contains from 70 to 99 weight percent of non-glassy phase and from 30 to 1 weight ?
percent glassy phase. The ceramic body preferably contains from 85 to 97 weight percent non-glassy phase and from 15 to 3 weight percent glassy phase.
The non-glassy-phase component of the ceramic body is desirably silicon nitride. The glassy-phase component of the ceramic body is desirably formed of a metallic oxide such as yttria, magnesia, alumina, ., ~ , . , , j.................. .
- . ' i , !
' Wo92JI~7~ 2 i ~ i, PC~ S~2tO192 silisa, zirco~ia, tantalum oxide, calcium oxide or a mixture of two or more o such oxides.
In order for the metal-containing material to diffuse into the ceramic body, t~o conditions must be met. First, the glassy-phase component must be in physical contact with the ~etal-containing material at least at an exterior surface portion of the ceramic body. Second, the glassy-phase component must extend at least partially into the ceramic body from that surface portion. The glassy-phase component may be continuous throughout the bulk of the ceramic body while the non--glassy phase component may be discontinuous throughout the remainder of the bulk of the ceramic body.
The ceramic body may be prepared by densifying a mixture of powders that will constitute the ~lassy-phase and non-glassy-phase components. For instance, silicon nitride, yttria, magnesia, and zirconia powders may be densified into a desired shape by cold pressing, or slip casting, the powders into a body and then sintering the body. The ceramic bodies desirably have a density of at least 95% of theoretical density. The density is preferably at least 98Z of theoretical density.
Metal-containing materiaLs suitable for purposes of the second aspect of the present invention, like those of the first aspect~ are metals, inorganic compounds containing a ~etal or having a metallic constituent, a metal alloy, or a metal o~ide. Metal oxides are commonly available me~al-con~aining materials. The metal or metallic constituent is suitably yttrium, magnesium, chromium, zirconium, molybdenum, vanadium, titanium or a rare earth metal WO 92/16670 PCr/US92/01928 (elements 57-71 of the Periodic Table). The ~etal or metallic constituent must differ from that contained in the glassy-phase component if alloying is to occur.
The metal-containing material may be solid or liquid when it is initially placed in contact with the ceramic bodyO As in the first aspect, it may be in the form of a powder or a foil when it is a solid. As the ceramic body is heated to soften the glassy-phase component, the metal-containing material may retain its 0 initial form or be converted to a liquidO
If d2sired, two or more differ~nt metal--containing materials may be placed in contact with exterior surface portions of either the cer~et of ~he first aspect of the invention or the ceramic of the seco~d aspect. If, for example, two different materials are placed in contact with exterior surface portions of a cermet or ceramic body, they are preferably not applied to the same surface portion.
During the heating step of the invention, the metal-containing material gradually diffuses into the cermet or ceramic body from the exterior surface portion 2~ in contact with said material. Before alloying i~
complete, alloying occurs in a gradient manner. The term "gradie~t manner" means that alloying occurs to a greater exten~ at or near the exterior surface portion and to a progressively lesser extent as distance from that portion increases as one travels in a direction perpendicular to the surface portion into the ceramic or cermet body~ Alloying may change only the chemistry of the matrix metal or glassy-phase component. It may also change the chemistry of the ceramic or non-glassy phase component thereby forming new phases. The alloying , .
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WO 92/16670 2 1 () ~ PC~/lJS92/01928 process may be conti~ued uutil the body is substantially free of chemical composition gradients. M~re typically, alloying is terminated while gradients are still present. Termination occurs by conventional means, such as cooling the cermet body or the ceramic body to a temperature ~ell below the respective matrix metal liquidus temperature or the glassy-phase component softening temperature.
After termination of alloying, any excess 0 metal-containing material on the surface of the cermet or the ceramic body may be removed by conventional processes. These processes include peeling or grinding.
The alloyed bodies of this iuvention are especially useful for making abrasion-resistant parts, such as cutting tools and drilling tools, and wear parts, such as automobile brakes.
The following examples are illustrative only and should not be construed as limiting the invention which is properly delineated in the appended claims.
Example _l A block-shaped porous body of boron carbide, measuring about 1 cm thick, was prepared by slip casting a dispersion of boron carbide powder. The slip-cast body had a de~sity of about 64% of the theoretical density of boron carbide. The porous body was 3 impregnated with aluminum by contacting the boron carbide body with aluminum and heated to 1180C to form a cermet body. At that temperature, sintering was effected and the cermet body comprised about 64 weight %
boron carbide, about 25 weight % aluminum and about 11 weight % reaction products containing aluminum. The , : :
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WO92/16670 PCT/US92/0l928 ~ Q '~J ~ -12-body had a den~ity of greater than 99% of the theoretical density. Table 2 shows typical reaction products.
Copper foil measuring about 0.75 mm thick was placed on one side of the cermet body, while a foil of nickel measuring about 0.75 mm thick was placed on the opposite side. The ~espective melting points of the matrix metal (aluminum), the copper, and the nickel are 660C, 1085C, and 1445C. The cermet body and the 0 associated copper and nickel foils were placed in a graphite crucible. The crucible ~as placed in an oven with a flo~ing argon atmosphere. The temperature of the oven was increased from room temperature to 1100 in about two hours and held at 1100C for one hour. The cermet body was then removed from the furnace and allowed to cool naturally to ambient temperature.
Cooling occurred over a period of about 1 1/2 hours.
Chemical analysis of the alloyed cermet body was completed using an MBX-CAMECA microprobe~ available from Cameca Co., France. The results are provided in Table 2 which shows the volume percent amounts of the various phases listed on the side of the table at three locations in the alloyed cermet body~ The first location was in copper side, the second location was in the bulk of the boron carbide cermet body, and the third location was in the nickel side.
The results summarized in Table 2 demonstrate that diffusion of the metal-containing materials occurred. The nickel co~ponent ranged from a high of 20 volume percent at the "nickel end" through an intermediate value of 12 volume percent in the middle of the cermet body to a low of not being detectable in the ... ..
wos2/t~70 2 1 9 ~ 2 ~ ~ PCT/US~2/01928 "copper end". The copper component (CuAl2) sho~ed a similar gradient. Furthermore, the boron carbide volume percent remained fairly consistent throughout the cermet body.
Table 2 Vol 96 Vol% of of phase in Vol ~ of phase in Middle of phase in Phase CoPPer end cermet body Niokel end o (NiCu)2Al3 nda 12 20 Al with about lO l5 20 2 wt% Cu CuAl2 with 20 8 nda about 0~4 wt%
AlE324C4 10 9 9 s4c 58 54 49 Al4BC <lb cl <l Al4C3 a = not detected b = present, but in an amount less than l vol Example 2 A boron carbide-aluminum cermet body was prepared by the method described in Example l. A copper foil, measuring about l mm thick, was placed on ~he cermet body. The cermet body was then heated to l100C, and the te~perature was maintained for l hour. After cooling the cermet body, the copper foil was removed.
It was fou~d that the copper content of the foil was reduced by 3.5 wt%.
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WO 92/l~ib~O PCI-/US92/i)192X
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Example 3 This example illustrates the use of a powder form of a metal-containing material. A densified ceramic body having a composition of 86.3 wtX Si3N4, 8.5 wt% Y203, 4.7 wt% MgO and 0.5 wt.% GaO was prepared by hot-pressing a mixture of the Si3N4 and oxide powders at 1825C for 1 hour. The ceramic body had a density of about 99.5% of the maximum theoretically possible density. The ceramic body was buried in a HfO2 powder 0 bed in a quartz container. The ceramic body and HfO2 bed were heated to 1400C and held at this temperature for 1 hour while in a flowing nitrogen atmosphere~ The ceramic body a~d the HfO2 bed were then allowed to cool.
After cooling, the ceramic body was separated from the HfO2 po~der, sectioned, and analyzed. 0~ the surface of the ceramic body, an alloyed layer rich in HfO2 measuring approximately 50 micrometers deep was observed. The diffusion of HfO2 altered the ceramic body's composition, but did not alter the chemistry or shape of the Si3N4 grains. Analysis indicated that the alloyed layer contained Si3N4 grains in two glassy phases: a phase relatively high in Mg, relatively low in Y, and having no Hf; and a phase havi~g a relatively intermediate levels of Mg and Y and a relatively high level of Hf.
Example 4 A densified ceramic body was prepared as in Example 3 and placed in a bed of Cr203 powder. After heating the ceramic body and Cr203 powder to 1400C, maintaining this temperature for 1 hour, then cooling, three alloyed layers near the surface of the ceramic body were observed. The first, or outside layer, .
- . , ~ - .
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, ' ~, ' ' ' :
WO92/16670 2 ~ PC~/USg2tO1928 consisted of Cr3Si, Cr2N, a relatively high level of yttria silicate crystals, and a mixture of two glassy phases. The glassy phases were: a phase having Y and Mg in a weight ratio of about 1:1; and a phase contai~ing a relatively low level of Y, and relatively high levels of Mg and Ca. The second, or middle layer, consisted of Si3N4, Cr3Si and a relatively low level of CaO glass. The third, or innermost, layer consisted of Si3N4 and glass containing a relatively intermediate amount of Y, a relatively intermediate amount of Mg, and no Ca. The weight ratio of Y to Mg in this inner~ost layer was about 0.6:1. The total thickness of all three layers was about 200 micrometers. This example illustrates that eve~ though diffusion occurred through the glassy phase, the majority of the Cr formed new cry5talli~e phases and the gla.q~ chemistry remained uncha~ged. Therefore, the properties of the Si3N4 body were changed without cha~ging the che~istry of the glassy phase.
The examples show that the processes of the present invention produce alloyed cermet or ceramic bodies. So~e of the resultant bodies optionally have chemical composition gradients. The main ad~antage is that the processes can alter the chemistry of a cermet or ceramic body without significantly altering the density or shape of the original body.
While our invention has been described in terms of a few specific embodiments, it will be appreciated that other embodiments could readily be adapted by one skilled in the art. Accordingly, the scope of our invention is to be considered limited only by the foLlowing claims.
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,
DENSIFIED CERAMIC OR CERMET BODY AND ALLOYED BODIES
PRODUCED THEREBY
This in~e~tion relates to processes for alloying metal, or an inorganic compound containing such a metal, into a ceramic or ceramic-metal (cermet) body that has a de~sity greater than or equal to 95% of the body's theoretical de~sity.
It is well known that metal alloys often have more desirable propertiec than pure metals. It would follow that alloyed cermets and ceramics may have more desirable properties than non-alloyed cermets and ceramics. It would thereore be desirable to have methods ~or making such alloyed cermets and ceramics. -It would also be desirable to be able to alter the properties of a ceramic or cermet body by alloying without significa~tly changing the shape or density of the body. It would further be desirable to be able to make a cermet or ceramic body tha~ has different properties such as improved oxidative resistance or wear ,' resistance at separate locations on the body.
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WO 92/16670 Pcr/uss2to1s2s One aspect of the presen~ invention is a process for alloying a ~etal or a metal-containing material into a densified cermet body comprising:
(a) placing an alloying metal or an inorganic compount containing an alloying metal in contact with at least a portion of an exterior surface of a cermet body that has a densi~y of at least 95% of the theoretical full density and is formed of a ceramic that has a ~atrix metal di persed therein, the matrix ~etal 0 extending fro~ the exterior surface portion at least partially into the cermet body; and (b) heating ~he cermet body, while it is in contact with the alloying metal or the inorganic 1~ compound containing the alloying metal~ to a temperature that is greater than or equal to 50C belo~ the lesser of the ~atrix metal's melting point and the temperature at which the matrix metal and the alloying metal form an eutectic, to diffuse the alloying metal into the cermet body and form an alloy between the alloying metal and the matrix metal.
A second aspect of the invention includes a method for alloying a metal or a metal-containing material into a densified ceramic body comprising:
(a) placing an alloying metal or an inorganic compound containing an alloying metal in contact with at least a portion of an exterior surface of a ceramic body that has a density of at least 95% of the theoretical full density and is formed of a glassy-phase component ~, and a non-glassy-phase component, the glassy-phase component extending from the exterior surface portion at least partially into the ceramic body; and ~ ' . - I ' ':
.
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WO 92~T6670 2 1 a ~ 2 X ~ PCT/US92/01928 (b) heating the ceramic body to a temperature ~t least nea~ that at which the glassy-phase component softens while the alloying me~al or the inorganic compound containing an alloying metal is in contact with the ceramic body to diffuse the alloying metal into the ceramic body and form an alloy between the alloyi~g metal and the glassy-phase component.
Bodies prepared by the methods described immediately above are also disclosed.
The first aspect of the invention concerns a method for alloying a metal, or a material containlng a metal, into a densified cermet body. The term 'Imetal--containing maeerial" collectivel~ refers to alloying metals and inorganic compounds co~taining an alloying metal. The metal-containing material is ~uitably selected fro~ pure metals, alloys of two or more metals, and inorganic compounds containing at lea~t one metal.
A "metal" is an element from the Periodic Table of the Elements that forms positive ions when its compounds are in solution and whose oxides form hydroxides rather than acids with water. De~irable metals include nickel, chromium, copper, vanadium, titanium, silicon, magnesium, hafnium, tungsten, molybdenum, manganese, iron, copper or tantalum. Satisfactory inorganic compounds relea~e or give up metal under conditions of the present invention to form a metal alloy with the matrix metal of the cermet. Inorganic compounds that 3 are stable, in that they do not release metal to form an alloy under conditions of the present invention, are not suitable. Illustrative inorganic compounds include nitrides, oxides, carbides, borides or silicides of the WO92/l~70 PCT/US~2/0192B
~ ' -4-metals. Carbides, nitrides and oxides are preferred inorganic compound~.
The metal component of the metal-containing -;
material is preferably different from the matrix metal of the cermet body~ The metal-containing material may be either solid or molten when it is initially placed in contact with the cermet body. When the metal-containing material is solid, it may be in any form including powder or foil. When the metal-containi~g material is in the form of a foil, the foil is desirably less than 0.75 mm thick, more desirably~ less than 0.5 mm thick, and, preferably, less than 0.1 mm thick.
Examples of cermet/alloying metal combinations suitable for this invention include those provided in Table 1.
Table 1 Cermet Possible AlloYinq Metals B4C/Al Ni, Cr, Cu, V, Ti, Si, Mg, ~f, W
SiC/Al Ni, Cr, Cu, Mn, V, Ti, Mg, Si, Hf, W
Tis2/Al Ni, Cr, Cu, Mn, Ti TiB2/Cu Al, Ti, Si, Ta, Fe, Co Si3N4/Al Cr, Mn, Ti Si3N4/Ni Ti, Fe, Co, Mn SiB6/Al Ni, Cr, Cu, Mn, Tl, Si The cermet body, prior to contact with the metal-contai?ning material, has a ceramic component and a matrix metal component. The cermet body desirably cont~ins from 15 to 99 weight percent ceramic component ?
and from 85 to 1 weight percent matrix metal component.
The cermet body preferably contains from 60 to 80 weight :~ t~
WO92/1~70 ~1 a i 2 .~ ~ PCT/U~92/0i928 percent ceramic component and from 40 to 20 weight percent matrix metal component. The weight percen~ages total lO0 percent. The ceramic component is desirably boron carbide, silicon carbide, titanium boride, alumina, or silicon nitride. The matrix me~al component is desirably aluminumt titanium, copper or nickel. In order for the metal-containing material to d;ffuse into the cermet body, two conditions must exist. First, the matrix metal must be in physical contact with the metal--containing material at least at an exterior surface portion of the cermet body. Second, the matrix metal must extend at least partially i~to the cermet body from that surface portion. The matrix ~etal may be continuous throughout the bulk of the cermet body with the ceramic being the discontinuous phase.
The non-alloyed cermet body may be prepared by any conventional method. For example, the cer~et body may be prepared by densifying a mixture of ceramic and matrix metal powders into a desired shape. The densification may be accomplished by conventional processes such as cold pressing or slip casting. If desired, these processes may be follo~ed by sintering to further densify the cermet body.
Another method of preparing a non-alloyed cermet body includes a first step of forming a porous ceramic body. Conventional procedures, such as slip casting a ceramic dispers~on or cold pressing ceramic pcwder, produce porous bodies with a desired shape.
Molten matrix metal is then placed in contact ~ith the porous ceramic body. The molten metal infiltrates into the porous ceramic body by capillary actisn. Such WO92~l~7~ PCT/US92/0!928 ~ ?,~3 -6-methods are di~closed in U.S. Patent Nos. 4,702,770, 4,718,941, and 4,834,938.
U.S~-A 4,702,770 describes, at column 6, lines 5-25, a four ~tep method for producing low density boron carbide-aluminum ~omposites. The first three ~teps yield a satisfactory cermet body. In step one, a colloidal consolidation technique is u~ed to form a porous boron carbide compact from a homogeneous dispersion of boron carbide. In step two, the compact in enriched with carbon by heat treating or sintering the boron carbide in the pre~ence of graphite. In step three, aluminum is infiltrated into the enriched compact.
U.S.-A 4,718,941 discloses the infiltration of molten reactive metals into chemically pretreated boron carbide, boron or boride starting material~. The chemical pretreatment procedure is described in detail at column 7, line 8 through column 8, line 12. The starting materials are immersed in a chemical substance that reacts with B203, BH303, or both, for as long as necessary to change the surface chemistry by forming boron-carbon-hydrogen-oxygen complexes that pyrolyze upon heating, either prior to, or during, infiltration.
Suitable chemical substances include various alcohols, such as methanol, isopropyl alcohol and denatured ethanol.
U.S.-A 4~834,938 outlines a process for making a composite article having an internal surface or cavity. A porous compact is formed about an insert body that has an external surface corresponding to the internal surface of the composite. The article is heated to the wetting temperature of the insert body to ~ . . .
`
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wos2/l667o PCT/US92/0192~
~:la~ ,f.~) melt the insert and cause it to infiltrate into the porous compact.
The non-alloyed cermet body required for purposes of the present invention has a density o at least 95% of theoretical density. The density is more preferably at least 99% of theoretical de~sity.
Alloying, or the diffu~ion of an alloying metal into a matrix metal, is desirably initiated by heating the cermet body to a temperature greater than or equal to that at which the matrix metal melt~. If an eutectic alloy is formed between the matrix metal and the alloying metal, the eutectic alloy typically ha~ a melting point lower than that of the matrix metal. If an eutectic alloy i9 formed, the temperature may be decreased to equal or exceed the melting point of the eutectic alloy. If no eutectic alloy is formed, the temperature is preferably maintained at or above the melting temperaturc of the matrix metal until alloying reaches a desired level.
Temperature plays an important role in determining the rate at which alloys between the matrix metal and the alloying metal form. Diffusion occurs so slowly at room temperature that it is not readily detected over a period of several days. As the temperature approaches the melting temperature of the matrix metal, diffusion becomes more discernible. At the melting temperature, diffusion is rapid enough to yield a readily detectable amount of alloy. At temperatures in excess of the melting temperature, diffusion occurs very rapidly. The temperature must not, however, be 30 high that the ceramic portion of the cermet begin~ to decompose or dissociate. The term "at . :
: , `: :
W092/1~70 PC~/~JS92/01928 A a~ ;s~ -8-least near" means greater than or equal to a temperature that is 50C below the melting temperature of the matrix metal. The temperature preferably equals or exceed~ the melting temperature of the matrix metal, but is less than the di~sociation temperature of the ceramic portion 5 of the cermet.
During the alloying process, the metal--containing material ~ay or may not become molten, depending on its melting po;nt. A satisfactory degree 0 of alloying is attainable if only the matrix metal becomes liquefied. When foils are used and the metal--containing material is to become molten during the alloying process, thin foils are preferred as they melt 15 faster and result in more uniform diffusion across the contacted susface of the cermet body. The matrix metal preferably has a melting point that is less than or equal to the melting point of the metal-containing material.
The second aspect of the invention is a method for alloying a metal-containing material into a densified ceramic body. The ceramic body contains a glassy-phase compone~t and a ~on-glassy-phase component.
25 The ceramic body desirably contains from 70 to 99 weight percent of non-glassy phase and from 30 to 1 weight ?
percent glassy phase. The ceramic body preferably contains from 85 to 97 weight percent non-glassy phase and from 15 to 3 weight percent glassy phase.
The non-glassy-phase component of the ceramic body is desirably silicon nitride. The glassy-phase component of the ceramic body is desirably formed of a metallic oxide such as yttria, magnesia, alumina, ., ~ , . , , j.................. .
- . ' i , !
' Wo92JI~7~ 2 i ~ i, PC~ S~2tO192 silisa, zirco~ia, tantalum oxide, calcium oxide or a mixture of two or more o such oxides.
In order for the metal-containing material to diffuse into the ceramic body, t~o conditions must be met. First, the glassy-phase component must be in physical contact with the ~etal-containing material at least at an exterior surface portion of the ceramic body. Second, the glassy-phase component must extend at least partially into the ceramic body from that surface portion. The glassy-phase component may be continuous throughout the bulk of the ceramic body while the non--glassy phase component may be discontinuous throughout the remainder of the bulk of the ceramic body.
The ceramic body may be prepared by densifying a mixture of powders that will constitute the ~lassy-phase and non-glassy-phase components. For instance, silicon nitride, yttria, magnesia, and zirconia powders may be densified into a desired shape by cold pressing, or slip casting, the powders into a body and then sintering the body. The ceramic bodies desirably have a density of at least 95% of theoretical density. The density is preferably at least 98Z of theoretical density.
Metal-containing materiaLs suitable for purposes of the second aspect of the present invention, like those of the first aspect~ are metals, inorganic compounds containing a ~etal or having a metallic constituent, a metal alloy, or a metal o~ide. Metal oxides are commonly available me~al-con~aining materials. The metal or metallic constituent is suitably yttrium, magnesium, chromium, zirconium, molybdenum, vanadium, titanium or a rare earth metal WO 92/16670 PCr/US92/01928 (elements 57-71 of the Periodic Table). The ~etal or metallic constituent must differ from that contained in the glassy-phase component if alloying is to occur.
The metal-containing material may be solid or liquid when it is initially placed in contact with the ceramic bodyO As in the first aspect, it may be in the form of a powder or a foil when it is a solid. As the ceramic body is heated to soften the glassy-phase component, the metal-containing material may retain its 0 initial form or be converted to a liquidO
If d2sired, two or more differ~nt metal--containing materials may be placed in contact with exterior surface portions of either the cer~et of ~he first aspect of the invention or the ceramic of the seco~d aspect. If, for example, two different materials are placed in contact with exterior surface portions of a cermet or ceramic body, they are preferably not applied to the same surface portion.
During the heating step of the invention, the metal-containing material gradually diffuses into the cermet or ceramic body from the exterior surface portion 2~ in contact with said material. Before alloying i~
complete, alloying occurs in a gradient manner. The term "gradie~t manner" means that alloying occurs to a greater exten~ at or near the exterior surface portion and to a progressively lesser extent as distance from that portion increases as one travels in a direction perpendicular to the surface portion into the ceramic or cermet body~ Alloying may change only the chemistry of the matrix metal or glassy-phase component. It may also change the chemistry of the ceramic or non-glassy phase component thereby forming new phases. The alloying , .
. : . . ... i , - ~ . , ~ ' ', . . . :. .
. . - . - ~ :- :
.~ . . .
WO 92/16670 2 1 () ~ PC~/lJS92/01928 process may be conti~ued uutil the body is substantially free of chemical composition gradients. M~re typically, alloying is terminated while gradients are still present. Termination occurs by conventional means, such as cooling the cermet body or the ceramic body to a temperature ~ell below the respective matrix metal liquidus temperature or the glassy-phase component softening temperature.
After termination of alloying, any excess 0 metal-containing material on the surface of the cermet or the ceramic body may be removed by conventional processes. These processes include peeling or grinding.
The alloyed bodies of this iuvention are especially useful for making abrasion-resistant parts, such as cutting tools and drilling tools, and wear parts, such as automobile brakes.
The following examples are illustrative only and should not be construed as limiting the invention which is properly delineated in the appended claims.
Example _l A block-shaped porous body of boron carbide, measuring about 1 cm thick, was prepared by slip casting a dispersion of boron carbide powder. The slip-cast body had a de~sity of about 64% of the theoretical density of boron carbide. The porous body was 3 impregnated with aluminum by contacting the boron carbide body with aluminum and heated to 1180C to form a cermet body. At that temperature, sintering was effected and the cermet body comprised about 64 weight %
boron carbide, about 25 weight % aluminum and about 11 weight % reaction products containing aluminum. The , : :
.
WO92/16670 PCT/US92/0l928 ~ Q '~J ~ -12-body had a den~ity of greater than 99% of the theoretical density. Table 2 shows typical reaction products.
Copper foil measuring about 0.75 mm thick was placed on one side of the cermet body, while a foil of nickel measuring about 0.75 mm thick was placed on the opposite side. The ~espective melting points of the matrix metal (aluminum), the copper, and the nickel are 660C, 1085C, and 1445C. The cermet body and the 0 associated copper and nickel foils were placed in a graphite crucible. The crucible ~as placed in an oven with a flo~ing argon atmosphere. The temperature of the oven was increased from room temperature to 1100 in about two hours and held at 1100C for one hour. The cermet body was then removed from the furnace and allowed to cool naturally to ambient temperature.
Cooling occurred over a period of about 1 1/2 hours.
Chemical analysis of the alloyed cermet body was completed using an MBX-CAMECA microprobe~ available from Cameca Co., France. The results are provided in Table 2 which shows the volume percent amounts of the various phases listed on the side of the table at three locations in the alloyed cermet body~ The first location was in copper side, the second location was in the bulk of the boron carbide cermet body, and the third location was in the nickel side.
The results summarized in Table 2 demonstrate that diffusion of the metal-containing materials occurred. The nickel co~ponent ranged from a high of 20 volume percent at the "nickel end" through an intermediate value of 12 volume percent in the middle of the cermet body to a low of not being detectable in the ... ..
wos2/t~70 2 1 9 ~ 2 ~ ~ PCT/US~2/01928 "copper end". The copper component (CuAl2) sho~ed a similar gradient. Furthermore, the boron carbide volume percent remained fairly consistent throughout the cermet body.
Table 2 Vol 96 Vol% of of phase in Vol ~ of phase in Middle of phase in Phase CoPPer end cermet body Niokel end o (NiCu)2Al3 nda 12 20 Al with about lO l5 20 2 wt% Cu CuAl2 with 20 8 nda about 0~4 wt%
AlE324C4 10 9 9 s4c 58 54 49 Al4BC <lb cl <l Al4C3 a = not detected b = present, but in an amount less than l vol Example 2 A boron carbide-aluminum cermet body was prepared by the method described in Example l. A copper foil, measuring about l mm thick, was placed on ~he cermet body. The cermet body was then heated to l100C, and the te~perature was maintained for l hour. After cooling the cermet body, the copper foil was removed.
It was fou~d that the copper content of the foil was reduced by 3.5 wt%.
.
.
WO 92/l~ib~O PCI-/US92/i)192X
~a ~ 4- `
Example 3 This example illustrates the use of a powder form of a metal-containing material. A densified ceramic body having a composition of 86.3 wtX Si3N4, 8.5 wt% Y203, 4.7 wt% MgO and 0.5 wt.% GaO was prepared by hot-pressing a mixture of the Si3N4 and oxide powders at 1825C for 1 hour. The ceramic body had a density of about 99.5% of the maximum theoretically possible density. The ceramic body was buried in a HfO2 powder 0 bed in a quartz container. The ceramic body and HfO2 bed were heated to 1400C and held at this temperature for 1 hour while in a flowing nitrogen atmosphere~ The ceramic body a~d the HfO2 bed were then allowed to cool.
After cooling, the ceramic body was separated from the HfO2 po~der, sectioned, and analyzed. 0~ the surface of the ceramic body, an alloyed layer rich in HfO2 measuring approximately 50 micrometers deep was observed. The diffusion of HfO2 altered the ceramic body's composition, but did not alter the chemistry or shape of the Si3N4 grains. Analysis indicated that the alloyed layer contained Si3N4 grains in two glassy phases: a phase relatively high in Mg, relatively low in Y, and having no Hf; and a phase havi~g a relatively intermediate levels of Mg and Y and a relatively high level of Hf.
Example 4 A densified ceramic body was prepared as in Example 3 and placed in a bed of Cr203 powder. After heating the ceramic body and Cr203 powder to 1400C, maintaining this temperature for 1 hour, then cooling, three alloyed layers near the surface of the ceramic body were observed. The first, or outside layer, .
- . , ~ - .
. , . : .
, ' ~, ' ' ' :
WO92/16670 2 ~ PC~/USg2tO1928 consisted of Cr3Si, Cr2N, a relatively high level of yttria silicate crystals, and a mixture of two glassy phases. The glassy phases were: a phase having Y and Mg in a weight ratio of about 1:1; and a phase contai~ing a relatively low level of Y, and relatively high levels of Mg and Ca. The second, or middle layer, consisted of Si3N4, Cr3Si and a relatively low level of CaO glass. The third, or innermost, layer consisted of Si3N4 and glass containing a relatively intermediate amount of Y, a relatively intermediate amount of Mg, and no Ca. The weight ratio of Y to Mg in this inner~ost layer was about 0.6:1. The total thickness of all three layers was about 200 micrometers. This example illustrates that eve~ though diffusion occurred through the glassy phase, the majority of the Cr formed new cry5talli~e phases and the gla.q~ chemistry remained uncha~ged. Therefore, the properties of the Si3N4 body were changed without cha~ging the che~istry of the glassy phase.
The examples show that the processes of the present invention produce alloyed cermet or ceramic bodies. So~e of the resultant bodies optionally have chemical composition gradients. The main ad~antage is that the processes can alter the chemistry of a cermet or ceramic body without significantly altering the density or shape of the original body.
While our invention has been described in terms of a few specific embodiments, it will be appreciated that other embodiments could readily be adapted by one skilled in the art. Accordingly, the scope of our invention is to be considered limited only by the foLlowing claims.
, . . .
,
Claims (25)
1. A process for alloying a metal-containing material into a densified cermet body comprising:
(a) placing an alloying metal or an inorganic compound containing an alloying metal in contact with at least a portion of an exterior surface of a cermet body that has a density of at least 95% of the theoretical full density and is formed of a ceramic that has a matrix metal dispersed therein, the matrix metal extending from the exterior surface portion at least partially into the cermet body; and (b) heating the cermet body, while it is in contact with the alloying metal or the inorganic compound containing the alloying metal, to a temperature that is greater than or equal to 50°C below the lesser of the matrix metal's melting point and the temperature at which the matrix metal and the alloying metal form an eutectic, to diffuse the alloying metal into the cermet body and form an alloy between the alloying metal and the matrix metal.
(a) placing an alloying metal or an inorganic compound containing an alloying metal in contact with at least a portion of an exterior surface of a cermet body that has a density of at least 95% of the theoretical full density and is formed of a ceramic that has a matrix metal dispersed therein, the matrix metal extending from the exterior surface portion at least partially into the cermet body; and (b) heating the cermet body, while it is in contact with the alloying metal or the inorganic compound containing the alloying metal, to a temperature that is greater than or equal to 50°C below the lesser of the matrix metal's melting point and the temperature at which the matrix metal and the alloying metal form an eutectic, to diffuse the alloying metal into the cermet body and form an alloy between the alloying metal and the matrix metal.
2.A process as claimed in claim 1, wherein the ceramic is boron carbide, alumina, silicon carbide, titanium boride, or silicon nitride; the matrix metal is aluminum, copper, titanium, or nickel; the alloying metal or the inorganic compound containing an alloying metal has a metal component that is nickel, chromium, copper, vanadium, titanium, silicon, magnesium, hafnium, tungsten, molybdenum, manganese, iron, copper, or tantalum; and the matrix metal and the alloying metal are different metals.
3.A process as claimed in claim 1 or claim 2 wherein the density of the cermet body is at least about 99% of the theoretical full density.
4.A process as claimed in any of the preceding claims wherein the alloying metal or the inorganic compound is in the form of a foil having a thickness less than 0.75 mm during step (a).
5.A process as claimed in any of the preceding claims wherein the matrix metal has a lower melting point than that of the alloying metal or the inorganic compound.
6.A process as claimed in any of the preceding claims wherein a first alloying metal or inorganic compound containing an alloying metal is in contact with a first exterior surface portion of the cermet body and at least one additional alloying metal or inorganic compound containing an alloying metal is in contact with at least one additional exterior surface portion of the cermet body, the first alloying metal or inorganic compound differing from each additional alloying metal or inorganic compound, and the exterior surface portions are distinct from each other.
7.A process as claimed in any of the preceding claims wherein the heated cermet body is subsequently cooled to stop diffusion and provide a chemical composition gradient that penetrates into the cermet body perpendicular to the exterior surface portion in contact with the alloying metal.
8.An alloyed cermet body formed by the process of any of claims 1-7.
9.A process for alloying a metal-containing material into a densified ceramic body, comprising:
(a) placing an alloying metal or an inorganic compound containing an alloying metal in contact with at least a portion of an exterior surface of a ceramic body that has a density of at least 95% of the theoretical full density and is formed of a glassy-phase component and a non-glassy-phase component, the glassy-phase component extending from the exterior surface portion at least partially into the ceramic body; and (b) heating the ceramic body to a temperature at least near that at which the glassy-phase component its softens while the alloying metal or the inorganic compound containing an alloying metal is in contact with the ceramic body to diffuse the alloying metal into the ceramic body and form an alloy between the alloying metal and the glassy-phase component.
(a) placing an alloying metal or an inorganic compound containing an alloying metal in contact with at least a portion of an exterior surface of a ceramic body that has a density of at least 95% of the theoretical full density and is formed of a glassy-phase component and a non-glassy-phase component, the glassy-phase component extending from the exterior surface portion at least partially into the ceramic body; and (b) heating the ceramic body to a temperature at least near that at which the glassy-phase component its softens while the alloying metal or the inorganic compound containing an alloying metal is in contact with the ceramic body to diffuse the alloying metal into the ceramic body and form an alloy between the alloying metal and the glassy-phase component.
10.A process as claimed in claim 9 wherein the ceramic body is made of silicon nitride and the alloying metal or the inorganic compound has a metal component that is selected from metals, metal alloys, and metal oxides.
11.A process as claimed in claim 9 or claim 10 wherein the glassy phase component has a softening point that is lower than the melting point of the alloying metal or the inorganic compound containing the alloying metal.
12.A process as claimed in any one of claims 9-11 wherein a first alloying metal or inorganic compound containing an alloying metal is in contact with a first exterior surface portion of the ceramic body and at least one additional alloying metal or inorganic compound containing an alloying metal is in contact with at least one additional exterior surface portion of the ceramic body, the first alloying metal or inorganic compound differing from each additional alloying metal or inorganic compound, and the exterior surface portions are distinct from each other.
13.A process as claimed in any one of claims 9-12 wherein the heated ceramic body is subsequently cooled to stop infiltration and provide a chemical composition gradient that penetrates into the ceramic body perpendicular to the exterior surface portion in contact with the alloying metal.
14.An alloyed ceramic body formed by the process of any of claims 9-13.
15.A process as claimed in claim 1 wherein the density of the cermet body is at least about 99% of the theoretical full density.
16.A process as claimed in claim 1 wherein the alloying metal or the inorganic compound is in the form of a foil having a thickness less than about 0.75 mm during step (a).
17.A process as claimed in claim 1 wherein the matrix metal has a lower melting point than that of the alloying metal or the inorganic compound.
18.A process as claimed in claim 1 wherein a first alloying metal or inorganic compound containing an alloying metal is in contact with a first exterior surface portion of the cermet body and at least one additional alloying metal or inorganic compound containing an alloying metal is in contact with at least one additional exterior surface portion of the cermet body, the first alloying metal or inorganic compound differing from each additional alloying metal or inorganic compound, and the exterior surface portions are distinct from each other.
19.A process as claimed in claim 1 wherein the heated cermet body is subsequently cooled to stop diffusion and provide a chemical composition gradient that penetrates into the cermet body perpendicular to the exterior surface portion in contact with the alloying metal.
20.An alloyed cermet body formed by the process of claim 1.
21.A process as claimed in claim 9 wherein the ceramic body is made of silicon nitride and the alloying metal or the inorganic compound has a metal component that is selected from the group consisting of metals, metal alloys, and metal oxides.
22.A process as claimed in claim 9 wherein the glassy-phase component has a softening point that is lower than the melting point of the alloying metal or the inorganic compound containing the alloying metal.
23.A process as claimed in claim 9 wherein a first alloying metal or inorganic compound containing an alloying metal is in contact with a first exterior surface portion of the ceramic body and at least one additional alloying metal or inorganic compound containing an alloying metal is in contact with at least one additional exterior surface portion of the ceramic body, the first alloying metal or inorganic compound differing from each additional alloying metal or inorganic compound, and the exterior surface portions are distinct from each other.
24.A process as claimed in claim 9 wherein the heated ceramic body is subsequently cooled to stop infiltration and provide a chemical composition gradient that penetrates into the ceramic body perpendicular to the exterior surface portion in contact with the alloying metal.
25.An alloyed ceramic body formed by the process of claim 9.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US66917891A | 1991-03-14 | 1991-03-14 | |
US07/669,178 | 1991-03-14 |
Publications (1)
Publication Number | Publication Date |
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CA2104288A1 true CA2104288A1 (en) | 1992-09-15 |
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ID=24685386
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA 2104288 Abandoned CA2104288A1 (en) | 1991-03-14 | 1992-03-11 | Methods for alloying a metal containing material into a densified ceramic or cermet body and alloyed bodies produced thereby |
Country Status (4)
Country | Link |
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EP (1) | EP0575493A1 (en) |
JP (1) | JPH06506265A (en) |
CA (1) | CA2104288A1 (en) |
WO (1) | WO1992016670A2 (en) |
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FR2843896A1 (en) * | 2002-12-09 | 2004-03-05 | Commissariat Energie Atomique | Porous substrate containing a metallic phase for the production of fuel cell electrodes and connections for micro-electronic components has controlled concentration varying with depth |
GB2548855A (en) * | 2016-03-30 | 2017-10-04 | Imp Innovations Ltd | Oxidation resistant coating and methods of manufacturing thereof |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
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FR1098067A (en) * | 1953-12-22 | 1955-07-18 | Onera (Off Nat Aerospatiale) | Improvements to processes for the formation of surface diffusion alloys, in particular on refractory parts |
US3556744A (en) * | 1965-08-16 | 1971-01-19 | United Aircraft Corp | Composite metal article having nickel alloy having coats containing chromium and aluminum |
US3367398A (en) * | 1965-10-19 | 1968-02-06 | Atomic Energy Commission Usa | Method of preventing segregation during casting of composites |
FR2043989A5 (en) * | 1969-05-05 | 1971-02-19 | Sherritt Gordon Mines Ltd | Dispersion-reinforced nickel-chrome alloys |
US4101714A (en) * | 1977-03-31 | 1978-07-18 | General Electric Company | High temperature oxidation resistant dispersion strengthened nickel-chromium alloys |
US4847044A (en) * | 1988-04-18 | 1989-07-11 | Rockwell International Corporation | Method of fabricating a metal aluminide composite |
US5000248A (en) * | 1988-11-10 | 1991-03-19 | Lanxide Technology Company, Lp | Method of modifying the properties of a metal matrix composite body |
-
1992
- 1992-03-11 CA CA 2104288 patent/CA2104288A1/en not_active Abandoned
- 1992-03-11 JP JP4508319A patent/JPH06506265A/en active Pending
- 1992-03-11 WO PCT/US1992/001928 patent/WO1992016670A2/en not_active Application Discontinuation
- 1992-03-11 EP EP19920908117 patent/EP0575493A1/en not_active Withdrawn
Also Published As
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WO1992016670A2 (en) | 1992-10-01 |
WO1992016670A3 (en) | 1992-12-23 |
EP0575493A1 (en) | 1993-12-29 |
JPH06506265A (en) | 1994-07-14 |
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