CA2049636A1 - Ceramic-metal articles and methods of manufacture - Google Patents
Ceramic-metal articles and methods of manufactureInfo
- Publication number
- CA2049636A1 CA2049636A1 CA002049636A CA2049636A CA2049636A1 CA 2049636 A1 CA2049636 A1 CA 2049636A1 CA 002049636 A CA002049636 A CA 002049636A CA 2049636 A CA2049636 A CA 2049636A CA 2049636 A1 CA2049636 A1 CA 2049636A1
- Authority
- CA
- Canada
- Prior art keywords
- titanium
- tungsten
- article
- hafnium
- tantalum
- 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 56
- 239000002184 metal Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000010936 titanium Substances 0.000 claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 37
- 239000006104 solid solution Substances 0.000 claims abstract description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010937 tungsten Substances 0.000 claims abstract description 20
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 18
- 150000004767 nitrides Chemical class 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 16
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 16
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 14
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 13
- 239000010955 niobium Substances 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 12
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 229910052796 boron Inorganic materials 0.000 claims abstract description 11
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 11
- 239000011651 chromium Substances 0.000 claims abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 11
- 239000010941 cobalt Substances 0.000 claims abstract description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 11
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011733 molybdenum Substances 0.000 claims abstract description 10
- 238000001513 hot isostatic pressing Methods 0.000 claims abstract description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 6
- 229910001005 Ni3Al Inorganic materials 0.000 claims description 16
- 150000001247 metal acetylides Chemical class 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 claims description 9
- 229910010293 ceramic material Inorganic materials 0.000 claims description 8
- 229910001275 Niobium-titanium Inorganic materials 0.000 claims description 5
- GAYPVYLCOOFYAP-UHFFFAOYSA-N [Nb].[W] Chemical compound [Nb].[W] GAYPVYLCOOFYAP-UHFFFAOYSA-N 0.000 claims description 5
- DZZDTRZOOBJSSG-UHFFFAOYSA-N [Ta].[W] Chemical compound [Ta].[W] DZZDTRZOOBJSSG-UHFFFAOYSA-N 0.000 claims description 5
- VSTCOQVDTHKMFV-UHFFFAOYSA-N [Ti].[Hf] Chemical compound [Ti].[Hf] VSTCOQVDTHKMFV-UHFFFAOYSA-N 0.000 claims description 5
- MGPRQEHECDTSNH-UHFFFAOYSA-N [W].[Hf] Chemical compound [W].[Hf] MGPRQEHECDTSNH-UHFFFAOYSA-N 0.000 claims description 5
- INIGCWGJTZDVRY-UHFFFAOYSA-N hafnium zirconium Chemical compound [Zr].[Hf] INIGCWGJTZDVRY-UHFFFAOYSA-N 0.000 claims description 5
- ZPZCREMGFMRIRR-UHFFFAOYSA-N molybdenum titanium Chemical compound [Ti].[Mo] ZPZCREMGFMRIRR-UHFFFAOYSA-N 0.000 claims description 5
- RJSRQTFBFAJJIL-UHFFFAOYSA-N niobium titanium Chemical compound [Ti].[Nb] RJSRQTFBFAJJIL-UHFFFAOYSA-N 0.000 claims description 5
- VSSLEOGOUUKTNN-UHFFFAOYSA-N tantalum titanium Chemical compound [Ti].[Ta] VSSLEOGOUUKTNN-UHFFFAOYSA-N 0.000 claims description 5
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 claims description 5
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 claims description 5
- 230000001464 adherent effect Effects 0.000 claims description 4
- 239000011195 cermet Substances 0.000 abstract description 4
- 238000007731 hot pressing Methods 0.000 abstract description 3
- OSIVBHBGRFWHOS-UHFFFAOYSA-N dicarboxycarbamic acid Chemical compound OC(=O)N(C(O)=O)C(O)=O OSIVBHBGRFWHOS-UHFFFAOYSA-N 0.000 abstract 2
- 229910020012 Nb—Ti Inorganic materials 0.000 abstract 1
- 238000005520 cutting process Methods 0.000 description 33
- 239000000843 powder Substances 0.000 description 27
- 239000000463 material Substances 0.000 description 17
- 229910000831 Steel Inorganic materials 0.000 description 16
- 239000011230 binding agent Substances 0.000 description 16
- 239000010959 steel Substances 0.000 description 16
- 238000003801 milling Methods 0.000 description 14
- 238000000576 coating method Methods 0.000 description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 238000003754 machining Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910009043 WC-Co Inorganic materials 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000005240 physical vapour deposition Methods 0.000 description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910003310 Ni-Al Inorganic materials 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 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 4
- 238000007792 addition Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- -1 mol~bdenum Chemical compound 0.000 description 2
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 2
- 229910033181 TiB2 Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007596 consolidation process Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000003870 refractory metal Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910003178 Mo2C Inorganic materials 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- SMDHCQAYESWHAE-UHFFFAOYSA-N benfluralin Chemical compound CCCCN(CC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O SMDHCQAYESWHAE-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004836 empirical method Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- WHJFNYXPKGDKBB-UHFFFAOYSA-N hafnium;methane Chemical compound C.[Hf] WHJFNYXPKGDKBB-UHFFFAOYSA-N 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000004544 sputter deposition Methods 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
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
-
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
- B22F3/15—Hot isostatic pressing
-
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/23—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces involving a self-propagating high-temperature synthesis or reaction sintering step
-
- 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
- C22C29/067—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 comprising a particular metallic binder
Abstract
CERAMIC-METAL ARTICLES AND METHODS OF MANUFACTURE
ABSTRACT
A dense cermet article includiny about 80-95% by volume of a granular hard phase and about 5-20% by volume of a metal phase. The hard phase is a carbide, nitride, carbonitride, oxycarbide, oxynitride, or carboxynitride of a cubic solid solution selected from W-Ti, W-Hf, W-Nb, W-Ta, Zr-Ti, Hf-Ti, Hf-Zr, V-Ti, Nb-Ti, Ta-Ti, or Mo-Ti.
The metal phase consists essentially of a combination of nickel and aluminum having a ratio of nickel to aluminum of from about 90:10 to about 70:30 by weight, and 0-5% by weight of an additive selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, boron, and/or carbon. The article may be produced by presintering the hard phase -metal phase component mixture in a vacuum or inert atmosphere at about 1475° 1675°C, then densifying by hot isostatic pressing at a temperature of about 1575°-1675°C, in an inert atmosphere, and at about 34-207 MPa pressure.
Limiting the presintering temperature to 1475°-1575°C and keeping the presintering temperature at least 50°C below the hot pressing temperature produces an article of gradated hardness, harder at the surface than at the core.
In this gradated product, the hard phase may alternatively be a carbide, nitride, carbonitride, oxycarbide, oxynitride, carboxynitride, or boride of an element selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, or B.
ABSTRACT
A dense cermet article includiny about 80-95% by volume of a granular hard phase and about 5-20% by volume of a metal phase. The hard phase is a carbide, nitride, carbonitride, oxycarbide, oxynitride, or carboxynitride of a cubic solid solution selected from W-Ti, W-Hf, W-Nb, W-Ta, Zr-Ti, Hf-Ti, Hf-Zr, V-Ti, Nb-Ti, Ta-Ti, or Mo-Ti.
The metal phase consists essentially of a combination of nickel and aluminum having a ratio of nickel to aluminum of from about 90:10 to about 70:30 by weight, and 0-5% by weight of an additive selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, boron, and/or carbon. The article may be produced by presintering the hard phase -metal phase component mixture in a vacuum or inert atmosphere at about 1475° 1675°C, then densifying by hot isostatic pressing at a temperature of about 1575°-1675°C, in an inert atmosphere, and at about 34-207 MPa pressure.
Limiting the presintering temperature to 1475°-1575°C and keeping the presintering temperature at least 50°C below the hot pressing temperature produces an article of gradated hardness, harder at the surface than at the core.
In this gradated product, the hard phase may alternatively be a carbide, nitride, carbonitride, oxycarbide, oxynitride, carboxynitride, or boride of an element selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, or B.
Description
: ~ :. 3 ~ ~i t, ~9 3-643 -1-CE~A~IC-METAL ARTICLES ~ND MET~ODS OE MANUFACT~RE
This invention relates to metal bonded ceramic, e.g.
carbide, nitride, and carbonitride, articles for use as cutting tools, wear parts, and the like. In particular the invention relates to such articles bonded with a binder including both nickel and aluminum and methods for producing such articles.
The discovery and implementation of cobalt bonded 10 tungsten carbide (WC-Co) as a tool material for cutting metal greatly extended the range of applications beyond that of conventional tool steels. Over the last 50 years process and compositional modifications to WC-Co materials have led to further benefits in wear resistance, yet the potential of these materials is inherently limited by the physical properti.es of the cobalt binder phase. This becomes evident when cutting speeds are increased to a level which generates sufficient heat to soften the metal binder. The high speed finishing of steel rolls serves as 20 an example of a metal cutting application where the tool insert must maintain its cutting edge geometry at high temperature and resist both wear and deformation.
Unfortunately, the wear characteristics of WC-Co based cemented carbides are also affected by the high temperature chemical interaction at the interface between the ferrous alloy workpiece and the cemented carbide tool surface. Additions of cubic carbides (i.e. TiC) to the WC-Co system have led to some improvement in tool performance during steel machining, due in part to the 30 resulting increased hardness and increased resistance to chemical interaction. However, the performance of such TiC-rich WC-Co alloys is influenced by the low fracture toughness of the TiC phase, which can lead to a tendency toward fracture during machining operations involving intermittent cutting, for example milling.
Accordingly, a cemented carbide material suitable for cutting tools capable of withstanding the demands of hard steel turning (wear resistance) and steel milling (impact resistance) would be of great value. Such a new and improved material is described herein.
According to one aspect of the invention, there is provided a ceramic-metal article comprising: about 80-95%
by volume of a granular hard phase consisting essentially lO of a ceramic material selec-ted from the group consisting of the hard rafractory carbides, nitrides, carbonitrides, oxycarbides, oxynitrides, carboxynitrides, and mixtures thereof of a cubic solid solution selected from the group consisting of zirconium-titanium, hafnium-titanium, hafnium-zirconium, vanadium titanium, niobium-titanium, tantalum-titanium, molybdenum titanium, tungsten-titanium, tungsten-hafnium, tungsten-niobium, and tungsten-tantalum;
and about 5-20% by volume of a metal phase, wherein said metal phase consists essentially of a combination of 20 nickel and aluminum having a ratio of nickel to aluminum of from about 90:10 to about 70:30 by weight and 0-5% by weight of an additive selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, boron, carbon, and combinations thereof; wherein said article has a density of at least about 95% of theoretical.
More specifically we provide an article in accordance wherein said metal phase consists essentially of a Ni3Al 30 ordered crystal structure or of a Ni3Al ordered crystal structure coexistent with or modified by said additive.
According to another aspect of the invention, there is provided a process for producing a ceramic-metal article comprisin~ the steps of: presintering, in a vacuum or inert atmosphere at about 1475-1675C and for a time sufficient to permit developmant of a microstructure with closed porosity, a mixture of about 80-95% by ~011lme of a granular hard phase component consisting essentially of a ceramic material selected from the group consisting of (a) the hard refractory carbides, nitrides, carbonitrides, o~ycarbides, oxynitrides, carboxynitrides, borides, and mixtures thereof of the elements selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, and lO boron, and (b) the hard refractory carbides, nitrides, carbonitrides, oxycarbides, oxynitrides, and carboxy-nitrides, and mixtures thereof of a cubic solid solution selected from the group consisting of zirconium-titanium, hafnium-titanium, hafnium-zirconium, vanadium-titanium, niobium-titanium, tantalum-titanium, molybdenum-titanium, tungsten- titanium, tungsten-hafnium, tungsten-niobium, and tungsten-tantalum; and about 5-20% by volume of a metal phase component, wherein said metal phase component consists essentially of nickel and aluminum, in a ratio of 20 nickel to aluminum of from about 85:15 to about 88:12 by weight, and 0-5% ~y weight of an additive selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, mol~bdenum, tungsten, cobalt, boron, carbon, and combinations thereof;
and densifying said presintered mixture by hot isostatic pressing at a temperature of about 1575-1675C, in an inert atmosphere, and at about 34~207 MPa pressure for a time sufficient to produce an article having a density o at least about 95% of theoretical.
More specifically we provide a process wherein said presintering step is carried out at about 1475-1575C and said presintering step is carried out at a temperature at least 50C lower than that of said densifying step.
Also, more specifically, we provide a process wherein said ratio of nickel to aluminum is selected such that during said densifying step said metal phase component is substantially converted to a Ni3Al ordered crystal structure or a Ni3Al ordered crystal structure coexistent with or modified by said additive.
Some embodiments of the invention will now be described, by way o~ example, with reference to the accompanying drawings in which:
FIG. 1 is a graphical representation comparing the ma-chining performance of a cutting tool shaped article according to one aspect of the invention and commercially available tools;
FIG. 2 is a graphical representation comparing the milling performance of cutting tool shaped articles according to two aspects of the invention and commercially available tools;
FIGS. 3-6 are photomicrographs illustrating wear characteristics of various tools of related compositions, 20 including one tool according- to one aspect of the invention.
Described herein as exemplary ceramic materials are those including one or more hard refractory carbides, nitrides, oxycarbides, oxynitrides, carbonitrides, carboxynitrides, or borides of a tungsten-titanium solid solution, or one or more hard refractory carbides, nitrides, oxycarbides, oxynitrides, carbonitrides, or carboxynitrides of tungsten, bonded by an intermetallic binder combining nickel and aluminum. These exemplary 30 materials are considered typical o~ those claimed, and the following description thereof is not intended to limit the invention as recited in the claims.
A typical densified, metal bonded hard ceramic body or article is prepared from a powder mixture including cubic solid solution powders as the hard phase component, and a combination of both Mi and Al powders in an amount of J
about 5~20yO by volume as the binder component. Typical solid solution powders include (WX,Til~x3C, (WX,Til_x)N, (~x,Til_x)(C,N), (Wx,Til_x)(O,C~, (Wx,Til_x~(O,N), (WX,Til x)(O,C,N), or combinations thereof. Most preferably, x is a weight fraction o about 0.3 0.7. The best combination of properties (hardness and fracture toughness) is obtained when total metal binder addition is in the range of about 7-15% by volume. For best results in sintering and in both physical and chemical property lO balance, the weight ratio in the solid solution hard phase of tungsten to titanium should be in the range of about 0.3-3.0 and more preferably about 0.6-1.5. Materials with a W:Ti ratio lower than about 0.3 exhibit lowered fracture toughnass and impact resistance, which can be important in some applications, e.g. when used as cutting tools for steel milling. A ratio of about 3.0 or less can enhance wear resistance, which can also be important in some applications, e.g. when used as cutting tools for steel turning.
Alternatively, the ceramic materials may typically include compounds of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, boron, or mixtures thereof. Typical of these hard phase components are TiC, HfC, VC, TaC, Mo2C, WC, B4C, TiN, Ti(C,N), TiB2, or WB. The powder mixture contains the hard phase component, for example a tungstan carbide powder, and a combination of both Ni powder and Al powder in an amount of about 5-20% by volume as the metal component. The best combination of properties ~hardness 30 and fracture toughness) is obtained when total metallic phase addition is in the range of about 7-15% by volume.
In this exemplary material, the tungsten carbide ceramic component provides excellent wear resistance, which is important in applications such as cutting tools for steel turning. The metallic phase provides greater fracture toughness for the material than the sintered ceramic ! ~ ?
material alone, and the metallic phase combining aluminum and nickel in the above ratios provides improved high temperature properties such as creep resistance over cobalt or other single metal.
In any of these materials, as stated above, the metal powder component represents about 5-20% by volume and preferably about 7-15% by volume of the total starting formulation. The binder metal powder includes nickel in an amount of about 85-88% by weight, and aluminum in an lO amount of about 12-15% by weight, both relative to the total weight of the binder metal powder. A minor amount of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, boron and/or carbon, not to exceed about 5% by weight of total binder metal, may also be included. The preferred composition is 12-14% by weight Al, balance Ni. In the most preferred binder compositions the Ni:Al ratio results in the formation o~ a substantially Ni3Al binder, having the Ni~Al ordered crystal structure. The amount of Ni3Al 20 is also dependent on the processing, e.g. the processing temperatures, and may be selectecl to achieve various properties in the cermet, e.g. 100%, 40-80%, less than 50%, etc. of the metal phase. The ratio of Ni:Al powders required to achieve the desired amount of Ni3Al may be readily determined by empirical methods. Alternatively, prereacted Ni3Al may be used in the starting formulation.
In some compositions, this ordered crystal structure may coexist or be modified by the above-mentioned additives. The preferred average grain size of the hard 30 phase in a densi~ied body of this material for cutting tool use is about 0.5-5.0 ~m. In other articles for applications where deformation resistance requirements are lower, e.g. sand blasting nozzles, a larger range of grain sizes, e.g. about 0.5-20 ~m, may prove satisfactory. The material may be densified by known methods, for example ,1, . ' I C ~
89-3-~43 -7-sintering, continuous cycle sinterhip, two step sinter-plus-HIP, or hot pressing, all known in the art.
An alternate densified, metal bonded hard ceramic body or article has the same overall composition as those described above, but differs in that it exhibits a gradat~d hardness, most preferably exhibiting lower hardness in the center portion of the body and progressively increasing hardness toward the tool surface.
To obtain a body with these characteristics, the 10 densification process includes a presintering step in which the starting powder mixture is subjected to temperatures of about 1475-1575C, preferably 1475-1550C, in vacuum (e.g. about 0.1 Torr) or in an inert atmosphere (e.g. at about 1 atm) for a time sufficient to develop a microstructure with closed porosity, e.g. about 0.5-2 hr. As used herein, the term "microstructure with closed porosity" is intended to mean a microstructure in which the remaining pores are no longer interconnected. Subsequently, the body is fully 20 densified in an inert atmospheric overpressure of about 34-207 MPa and temperature of about 1575-1675C, preferably 1600-1675C, for a time sufficient to achieve full density, e.g. about 0.5-2 hr. The presintering temperature is at least 50C lower than the ~inal densification temperature. These gradated bodies exhibit outstanding impact resistance, and are particularly useful as milling tool inserts and as tools for interrupted cutting of steel.
The depth to which the gradated hardness is effected 30 is dependent on the presintering temperature. Thus, if a fully gradated hardness is not critical a similar process, but with a broader range of presintering temperatures, about 1475-1575C, may be used, and a 50C difference between the presintering and hot pressing temperatures is not required.
s For certain applications such as cutting -tools the articles described herein may be coated with refractory materials to provide certain desired surface characteristics. The preferred coatings have one or more adherent, compositionally distinct layers of refractory msotal carbides, nitrides, and/or carbonitrides, e.g. of titanium, tantalum, or hafnium, or oxides, e.g. of aluminum or zirconium, or combinations of these materials as different layers and/or solid solutions. Such coatings may be deposited by methods such as chemical vapor deposition (CVD~ or physical vapor deposition (PVD), and preferably to a total thickness of about 0.5-lO ~m. CVD
or PVD techni~ues known in the art to be suitable for coating cemented carbides are preferred for coating the articles described herein.
Coatings of alumina, titanium carbide, titanium nitride, titanium carbonitride, hafnium carbide, hafnium nitride, or hafnium carbonitride are typically applied by CVD. The other coatings described above may be applied either by CVD techniques, where such techniques are applicable, or by PVD techniques. Suitable PVD techniques include but are not limited to direct evaporation and sputtering. ~lternatively, a refractory metal or precursor material may be deposited on the above-described bodies by chemical or physical deposition techniques and subsequently nitrided and/or carburized to produce a refractory metal carbide, carbonitride, or nitride coating. Useul characteristics of the preferred ~VD
method are the purity of the deposited coating and the en~lanced layer adherency often produced by diffusional interaction between the layer being deposited and the substrate or intermediate adherent coating layer during the early stages of the deposition process.
For certain applications, for example cutting tools, combinations of the various coatings described above may be tailored to enhance the overall performance, the 89-3-643 ~9-combination selected depending, for cutting tools, on the machining application and the workpiece material. This is achieved, for example, through selection of coating combinations which improve adherence of coating to substrate and coating to coating, as well as through improvement of microstructurally influenced properties of the substrate body. Such properties include hardness, fracture toughness, impact resistance, and chemical inertness of the substrate body.
The following Examples are presented to enable those skilled in the art to more clearly understand and practice the present invention. These Examples should not be considered as a limitation upon the scope of the present invention, but merely as being illustrative and representative thereof.
EXAMPLES
Cutting tools were prepared from a powder mixture of 10% by volume metal binder (86.7% Ni, 13.3% Al, both by 20 weight, corresponding to a Ni3Al stoichiometric ratio) and 90% by volume hard phase ~either a non-solid solution carbide or boride, or a (W,Ti)C in a 50:50 ratio by weight solid solution W:Ti).
~XAMPLE 1 A charge of 111.52 g of the (W,Ti)C and metal powder mixture, 0.0315 g of carbon, 4.13 g of paraffin, and 150 cc of heptane was milled in a 500 cc capacity tungsten carbide attritor mill using 2000 g of 3.2 mm cemented 30 tungsten carbide ball media for 2~ hr at 120 rpm. After milling, the powder was separated from the milling media by washing with additional heptane through a stainless steel screen. The excess heptane was slowly evaporated.
To prevent binder (wax) inhomogeneity, the thickened slurry was mixed continuously during evaporation, and the caking powder broken up with a plastic spatula into small, '. ~ ! j dry granules. The dry granules were then sieved in two steps using 40~ and 80-mesh screens. The screened powder was then pressed at 138 MPa, producing green co~pacts measuring 16 x 16 x 6.6 mm and containing 50-60% by volume o solids loading.
The pressed compacts were placed in a graphite boat, covered with alumina sand, and placed in a hydrogen furnace at room temperature. The temperature then was raised in increments of 100 every hour and held at 300C
10 for 2 hr to complete the removal of the organic binder.
The dewaxed samples were then taken from the hot zone, cooled to room temperature, and removed from the hydrogen furnace.
The dewaxed samples were then densified in two steps:
presintering and hot isostatic pressing (HIPing). The dewaxed compacts, on graphite plates which had been sprinkled with coarse alumina sand, were presintered at 1650C for 1 hr at about 0.1 Torr in a cold wall graphite vacuum furnace. The initial rise in temperature was 20 rapid, 15C/min up to 800C. From 800C the rise was reduced to 4.5C~min, allowing the sample to outgas.
Throughout the entire presintering cycle, the chamber pressure was maintained at about 0.1 Torr.
The final consolidation was carried out in a HIP unit at 1650C and 207 MPa of argon for 1 hr, using a heating rate of about 10C/min. The maximum temperature (1650C) and pressure (207 MPa) were reached at the same time and were maintained for about 1 hr, followed by oven cooling to room temperature. Cutting tools prepared by this 30 process exhibited improved performance over that of commercially available cutting tools in machining of steel, as shown in FIG. 1. The tools were used in the dry turning of 1045 steel, 600 ft/min, 0.016 in/rev, 0.050 in D.O.C. (depkh of cut). The wear values shown in FIG. 1 are averages of the wear induced at three corners;
29 1 in3 of metal were removed. As may be seen in FIG. 1, the tool of this Example compared avorably in turning performance with commercial tool #1, showing significantly superior notch wear, and was far superior to commercial tool #2. The composition and room temperature hardness of the commercial materials of FIG. 1 and of the tools of this Example are compared in Table 1 below.
The cutting tools of this Example were prepared as de-10 scribed above for Example 1, except that the dewaxedcompacts were presintered at 1500C for 1 hr. at 0.1 Torr in the same cold wall graphite vacuum furnace. The rise in temperature was the same as in Example 1: initially rapid, 15C/min. up to 800C. From 800C, the rise was reduced to 4.5C/min., allowing the sample to outgas.
The metal bonded carbide cutting tool of Example 2 was characterized by a specific microstructure in which a gradient of hardness ~as shown in Table 1) and fracture toughness was developed from the surface of the densified article to its core. The performance of the gradated cutting tool material was measured by machining tests, the results of which are shown in FIG. 2. The impact resistances of the tool of khis Example (with gradated hardness), the kool of Example 1 (without gradated hardness), and two commercial grade tools were determined by a dry flycutter milling test on a steel workpiece (Rockwell hardness, Rc = 24) using a standard milling cutter (available from GTE Valenite Corporation, Troy, MI, U.S.A.) at 750 ft/min, 4.2 in/rev, 0.125 in D.O.C. The wear values shown in FIG. 2 are four corner averages at 341 impacts per corner. The specific cutting tools used in the machining tests are listed in Table 1 with their compositions and room temperature hardness.
As shown in FIG. 2, the tool of this Example was superior in milling performance to both commercial tools.
Further, although the tool of Example 2 was mosk suitable for this application, the tool of Example 1 also proved to have commercial value for such high impact machining.
Hardness*, Hardness*, SampleCompositionKnoop, GPa Vickers, GPa Example(W,Ti)C +15.4 + 0.3 13.8 + 0.3 110 v/o (Ni ~ Al) Example(W,Ti)C +Gradated** -210 v/o (Ni -~ Al)core: 18.10 surface: 20.34 Commer- TiC 14.5 + 0.2 16.53 + 0.16 cial10 Ni + 10 Mo (v/o) Tool #l Commer-10 Co + 10 Ni13.4 + 0.2 cial+ 80 other~ (v/o) Tool #2 * l.ON load.
** 0.5N load.
~ MoC, TiC, TiN, VC, WC (proprietary composition) Cutting tools were prepared as described above for Examples 1 and 2, using the same hard phase/metal phase powder ratio, but were presintered and some of them hot isostatically pressed at the temperatures and for the times shown in Table 2. The rise in temperature was the same as in Example 1: initially rapid, 15C/min. up to 30 800C. From 800C, the rise was reduced to 4.5C/min.
Characterization by X-ray diffraction determined that the compacts evidenced varying amounts of ~' crystal ~tructure Ni7Al formation in their metal phases.
, `, . S,;3 .'., 8 9- 3 - 6 ~ 3 - 13 -Sinter Sinter HIP HIP
Fx.Composition Temp., C Time, hrTemp., C Time, hr -3CW,TI)C +
10 v/o Ni-Al1650 1 1650 4CW, Ti )C ~
10 v/o Ni-Al1550 1 1650 10 5(W,Ti~C ~
10 v/o Ni-Al1650 6(W,Ti)C +
10 v/o Ni-Al1500 1 -- --8g-3-643 -14-EXAMPLES 7-lO
Ceramic-metal cutting tools with a nickel and aluminum metal phase were prepared as described above for Example 1, except that the compositions were as shown in Table 3. Th0 performance of the cubic solid solution (W,Ti)C-based ceramic-metal cutting tools was compared to that of similar tools not containing solid solution carbide in the dry -turnlng of 1045 steel, 475 ft/min, 0.012 in/rev, 0.050 in D.O.C. (depth of cut).
Nose FlanX Crater Metal Ex. Composition Wear, Wear, Wear, Removed, in in in in3 -7 WC ~ Tool 10 v/o Ni-Al -- -- -- failed 8 TiC +
20 10 v/o Ni-Al 0.0090.006<0.001 70 9Mixture WC ~ TiC* +
10 v/o Ni-Al 0.00750.0070.004 64.8 10Solid soln.
(W,Ti)C*
10 v/o Ni-Al 0.0080.0035<0.001 70 * W:Ti = 50:50 by weight.
The wear values shown in Table 3 are averages of the 30 wear induced at three corners during extended cutting tests. The WC-based cermet tool failed before the extended cutting tests were completed. About 65-70 in3 of metal were removed in the remaining tests. As shown in Table 3, the titanium carbide-based cermet tool was superior in extended wear performance to the similar tungsten carbide-based tool (which failed before the extended cutting test was completed), and surpassed the crater wear performance of a similar tool based on a mixture of tungsten carbide and ti-tanium carbide.
The tool of Example 10 was similar in every way to those of Examples 7, 8, and 9, except that it included a cubic solid solution carbide of tungsten and titanium.
The tools of Examples 9 and 10 were actually of an identical chemical composition, both including tungsten lO and titanium in a 50:50 weight ratio. Surprisingly, however, it was found that this solid solution carbide-containing tool outperformed the WC-based tool and even the (TiC + WC)-based tool in the machining tests.
The solid solution carbide-based tool also showed superior flank wear performance and equivalent crater wear performance to the presumably harder TiC-based tool of --Example 8.
The surprising superiority of the cubic solid solution carbide-based tool may be clearly seen in FIGS. 3-6, which 20 are photomicrographs of the wear induced at one corner of each of the tools listed in Table 3 af-ter 20 in3 of metal removal. As illustrated in FIG. 3, the tungsten carbide-based tool exhibits the severe cratering which ultimately led to failure of the tool. FIG. 4 illustrates the severe nose deformation o the titanium carbide-based tool; this tool, however, exhibits essentially no cratering. In FIG. 5 is illustrated the effect of combining the cratering resistance of titanium carbide with the resistance to nose deformation of tungsten 30 carbide in the (WC ~ TiC~-based tool: the tool exhibits little deformation and only slight cratering. The superiority of the tool in accordance with one aspect of the invention, the solid solution carbide-based tool of Example 7 is illustrated in FIG. 6, in which the tool exhibits essentially no cratering and far less deformation and wear than any of the similar tools.
~XAMPLES 11~16 Ceramic-metal compacts were prepared from a powder mixture of 10% by volume metal phase (86.7% Ni, 13.3% Al, both by weight, corresponding to a Ni3Al stoichiometric ratio) and 90% by volume ceramic hard phase.
A charge of 221.28 g of the tungsten carbide and metal powder mixture, 0.0315 g of carbon, 4.13 g of paraffin, and 150 cc of heptane was milled in a 500 cc capacity tungsten carbide attritor mill using 2000 g of 3.2 mm 10 cemented tungsten carbide ball media for 2l~2 hr at 120 rpm.
For the compacts including other hard phase components, the milling process was repeated, using a weight of hard phase powder which would produce an equivalent volume percent.
After milling, each batch of powder was separated ~rom the milling media by washing with additional heptane through a stainless steel screen. The excess heptane was slowly evaporated. To prevent binder ~wax) inhomogeneity, the thickened slurry was mixed continuously during 20 evaporation, and the caking powder broken up with a plastic spatula into small, dry granules. The dry granules were then sieved in two steps using 40- and 80-mesh screens. Each screened powder was then pressed at 138 MPa, producing green compacts measuring 16 ~ 16 x 6.6 mm and containing 50-60% by volume of solids loading.
The pressed compacts were placed in a graphite boat, covered with alumina sand, and placed in a hydrogen furnace at room temperature. The temperature then was 30 raised in increments of 100 every hour and held at 300C
for 2 hr to complete the removal of the organic binder.
The dewaxed samples were then taken from the hot zone, cooled to room temperature, and removed from the hydrogen furnace.
The dewaxed samples were then densified in two steps:
presintering and hot isostatic pressing ~HIPing). The ~g-3-643 -17~
dewaxed compacts, on graphite plates which had been sprinkled with coarse alumina sand, were presintered at 1650C for 1 hr at about 0.1 Torr in a cold wall graphite vacuum furnace. The initial rise in temperature was rapid, 15C/min up to 800C. From 800C the rise was reduced to 4.5C/min. Throughout the entire presintering cycle, the chamber pressure was maintained at about 0.1 Torr.
The final consolidation was carried out in a HIP unit 10 at 1650C and 207 MPa of argon for 1 hr, using a heating rate of about 10C/min. The maximum temperature (1650C) and pressure (207 MPa) were reached at the same time and were maintained for about 1 hr, followed by oven cooling to room temperature. The Knoop hardness at the surface of each densified compact is shown in Table 4 below.
, ..~`..~`.J ~
-Powder Composition, v/oAve. Swrface _ Hardness~, S~mpla Ni+Al~ WCTiC TiB2 VC NbC TaC Knoop, MPa ~ _ _ 11 10 90 - -- -- -- -- 17.D8 12 10 -- 90 -- -- -- -- 17.69 13 10 -- -- 90 -- -- -- 20~50 14 10 -- -- -- 90 -- -- 15.17 1 89 -- -- -- -- 15.43 - 16 10 7~.168.30 -- -- ~.183.36 14.77 CommPrcial 14.5 Tool ~lt Co~mercial 13.4 Tool ~Zt l.ON load.
~ 13.3% by weight Al, balan~e Ni.
20 t See Table 1 for co~positions.
As shown in Table 4, carbide compacts prepared as de-scribed above axhibited improved hardness over that of commercially available cutting tools. Titanium and tungsten titanium carbide compacks prepared as described above exhibited good performance in the dry turning of 1045 steel, 475 ft/min, 0.012 in/rev, 0.050 in D.O.C.
(depth of cut).
Compacts are prepared as described above for Examples 11-16, using the same powders in the starting formulations and the same process, except that the dewaxed compacts are presintered at 1500C for 1 hr. at 0.1 Torr in the same ~9-3-643 -19-cold wall graphite vacuum furnace. The rise in temperature is the same as in Example 1: initially rapid, 15~C/min. up to 800C. From 800C, the rise is reduced to 4.5C/min.
The metal bonded carbide cutting tool of Example 17 is characterized by a specific microstructure in which a gradient of hardness is developed from the surface of the densified article to its core.
The present invention provides novel improved cutting lO tools capable of withstanding the demands of hard steel turning, which requires a high degree of wear resistance, and steel milling, which requires a high degree of impact resistance. It also provides wear parks and other structural parts of high strength and wear resistance.
While there has been shown and described what are at present considered the preferred embodiments of the invention, it will be obvious to those skilled in the art that various changes and modifications can be made therein without departing from the scope of the invention as 20 defined by the appended Claims.
This invention relates to metal bonded ceramic, e.g.
carbide, nitride, and carbonitride, articles for use as cutting tools, wear parts, and the like. In particular the invention relates to such articles bonded with a binder including both nickel and aluminum and methods for producing such articles.
The discovery and implementation of cobalt bonded 10 tungsten carbide (WC-Co) as a tool material for cutting metal greatly extended the range of applications beyond that of conventional tool steels. Over the last 50 years process and compositional modifications to WC-Co materials have led to further benefits in wear resistance, yet the potential of these materials is inherently limited by the physical properti.es of the cobalt binder phase. This becomes evident when cutting speeds are increased to a level which generates sufficient heat to soften the metal binder. The high speed finishing of steel rolls serves as 20 an example of a metal cutting application where the tool insert must maintain its cutting edge geometry at high temperature and resist both wear and deformation.
Unfortunately, the wear characteristics of WC-Co based cemented carbides are also affected by the high temperature chemical interaction at the interface between the ferrous alloy workpiece and the cemented carbide tool surface. Additions of cubic carbides (i.e. TiC) to the WC-Co system have led to some improvement in tool performance during steel machining, due in part to the 30 resulting increased hardness and increased resistance to chemical interaction. However, the performance of such TiC-rich WC-Co alloys is influenced by the low fracture toughness of the TiC phase, which can lead to a tendency toward fracture during machining operations involving intermittent cutting, for example milling.
Accordingly, a cemented carbide material suitable for cutting tools capable of withstanding the demands of hard steel turning (wear resistance) and steel milling (impact resistance) would be of great value. Such a new and improved material is described herein.
According to one aspect of the invention, there is provided a ceramic-metal article comprising: about 80-95%
by volume of a granular hard phase consisting essentially lO of a ceramic material selec-ted from the group consisting of the hard rafractory carbides, nitrides, carbonitrides, oxycarbides, oxynitrides, carboxynitrides, and mixtures thereof of a cubic solid solution selected from the group consisting of zirconium-titanium, hafnium-titanium, hafnium-zirconium, vanadium titanium, niobium-titanium, tantalum-titanium, molybdenum titanium, tungsten-titanium, tungsten-hafnium, tungsten-niobium, and tungsten-tantalum;
and about 5-20% by volume of a metal phase, wherein said metal phase consists essentially of a combination of 20 nickel and aluminum having a ratio of nickel to aluminum of from about 90:10 to about 70:30 by weight and 0-5% by weight of an additive selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, boron, carbon, and combinations thereof; wherein said article has a density of at least about 95% of theoretical.
More specifically we provide an article in accordance wherein said metal phase consists essentially of a Ni3Al 30 ordered crystal structure or of a Ni3Al ordered crystal structure coexistent with or modified by said additive.
According to another aspect of the invention, there is provided a process for producing a ceramic-metal article comprisin~ the steps of: presintering, in a vacuum or inert atmosphere at about 1475-1675C and for a time sufficient to permit developmant of a microstructure with closed porosity, a mixture of about 80-95% by ~011lme of a granular hard phase component consisting essentially of a ceramic material selected from the group consisting of (a) the hard refractory carbides, nitrides, carbonitrides, o~ycarbides, oxynitrides, carboxynitrides, borides, and mixtures thereof of the elements selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, and lO boron, and (b) the hard refractory carbides, nitrides, carbonitrides, oxycarbides, oxynitrides, and carboxy-nitrides, and mixtures thereof of a cubic solid solution selected from the group consisting of zirconium-titanium, hafnium-titanium, hafnium-zirconium, vanadium-titanium, niobium-titanium, tantalum-titanium, molybdenum-titanium, tungsten- titanium, tungsten-hafnium, tungsten-niobium, and tungsten-tantalum; and about 5-20% by volume of a metal phase component, wherein said metal phase component consists essentially of nickel and aluminum, in a ratio of 20 nickel to aluminum of from about 85:15 to about 88:12 by weight, and 0-5% ~y weight of an additive selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, mol~bdenum, tungsten, cobalt, boron, carbon, and combinations thereof;
and densifying said presintered mixture by hot isostatic pressing at a temperature of about 1575-1675C, in an inert atmosphere, and at about 34~207 MPa pressure for a time sufficient to produce an article having a density o at least about 95% of theoretical.
More specifically we provide a process wherein said presintering step is carried out at about 1475-1575C and said presintering step is carried out at a temperature at least 50C lower than that of said densifying step.
Also, more specifically, we provide a process wherein said ratio of nickel to aluminum is selected such that during said densifying step said metal phase component is substantially converted to a Ni3Al ordered crystal structure or a Ni3Al ordered crystal structure coexistent with or modified by said additive.
Some embodiments of the invention will now be described, by way o~ example, with reference to the accompanying drawings in which:
FIG. 1 is a graphical representation comparing the ma-chining performance of a cutting tool shaped article according to one aspect of the invention and commercially available tools;
FIG. 2 is a graphical representation comparing the milling performance of cutting tool shaped articles according to two aspects of the invention and commercially available tools;
FIGS. 3-6 are photomicrographs illustrating wear characteristics of various tools of related compositions, 20 including one tool according- to one aspect of the invention.
Described herein as exemplary ceramic materials are those including one or more hard refractory carbides, nitrides, oxycarbides, oxynitrides, carbonitrides, carboxynitrides, or borides of a tungsten-titanium solid solution, or one or more hard refractory carbides, nitrides, oxycarbides, oxynitrides, carbonitrides, or carboxynitrides of tungsten, bonded by an intermetallic binder combining nickel and aluminum. These exemplary 30 materials are considered typical o~ those claimed, and the following description thereof is not intended to limit the invention as recited in the claims.
A typical densified, metal bonded hard ceramic body or article is prepared from a powder mixture including cubic solid solution powders as the hard phase component, and a combination of both Mi and Al powders in an amount of J
about 5~20yO by volume as the binder component. Typical solid solution powders include (WX,Til~x3C, (WX,Til_x)N, (~x,Til_x)(C,N), (Wx,Til_x)(O,C~, (Wx,Til_x~(O,N), (WX,Til x)(O,C,N), or combinations thereof. Most preferably, x is a weight fraction o about 0.3 0.7. The best combination of properties (hardness and fracture toughness) is obtained when total metal binder addition is in the range of about 7-15% by volume. For best results in sintering and in both physical and chemical property lO balance, the weight ratio in the solid solution hard phase of tungsten to titanium should be in the range of about 0.3-3.0 and more preferably about 0.6-1.5. Materials with a W:Ti ratio lower than about 0.3 exhibit lowered fracture toughnass and impact resistance, which can be important in some applications, e.g. when used as cutting tools for steel milling. A ratio of about 3.0 or less can enhance wear resistance, which can also be important in some applications, e.g. when used as cutting tools for steel turning.
Alternatively, the ceramic materials may typically include compounds of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, boron, or mixtures thereof. Typical of these hard phase components are TiC, HfC, VC, TaC, Mo2C, WC, B4C, TiN, Ti(C,N), TiB2, or WB. The powder mixture contains the hard phase component, for example a tungstan carbide powder, and a combination of both Ni powder and Al powder in an amount of about 5-20% by volume as the metal component. The best combination of properties ~hardness 30 and fracture toughness) is obtained when total metallic phase addition is in the range of about 7-15% by volume.
In this exemplary material, the tungsten carbide ceramic component provides excellent wear resistance, which is important in applications such as cutting tools for steel turning. The metallic phase provides greater fracture toughness for the material than the sintered ceramic ! ~ ?
material alone, and the metallic phase combining aluminum and nickel in the above ratios provides improved high temperature properties such as creep resistance over cobalt or other single metal.
In any of these materials, as stated above, the metal powder component represents about 5-20% by volume and preferably about 7-15% by volume of the total starting formulation. The binder metal powder includes nickel in an amount of about 85-88% by weight, and aluminum in an lO amount of about 12-15% by weight, both relative to the total weight of the binder metal powder. A minor amount of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, boron and/or carbon, not to exceed about 5% by weight of total binder metal, may also be included. The preferred composition is 12-14% by weight Al, balance Ni. In the most preferred binder compositions the Ni:Al ratio results in the formation o~ a substantially Ni3Al binder, having the Ni~Al ordered crystal structure. The amount of Ni3Al 20 is also dependent on the processing, e.g. the processing temperatures, and may be selectecl to achieve various properties in the cermet, e.g. 100%, 40-80%, less than 50%, etc. of the metal phase. The ratio of Ni:Al powders required to achieve the desired amount of Ni3Al may be readily determined by empirical methods. Alternatively, prereacted Ni3Al may be used in the starting formulation.
In some compositions, this ordered crystal structure may coexist or be modified by the above-mentioned additives. The preferred average grain size of the hard 30 phase in a densi~ied body of this material for cutting tool use is about 0.5-5.0 ~m. In other articles for applications where deformation resistance requirements are lower, e.g. sand blasting nozzles, a larger range of grain sizes, e.g. about 0.5-20 ~m, may prove satisfactory. The material may be densified by known methods, for example ,1, . ' I C ~
89-3-~43 -7-sintering, continuous cycle sinterhip, two step sinter-plus-HIP, or hot pressing, all known in the art.
An alternate densified, metal bonded hard ceramic body or article has the same overall composition as those described above, but differs in that it exhibits a gradat~d hardness, most preferably exhibiting lower hardness in the center portion of the body and progressively increasing hardness toward the tool surface.
To obtain a body with these characteristics, the 10 densification process includes a presintering step in which the starting powder mixture is subjected to temperatures of about 1475-1575C, preferably 1475-1550C, in vacuum (e.g. about 0.1 Torr) or in an inert atmosphere (e.g. at about 1 atm) for a time sufficient to develop a microstructure with closed porosity, e.g. about 0.5-2 hr. As used herein, the term "microstructure with closed porosity" is intended to mean a microstructure in which the remaining pores are no longer interconnected. Subsequently, the body is fully 20 densified in an inert atmospheric overpressure of about 34-207 MPa and temperature of about 1575-1675C, preferably 1600-1675C, for a time sufficient to achieve full density, e.g. about 0.5-2 hr. The presintering temperature is at least 50C lower than the ~inal densification temperature. These gradated bodies exhibit outstanding impact resistance, and are particularly useful as milling tool inserts and as tools for interrupted cutting of steel.
The depth to which the gradated hardness is effected 30 is dependent on the presintering temperature. Thus, if a fully gradated hardness is not critical a similar process, but with a broader range of presintering temperatures, about 1475-1575C, may be used, and a 50C difference between the presintering and hot pressing temperatures is not required.
s For certain applications such as cutting -tools the articles described herein may be coated with refractory materials to provide certain desired surface characteristics. The preferred coatings have one or more adherent, compositionally distinct layers of refractory msotal carbides, nitrides, and/or carbonitrides, e.g. of titanium, tantalum, or hafnium, or oxides, e.g. of aluminum or zirconium, or combinations of these materials as different layers and/or solid solutions. Such coatings may be deposited by methods such as chemical vapor deposition (CVD~ or physical vapor deposition (PVD), and preferably to a total thickness of about 0.5-lO ~m. CVD
or PVD techni~ues known in the art to be suitable for coating cemented carbides are preferred for coating the articles described herein.
Coatings of alumina, titanium carbide, titanium nitride, titanium carbonitride, hafnium carbide, hafnium nitride, or hafnium carbonitride are typically applied by CVD. The other coatings described above may be applied either by CVD techniques, where such techniques are applicable, or by PVD techniques. Suitable PVD techniques include but are not limited to direct evaporation and sputtering. ~lternatively, a refractory metal or precursor material may be deposited on the above-described bodies by chemical or physical deposition techniques and subsequently nitrided and/or carburized to produce a refractory metal carbide, carbonitride, or nitride coating. Useul characteristics of the preferred ~VD
method are the purity of the deposited coating and the en~lanced layer adherency often produced by diffusional interaction between the layer being deposited and the substrate or intermediate adherent coating layer during the early stages of the deposition process.
For certain applications, for example cutting tools, combinations of the various coatings described above may be tailored to enhance the overall performance, the 89-3-643 ~9-combination selected depending, for cutting tools, on the machining application and the workpiece material. This is achieved, for example, through selection of coating combinations which improve adherence of coating to substrate and coating to coating, as well as through improvement of microstructurally influenced properties of the substrate body. Such properties include hardness, fracture toughness, impact resistance, and chemical inertness of the substrate body.
The following Examples are presented to enable those skilled in the art to more clearly understand and practice the present invention. These Examples should not be considered as a limitation upon the scope of the present invention, but merely as being illustrative and representative thereof.
EXAMPLES
Cutting tools were prepared from a powder mixture of 10% by volume metal binder (86.7% Ni, 13.3% Al, both by 20 weight, corresponding to a Ni3Al stoichiometric ratio) and 90% by volume hard phase ~either a non-solid solution carbide or boride, or a (W,Ti)C in a 50:50 ratio by weight solid solution W:Ti).
~XAMPLE 1 A charge of 111.52 g of the (W,Ti)C and metal powder mixture, 0.0315 g of carbon, 4.13 g of paraffin, and 150 cc of heptane was milled in a 500 cc capacity tungsten carbide attritor mill using 2000 g of 3.2 mm cemented 30 tungsten carbide ball media for 2~ hr at 120 rpm. After milling, the powder was separated from the milling media by washing with additional heptane through a stainless steel screen. The excess heptane was slowly evaporated.
To prevent binder (wax) inhomogeneity, the thickened slurry was mixed continuously during evaporation, and the caking powder broken up with a plastic spatula into small, '. ~ ! j dry granules. The dry granules were then sieved in two steps using 40~ and 80-mesh screens. The screened powder was then pressed at 138 MPa, producing green co~pacts measuring 16 x 16 x 6.6 mm and containing 50-60% by volume o solids loading.
The pressed compacts were placed in a graphite boat, covered with alumina sand, and placed in a hydrogen furnace at room temperature. The temperature then was raised in increments of 100 every hour and held at 300C
10 for 2 hr to complete the removal of the organic binder.
The dewaxed samples were then taken from the hot zone, cooled to room temperature, and removed from the hydrogen furnace.
The dewaxed samples were then densified in two steps:
presintering and hot isostatic pressing (HIPing). The dewaxed compacts, on graphite plates which had been sprinkled with coarse alumina sand, were presintered at 1650C for 1 hr at about 0.1 Torr in a cold wall graphite vacuum furnace. The initial rise in temperature was 20 rapid, 15C/min up to 800C. From 800C the rise was reduced to 4.5C~min, allowing the sample to outgas.
Throughout the entire presintering cycle, the chamber pressure was maintained at about 0.1 Torr.
The final consolidation was carried out in a HIP unit at 1650C and 207 MPa of argon for 1 hr, using a heating rate of about 10C/min. The maximum temperature (1650C) and pressure (207 MPa) were reached at the same time and were maintained for about 1 hr, followed by oven cooling to room temperature. Cutting tools prepared by this 30 process exhibited improved performance over that of commercially available cutting tools in machining of steel, as shown in FIG. 1. The tools were used in the dry turning of 1045 steel, 600 ft/min, 0.016 in/rev, 0.050 in D.O.C. (depkh of cut). The wear values shown in FIG. 1 are averages of the wear induced at three corners;
29 1 in3 of metal were removed. As may be seen in FIG. 1, the tool of this Example compared avorably in turning performance with commercial tool #1, showing significantly superior notch wear, and was far superior to commercial tool #2. The composition and room temperature hardness of the commercial materials of FIG. 1 and of the tools of this Example are compared in Table 1 below.
The cutting tools of this Example were prepared as de-10 scribed above for Example 1, except that the dewaxedcompacts were presintered at 1500C for 1 hr. at 0.1 Torr in the same cold wall graphite vacuum furnace. The rise in temperature was the same as in Example 1: initially rapid, 15C/min. up to 800C. From 800C, the rise was reduced to 4.5C/min., allowing the sample to outgas.
The metal bonded carbide cutting tool of Example 2 was characterized by a specific microstructure in which a gradient of hardness ~as shown in Table 1) and fracture toughness was developed from the surface of the densified article to its core. The performance of the gradated cutting tool material was measured by machining tests, the results of which are shown in FIG. 2. The impact resistances of the tool of khis Example (with gradated hardness), the kool of Example 1 (without gradated hardness), and two commercial grade tools were determined by a dry flycutter milling test on a steel workpiece (Rockwell hardness, Rc = 24) using a standard milling cutter (available from GTE Valenite Corporation, Troy, MI, U.S.A.) at 750 ft/min, 4.2 in/rev, 0.125 in D.O.C. The wear values shown in FIG. 2 are four corner averages at 341 impacts per corner. The specific cutting tools used in the machining tests are listed in Table 1 with their compositions and room temperature hardness.
As shown in FIG. 2, the tool of this Example was superior in milling performance to both commercial tools.
Further, although the tool of Example 2 was mosk suitable for this application, the tool of Example 1 also proved to have commercial value for such high impact machining.
Hardness*, Hardness*, SampleCompositionKnoop, GPa Vickers, GPa Example(W,Ti)C +15.4 + 0.3 13.8 + 0.3 110 v/o (Ni ~ Al) Example(W,Ti)C +Gradated** -210 v/o (Ni -~ Al)core: 18.10 surface: 20.34 Commer- TiC 14.5 + 0.2 16.53 + 0.16 cial10 Ni + 10 Mo (v/o) Tool #l Commer-10 Co + 10 Ni13.4 + 0.2 cial+ 80 other~ (v/o) Tool #2 * l.ON load.
** 0.5N load.
~ MoC, TiC, TiN, VC, WC (proprietary composition) Cutting tools were prepared as described above for Examples 1 and 2, using the same hard phase/metal phase powder ratio, but were presintered and some of them hot isostatically pressed at the temperatures and for the times shown in Table 2. The rise in temperature was the same as in Example 1: initially rapid, 15C/min. up to 30 800C. From 800C, the rise was reduced to 4.5C/min.
Characterization by X-ray diffraction determined that the compacts evidenced varying amounts of ~' crystal ~tructure Ni7Al formation in their metal phases.
, `, . S,;3 .'., 8 9- 3 - 6 ~ 3 - 13 -Sinter Sinter HIP HIP
Fx.Composition Temp., C Time, hrTemp., C Time, hr -3CW,TI)C +
10 v/o Ni-Al1650 1 1650 4CW, Ti )C ~
10 v/o Ni-Al1550 1 1650 10 5(W,Ti~C ~
10 v/o Ni-Al1650 6(W,Ti)C +
10 v/o Ni-Al1500 1 -- --8g-3-643 -14-EXAMPLES 7-lO
Ceramic-metal cutting tools with a nickel and aluminum metal phase were prepared as described above for Example 1, except that the compositions were as shown in Table 3. Th0 performance of the cubic solid solution (W,Ti)C-based ceramic-metal cutting tools was compared to that of similar tools not containing solid solution carbide in the dry -turnlng of 1045 steel, 475 ft/min, 0.012 in/rev, 0.050 in D.O.C. (depth of cut).
Nose FlanX Crater Metal Ex. Composition Wear, Wear, Wear, Removed, in in in in3 -7 WC ~ Tool 10 v/o Ni-Al -- -- -- failed 8 TiC +
20 10 v/o Ni-Al 0.0090.006<0.001 70 9Mixture WC ~ TiC* +
10 v/o Ni-Al 0.00750.0070.004 64.8 10Solid soln.
(W,Ti)C*
10 v/o Ni-Al 0.0080.0035<0.001 70 * W:Ti = 50:50 by weight.
The wear values shown in Table 3 are averages of the 30 wear induced at three corners during extended cutting tests. The WC-based cermet tool failed before the extended cutting tests were completed. About 65-70 in3 of metal were removed in the remaining tests. As shown in Table 3, the titanium carbide-based cermet tool was superior in extended wear performance to the similar tungsten carbide-based tool (which failed before the extended cutting test was completed), and surpassed the crater wear performance of a similar tool based on a mixture of tungsten carbide and ti-tanium carbide.
The tool of Example 10 was similar in every way to those of Examples 7, 8, and 9, except that it included a cubic solid solution carbide of tungsten and titanium.
The tools of Examples 9 and 10 were actually of an identical chemical composition, both including tungsten lO and titanium in a 50:50 weight ratio. Surprisingly, however, it was found that this solid solution carbide-containing tool outperformed the WC-based tool and even the (TiC + WC)-based tool in the machining tests.
The solid solution carbide-based tool also showed superior flank wear performance and equivalent crater wear performance to the presumably harder TiC-based tool of --Example 8.
The surprising superiority of the cubic solid solution carbide-based tool may be clearly seen in FIGS. 3-6, which 20 are photomicrographs of the wear induced at one corner of each of the tools listed in Table 3 af-ter 20 in3 of metal removal. As illustrated in FIG. 3, the tungsten carbide-based tool exhibits the severe cratering which ultimately led to failure of the tool. FIG. 4 illustrates the severe nose deformation o the titanium carbide-based tool; this tool, however, exhibits essentially no cratering. In FIG. 5 is illustrated the effect of combining the cratering resistance of titanium carbide with the resistance to nose deformation of tungsten 30 carbide in the (WC ~ TiC~-based tool: the tool exhibits little deformation and only slight cratering. The superiority of the tool in accordance with one aspect of the invention, the solid solution carbide-based tool of Example 7 is illustrated in FIG. 6, in which the tool exhibits essentially no cratering and far less deformation and wear than any of the similar tools.
~XAMPLES 11~16 Ceramic-metal compacts were prepared from a powder mixture of 10% by volume metal phase (86.7% Ni, 13.3% Al, both by weight, corresponding to a Ni3Al stoichiometric ratio) and 90% by volume ceramic hard phase.
A charge of 221.28 g of the tungsten carbide and metal powder mixture, 0.0315 g of carbon, 4.13 g of paraffin, and 150 cc of heptane was milled in a 500 cc capacity tungsten carbide attritor mill using 2000 g of 3.2 mm 10 cemented tungsten carbide ball media for 2l~2 hr at 120 rpm.
For the compacts including other hard phase components, the milling process was repeated, using a weight of hard phase powder which would produce an equivalent volume percent.
After milling, each batch of powder was separated ~rom the milling media by washing with additional heptane through a stainless steel screen. The excess heptane was slowly evaporated. To prevent binder ~wax) inhomogeneity, the thickened slurry was mixed continuously during 20 evaporation, and the caking powder broken up with a plastic spatula into small, dry granules. The dry granules were then sieved in two steps using 40- and 80-mesh screens. Each screened powder was then pressed at 138 MPa, producing green compacts measuring 16 ~ 16 x 6.6 mm and containing 50-60% by volume of solids loading.
The pressed compacts were placed in a graphite boat, covered with alumina sand, and placed in a hydrogen furnace at room temperature. The temperature then was 30 raised in increments of 100 every hour and held at 300C
for 2 hr to complete the removal of the organic binder.
The dewaxed samples were then taken from the hot zone, cooled to room temperature, and removed from the hydrogen furnace.
The dewaxed samples were then densified in two steps:
presintering and hot isostatic pressing ~HIPing). The ~g-3-643 -17~
dewaxed compacts, on graphite plates which had been sprinkled with coarse alumina sand, were presintered at 1650C for 1 hr at about 0.1 Torr in a cold wall graphite vacuum furnace. The initial rise in temperature was rapid, 15C/min up to 800C. From 800C the rise was reduced to 4.5C/min. Throughout the entire presintering cycle, the chamber pressure was maintained at about 0.1 Torr.
The final consolidation was carried out in a HIP unit 10 at 1650C and 207 MPa of argon for 1 hr, using a heating rate of about 10C/min. The maximum temperature (1650C) and pressure (207 MPa) were reached at the same time and were maintained for about 1 hr, followed by oven cooling to room temperature. The Knoop hardness at the surface of each densified compact is shown in Table 4 below.
, ..~`..~`.J ~
-Powder Composition, v/oAve. Swrface _ Hardness~, S~mpla Ni+Al~ WCTiC TiB2 VC NbC TaC Knoop, MPa ~ _ _ 11 10 90 - -- -- -- -- 17.D8 12 10 -- 90 -- -- -- -- 17.69 13 10 -- -- 90 -- -- -- 20~50 14 10 -- -- -- 90 -- -- 15.17 1 89 -- -- -- -- 15.43 - 16 10 7~.168.30 -- -- ~.183.36 14.77 CommPrcial 14.5 Tool ~lt Co~mercial 13.4 Tool ~Zt l.ON load.
~ 13.3% by weight Al, balan~e Ni.
20 t See Table 1 for co~positions.
As shown in Table 4, carbide compacts prepared as de-scribed above axhibited improved hardness over that of commercially available cutting tools. Titanium and tungsten titanium carbide compacks prepared as described above exhibited good performance in the dry turning of 1045 steel, 475 ft/min, 0.012 in/rev, 0.050 in D.O.C.
(depth of cut).
Compacts are prepared as described above for Examples 11-16, using the same powders in the starting formulations and the same process, except that the dewaxed compacts are presintered at 1500C for 1 hr. at 0.1 Torr in the same ~9-3-643 -19-cold wall graphite vacuum furnace. The rise in temperature is the same as in Example 1: initially rapid, 15~C/min. up to 800C. From 800C, the rise is reduced to 4.5C/min.
The metal bonded carbide cutting tool of Example 17 is characterized by a specific microstructure in which a gradient of hardness is developed from the surface of the densified article to its core.
The present invention provides novel improved cutting lO tools capable of withstanding the demands of hard steel turning, which requires a high degree of wear resistance, and steel milling, which requires a high degree of impact resistance. It also provides wear parks and other structural parts of high strength and wear resistance.
While there has been shown and described what are at present considered the preferred embodiments of the invention, it will be obvious to those skilled in the art that various changes and modifications can be made therein without departing from the scope of the invention as 20 defined by the appended Claims.
Claims (16)
1. A ceramic-metal article comprising:
about 80 95% by volume of a granular hard phase con-sisting essentially of a ceramic material selected from the group consisting of the hard refractory carbides, nitrides, carbonitrides, oxycarbides, oxynitrides, carboxynitrides, and mixtures thereof of a cubic solid solution selected from the group consisting of zirconium-titanium, hafnium-titanium, hafnium-zirconium, vanadium-titanium, niobium-titanium, tantalum-titanium, molybdenum-titanium, tungsten-titanium, tungsten-hafnium, tungsten-niobium, and tungsten-tantalum; and about 5-20% by volume of a metal phase, wherein said metal phase consists essentially of a combination of nickel and aluminum having a ratio of nickel to aluminum of from about 90:10 to about 70:30 by weight and 0-5% by weight of an additive selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, boron, carbon, and combinations thereof;
wherein said article has a density of at least about 95% of theoretical.
about 80 95% by volume of a granular hard phase con-sisting essentially of a ceramic material selected from the group consisting of the hard refractory carbides, nitrides, carbonitrides, oxycarbides, oxynitrides, carboxynitrides, and mixtures thereof of a cubic solid solution selected from the group consisting of zirconium-titanium, hafnium-titanium, hafnium-zirconium, vanadium-titanium, niobium-titanium, tantalum-titanium, molybdenum-titanium, tungsten-titanium, tungsten-hafnium, tungsten-niobium, and tungsten-tantalum; and about 5-20% by volume of a metal phase, wherein said metal phase consists essentially of a combination of nickel and aluminum having a ratio of nickel to aluminum of from about 90:10 to about 70:30 by weight and 0-5% by weight of an additive selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, boron, carbon, and combinations thereof;
wherein said article has a density of at least about 95% of theoretical.
2. An article in accordance with claim 1 wherein said metal phase consists essentially of a Ni3Al ordered crystal structure or of a Ni3Al ordered crystal structure coexistent with or modified by said additive.
3. An article in accordance with claim 1 wherein said article is coated with one or more adherent, compositionally distinct layers, each layer being a carbide, nitride or carbonitride of titanium, tantalum or hafnium, an oxide of aluminum or zirconium, or a mixture or solid solution of these.
4. An article in accordance with claim 1 wherein said hard phase consists essentially of a cubic solid solution tungsten titanium carbide.
5. An article in accordance with claim 4 wherein the weight ratio of tungsten to titanium in said hard phase is about 1:3 to about 3:1.
6. A ceramic-metal article comprising:
about 80 95% by volume of a granular hard phase con-sisting essentially of a ceramic material selected from the group consisting of (a) the hard refractory carbides, nitrides, carbonitrides, oxycarbides, oxynitrides, carboxynitrides, borides, and mixtures thereof of an element selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, molybdenum, tungsten, and boron, and (b) the hard refractory carbides, nitrides, carbonitrides, oxycarbides, oxynitrides, carboxy-nitrides, and mixtures thereof of a cubic solid solution selected from the group consisting of zirconium-titanium, hafnium-titanium, hafnium-zirconium, vanadium-titanium, niobium-titanium, tantalum-titanium, molybdenum-titanium, tungsten-titanium, tungsten-hafnium, tungsten-niobium, and tungsten-tantalum; and about 5-20% by volume of a metal phase, wherein said metal phase consists essentially of a combination of nickel and aluminum having a ratio of nickel to aluminum of from about 90:10 to about 70:30 by weight and 0-5% by weight of an additive selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, boron, or carbon, or combinations thereof;
wherein said article has a hardness gradated from a greater hardness at its surface to a lesser hardness at its core and a density of at least about 95% of theoretical.
about 80 95% by volume of a granular hard phase con-sisting essentially of a ceramic material selected from the group consisting of (a) the hard refractory carbides, nitrides, carbonitrides, oxycarbides, oxynitrides, carboxynitrides, borides, and mixtures thereof of an element selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, molybdenum, tungsten, and boron, and (b) the hard refractory carbides, nitrides, carbonitrides, oxycarbides, oxynitrides, carboxy-nitrides, and mixtures thereof of a cubic solid solution selected from the group consisting of zirconium-titanium, hafnium-titanium, hafnium-zirconium, vanadium-titanium, niobium-titanium, tantalum-titanium, molybdenum-titanium, tungsten-titanium, tungsten-hafnium, tungsten-niobium, and tungsten-tantalum; and about 5-20% by volume of a metal phase, wherein said metal phase consists essentially of a combination of nickel and aluminum having a ratio of nickel to aluminum of from about 90:10 to about 70:30 by weight and 0-5% by weight of an additive selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, boron, or carbon, or combinations thereof;
wherein said article has a hardness gradated from a greater hardness at its surface to a lesser hardness at its core and a density of at least about 95% of theoretical.
7. An article in accordance with claim 6 wherein said metal phase comprises a Ni3Al ordered crystal structure or a Ni3Al ordered crystal structure coexistent with or modified by said additive, in an amount of about 15-80% by volume of said metal phase.
8. An article in accordance with claim 6 wherein said article is coated with one or more adherent, compositionally distinct layers, each layer being a carbide, nitride or carbonitride of titanium, tantalum or hafnium, an oxide of aluminum or zirconium, or a mixture or solid solution of these.
9. An article in accordance with claim 6 wherein said hard phase consists essentially of a cubic solid solution tungsten titanium carbide.
10. An article in accordance with claim 9 wherein the weight ratio of tungsten to titanium in said hard phase is about 1:3 to about 3:1.
11. A process for producing a ceramic-metal article comprising the steps of:
presintering, in a vacuum or inert atmosphere at about 1475°-1675°C and for a time sufficient to permit development of a microstructure with closed porosity, a mixture of about 80-95% by volume of a granular hard phase component consisting essentially of a ceramic material selected from the group consisting of (a) the hard refractory carbides, nitrides, carbonitrides, oxycarbides, oxynitrides, carboxynitrides, borides, and mixtures thereof of the elements selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, and boron, and (b) the hard refractory carbides, nitrides, carbonitrides, oxycarbides, oxynitrides, and carboxynitrides, and mixtures thereof of a cubic solid solution selected from the group consisting of zirconium-titanium, hafnium-titanium, hafnium-zirconium, vanadium-titanium, niobium titanium, tantalum-titanium, molybdenum-titanium, tungsten- titanium, tungsten-hafnium, tungsten-niobium, and tungsten-tantalum; and about 5-20% by volume of a metal phase component, wherein said metal phase component consists essentially of niekel and aluminum, in a ratio of nickel to aluminum of from about 85:15 to about 88:12 by weight, and 0-5% by weight of an additive selected from the group con-sisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, boron, carbon, and combinations thereof;
and densifying said presintered mixture by hot isostatic pressing at a temperature of about 1575°-1675°C, in an inert atmosph.ere, and at about 34-207 MPa pressure for a time sufficient to produce an article having a density of at least about 95% of theoretical.
presintering, in a vacuum or inert atmosphere at about 1475°-1675°C and for a time sufficient to permit development of a microstructure with closed porosity, a mixture of about 80-95% by volume of a granular hard phase component consisting essentially of a ceramic material selected from the group consisting of (a) the hard refractory carbides, nitrides, carbonitrides, oxycarbides, oxynitrides, carboxynitrides, borides, and mixtures thereof of the elements selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, and boron, and (b) the hard refractory carbides, nitrides, carbonitrides, oxycarbides, oxynitrides, and carboxynitrides, and mixtures thereof of a cubic solid solution selected from the group consisting of zirconium-titanium, hafnium-titanium, hafnium-zirconium, vanadium-titanium, niobium titanium, tantalum-titanium, molybdenum-titanium, tungsten- titanium, tungsten-hafnium, tungsten-niobium, and tungsten-tantalum; and about 5-20% by volume of a metal phase component, wherein said metal phase component consists essentially of niekel and aluminum, in a ratio of nickel to aluminum of from about 85:15 to about 88:12 by weight, and 0-5% by weight of an additive selected from the group con-sisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, boron, carbon, and combinations thereof;
and densifying said presintered mixture by hot isostatic pressing at a temperature of about 1575°-1675°C, in an inert atmosph.ere, and at about 34-207 MPa pressure for a time sufficient to produce an article having a density of at least about 95% of theoretical.
12. A process in accordance with claim 11 wherein said presintering step is carried out at about 1475°-1575°C and said presintering step is carried out at a temperature at least 50°C lower than that of said densifying step.
13. A process in accordance with claim 11 wherein said ratio of nickel to aluminum is selected such that during said densifying step said metal phase component is substantially converted to a Ni3Al ordered crystal structure or a Ni3Al ordered crystal structure coexistent with or modified by said additive.
14. A process in accordance with claim 11 wherein the hard phase component consists essentially of a ceramic material selected from the group consisting of the carbides, nitrides, carbonitrides, oxycarbides, oxynitrides, and carboxynitrides of a cubic solid solution of tungsten and titanium.
15. A process in accordance with claim 14 wherein the ratio of tungsten to titanium in said hard phase component is about 1:3 to about 3:1.
16. Each and every novel feature or novel combination of features herein disclosed.
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
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US57624190A | 1990-08-31 | 1990-08-31 | |
US07/576,241 | 1990-08-31 | ||
US07/632,238 | 1990-12-20 | ||
US07/632,237 US5053074A (en) | 1990-08-31 | 1990-12-20 | Ceramic-metal articles |
US07/632,237 | 1990-12-20 | ||
US07/632,238 US5089047A (en) | 1990-08-31 | 1990-12-20 | Ceramic-metal articles and methods of manufacture |
US07/635,408 US5041261A (en) | 1990-08-31 | 1990-12-21 | Method for manufacturing ceramic-metal articles |
US07/635,408 | 1990-12-21 |
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CA002049636A Abandoned CA2049636A1 (en) | 1990-08-31 | 1991-08-21 | Ceramic-metal articles and methods of manufacture |
Country Status (3)
Country | Link |
---|---|
EP (2) | EP0476346A1 (en) |
JP (1) | JPH04297544A (en) |
CA (1) | CA2049636A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113118435A (en) * | 2021-04-23 | 2021-07-16 | 中国科学院金属研究所 | TiB-containing for 3D printing2TiC Al-Zn-Mg-Cu alloy powder and its preparing process |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4340652C2 (en) * | 1993-11-30 | 2003-10-16 | Widia Gmbh | Composite and process for its manufacture |
JP4105410B2 (en) * | 2001-07-03 | 2008-06-25 | 本田技研工業株式会社 | Multi-component carbonitride powder, method for producing the same, and sintered body using the same |
US7175686B2 (en) * | 2003-05-20 | 2007-02-13 | Exxonmobil Research And Engineering Company | Erosion-corrosion resistant nitride cermets |
JP4951958B2 (en) * | 2005-12-21 | 2012-06-13 | 株式会社タンガロイ | Cermet for cutting tools |
GB201209482D0 (en) * | 2012-05-29 | 2012-07-11 | Element Six Gmbh | Polycrystalline material,bodies comprising same,tools comprising same and method for making same |
CN104561726B (en) * | 2014-12-30 | 2016-11-02 | 广东工业大学 | A kind of high tenacity magnalium boron pottery and preparation method thereof |
CN106498208B (en) * | 2016-10-28 | 2017-11-07 | 成都理工大学 | Ni in Binder Phase3The generated in-situ cermet material preparation methods of Al |
CN106636835B (en) * | 2016-10-28 | 2018-05-22 | 成都理工大学 | A kind of preparation method of the hard alloy of the Binder Phase containing intermetallic compound |
CN106521207B (en) * | 2016-10-28 | 2017-11-14 | 成都理工大学 | A kind of preparation method of the hard alloy of high temperature resistance softening |
CN106498207B (en) * | 2016-10-28 | 2017-10-27 | 成都理工大学 | In-situ preparation contains Ni3The preparation method of the cermet of Al Binder Phase |
CN106636832B (en) * | 2016-10-28 | 2018-05-22 | 成都理工大学 | A kind of preparation method of the cermet material of the Binder Phase containing intermetallic compound |
CN106498257B (en) * | 2016-10-28 | 2017-10-27 | 成都理工大学 | In-situ preparation contains Ni3The preparation method of the hard alloy of Al Binder Phase |
CN106521206B (en) * | 2016-10-28 | 2017-11-14 | 成都理工大学 | A kind of preparation method of the cermet material of high temperature resistance softening |
CN113929463B (en) * | 2021-10-15 | 2022-08-16 | 哈尔滨理工大学 | Method for preparing titanium secondary group carbonitride solid solution multiphase ceramic material by sintering method |
CN116214664B (en) * | 2022-12-19 | 2023-12-08 | 有研(广东)新材料技术研究院 | Deep cavity welding wedge-shaped riving knife material and preparation method thereof |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5618068B2 (en) * | 1973-04-11 | 1981-04-25 | ||
DE3264742D1 (en) * | 1981-04-06 | 1985-08-22 | Mitsubishi Metal Corp | Tungsten carbide-base hard alloy for hot-working apparatus members |
US4919718A (en) * | 1988-01-22 | 1990-04-24 | The Dow Chemical Company | Ductile Ni3 Al alloys as bonding agents for ceramic materials |
JPH0271906A (en) * | 1988-09-06 | 1990-03-12 | Mitsubishi Metal Corp | Surface coated tungsten carbide base sintered hard alloy made cutting tool excellent in plastic deformation resistance |
-
1991
- 1991-08-21 CA CA002049636A patent/CA2049636A1/en not_active Abandoned
- 1991-08-22 EP EP91114098A patent/EP0476346A1/en not_active Withdrawn
- 1991-08-22 EP EP95116982A patent/EP0711844A1/en not_active Withdrawn
- 1991-08-30 JP JP3244276A patent/JPH04297544A/en not_active Withdrawn
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113118435A (en) * | 2021-04-23 | 2021-07-16 | 中国科学院金属研究所 | TiB-containing for 3D printing2TiC Al-Zn-Mg-Cu alloy powder and its preparing process |
Also Published As
Publication number | Publication date |
---|---|
JPH04297544A (en) | 1992-10-21 |
EP0711844A1 (en) | 1996-05-15 |
EP0476346A1 (en) | 1992-03-25 |
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