US20080257107A1 - Compositions of Hardmetal Materials with Novel Binders - Google Patents
Compositions of Hardmetal Materials with Novel Binders Download PDFInfo
- Publication number
- US20080257107A1 US20080257107A1 US12/099,737 US9973708A US2008257107A1 US 20080257107 A1 US20080257107 A1 US 20080257107A1 US 9973708 A US9973708 A US 9973708A US 2008257107 A1 US2008257107 A1 US 2008257107A1
- Authority
- US
- United States
- Prior art keywords
- binder
- hardmetals
- hardmetal
- based superalloy
- wax
- 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
- 239000011230 binding agent Substances 0.000 title claims abstract description 166
- 239000000463 material Substances 0.000 title claims abstract description 141
- 239000000203 mixture Substances 0.000 title abstract description 115
- 229910000601 superalloy Inorganic materials 0.000 claims abstract description 89
- 239000011159 matrix material Substances 0.000 claims abstract description 59
- 239000002245 particle Substances 0.000 claims abstract description 50
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 145
- 229910052759 nickel Inorganic materials 0.000 claims description 43
- 229910003178 Mo2C Inorganic materials 0.000 claims description 10
- 150000004767 nitrides Chemical class 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 229910021332 silicide Inorganic materials 0.000 claims description 4
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims description 3
- 229910033181 TiB2 Inorganic materials 0.000 claims description 3
- -1 VB2 Inorganic materials 0.000 claims description 3
- 229910007948 ZrB2 Inorganic materials 0.000 claims description 3
- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 claims description 3
- 229910003862 HfB2 Inorganic materials 0.000 claims description 2
- 229910015173 MoB2 Inorganic materials 0.000 claims description 2
- 229910020968 MoSi2 Inorganic materials 0.000 claims description 2
- 229910020044 NbSi2 Inorganic materials 0.000 claims description 2
- 229910004533 TaB2 Inorganic materials 0.000 claims description 2
- 229910004217 TaSi2 Inorganic materials 0.000 claims description 2
- 229910008814 WSi2 Inorganic materials 0.000 claims description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims 2
- 238000005245 sintering Methods 0.000 abstract description 51
- 238000000034 method Methods 0.000 abstract description 42
- 229910052702 rhenium Inorganic materials 0.000 abstract description 40
- 230000008569 process Effects 0.000 abstract description 36
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 abstract description 24
- 238000004519 manufacturing process Methods 0.000 description 21
- 150000001247 metal acetylides Chemical class 0.000 description 19
- 238000001513 hot isostatic pressing Methods 0.000 description 17
- 229910045601 alloy Inorganic materials 0.000 description 14
- 239000000956 alloy Substances 0.000 description 14
- 238000002844 melting Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- 238000005520 cutting process Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 229910017052 cobalt Inorganic materials 0.000 description 11
- 239000010941 cobalt Substances 0.000 description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 229910052750 molybdenum Inorganic materials 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 230000008901 benefit Effects 0.000 description 8
- 239000011651 chromium Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 239000011195 cermet Substances 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 239000007790 solid phase Substances 0.000 description 7
- 239000006104 solid solution Substances 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910000531 Co alloy Inorganic materials 0.000 description 5
- 238000005553 drilling Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000005496 eutectics Effects 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 238000005728 strengthening Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 101000959719 Rattus norvegicus AP-3 complex subunit mu-1 Proteins 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- 102200044494 rs28903098 Human genes 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 102220467760 Peroxisome proliferator-activated receptor gamma_P40A_mutation Human genes 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 102220007445 rs202088921 Human genes 0.000 description 3
- 102220029434 rs76346220 Human genes 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 238000006037 Brook Silaketone rearrangement reaction Methods 0.000 description 2
- 102220505519 Class E basic helix-loop-helix protein 40_P56A_mutation Human genes 0.000 description 2
- 101800000828 RNA-directed RNA polymerase 3D-POL Proteins 0.000 description 2
- 229910000691 Re alloy Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 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 2
- 238000001238 wet grinding Methods 0.000 description 2
- 238000005491 wire drawing Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 206010010144 Completed suicide Diseases 0.000 description 1
- 229910020706 Co—Re Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910020015 Nb W Inorganic materials 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910009043 WC-Co Inorganic materials 0.000 description 1
- WGQYCBTWBQPWIC-UHFFFAOYSA-N [Re].[Co].[Ni] Chemical compound [Re].[Co].[Ni] WGQYCBTWBQPWIC-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 102220073915 rs144744634 Human genes 0.000 description 1
- 102200160254 rs544215765 Human genes 0.000 description 1
- 102220041804 rs550499593 Human genes 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
-
- 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
-
- 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
- B22F3/16—Both compacting and sintering in successive or repeated steps
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- 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
-
- 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
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
-
- 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
- C22C29/16—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on nitrides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
-
- 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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Definitions
- This application relates to hardmetal compositions, their fabrication techniques, and associated applications.
- Hardmetals include various composite materials and are specially designed to be hard and refractory, and exhibit strong resistance to wear. Examples of widely-used hardmetals include sintered or cemented carbides or carbonitrides, or a combination of such materials. Some hardmetals, called cermets, have compositions that may include processed ceramic particles (e.g., TiC) bonded with binder metal particles. Certain compositions of hardmetals have been documented in the technical literature. For example, a comprehensive compilation of hardmetal compositions is published in Brookes' World Dictionary and Handbook of Hardmetals, sixth edition, International Carbide Data, United Kingdom (1996).
- Hardmetals may be used in a variety of applications. Exemplary applications include cutting tools for cutting metals, stones, and other hard materials, wire-drawing dies, knives, mining tools for cutting coals and various ores and rocks, and drilling tools for oil and other drilling applications. In addition, such hardmetals also may be used to construct housing and exterior surfaces or layers for various devices to meet specific needs of the operations of the devices or the environmental conditions under which the devices operate.
- hardmetals may be formed by first dispersing hard, refractory particles of carbides or carbonitrides in a binder matrix and then pressing and sintering the mixture. The sintering process allows the binder matrix to bind the particles and to condense the mixture to form the resulting hardmetals.
- the hard particles primarily contribute to the hard and refractory properties of the resulting hardmetals.
- the hardmetal materials described below include materials comprising hard particles having a first material, and a binder matrix having a second, different material.
- the hard particles are spatially dispersed in the binder matrix in a substantially uniform manner.
- the first material for the hard particles may include, for example, materials based on tungsten carbide, materials based on titanium carbide, and materials based on a mixture of tungsten carbide and titanium carbide.
- the second material for the binder matrix may include, among others, rhenium, a mixture of rhenium and cobalt, a nickel-based superalloy, a mixture of a nickel-based superalloy and rhenium, a mixture of a nickel-based superalloy, rhenium and cobalt, and these materials mixed with other materials.
- the nickel-based superalloy may be in the ⁇ - ⁇ ′ metallurgic phase.
- the volume of the second material may be from about 3% to about 40% of a total volume of the material.
- the binder matrix may comprise rhenium in an amount at or greater than 25% of a total weight of the binder matrix in the material.
- the second material may include a Ni-based superalloy.
- the Ni-based superalloy may include Ni and other elements such as Re for certain applications.
- Fabrication of the hardmetal materials of this application may be carried out by, according to one implementation, sintering the material mixture under a vacuum condition and performing a solid-phase sintering under a pressure applied through a gas medium.
- Advantages arising from these hardmetal materials and composition methods may include one or more of the following: superior hardness in general, enhanced hardness at high temperatures, and improved resistance to corrosion and oxidation.
- FIG. 1 shows one exemplary fabrication flow in making a hardmetal according to one implementation.
- FIG. 2 shows an exemplary two-step sintering process for processing hardmetals in a solid state.
- FIGS. 3 , 4 , 5 , 6 , 7 , and 8 show various measured properties of selected exemplary hardmetals.
- compositions of hardmetals are important in that they directly affect the technical performance of the hardmetals in their intended applications, and processing conditions and equipment used during fabrication of such hardmetals.
- the hardmetal compositions also can directly affect the cost of the raw materials for the hardmetals, and the costs associated with the fabrication processes. For these and other reasons, extensive efforts have been made in the hardmetal industry to develop technically superior and economically feasible compositions for hardmetals. This application describes, among other features, material compositions for hardmetals with selected binder matrix materials that, together, provide performance advantages.
- Material compositions for hardmetals of interest include various hard particles and various binder matrix materials.
- the hard particles may be formed from carbides of the metals in columns IVB (e.g., TiC, ZrC, HfC), VB (e.g., VC, NbC, TaC), and VIB (e.g., Cr 3 C 2 , Mo 2 C, WC) in the Periodic Table of Elements.
- nitrides formed by metals elements in columns IVB (e.g., TiN, ZrN, HfN) and VB (e.g., VN, NbN, and TaN) in the Periodic Table of Elements may also be used.
- one material composition for hard particles that is widely used for many hardmetals is a tungsten carbide, e.g., the mono tungsten carbide (WC).
- Various nitrides may be mixed with carbides to form the hard particles. Two or more of the above and other carbides and nitrides may be combined to form WC-based hardmetals or WC-free hardmetals. Examples of mixtures of different carbides include but are not limited to a mixture of WC and TiC, and a mixture of WC, TiC, and TaC.
- the binder matrix may include one or more transition metals in the eighth column of the Periodic Table of Elements, such as cobalt (Co), nickel (Ni), and iron (Fe), and the metals in the 6B column such as molybdenum (Mo) and chromium (Cr). Two or more of such and other binder metals may be mixed together to form desired binder matrices for bonding suitable hard particles.
- Some binder matrices for example, use combinations of Co, Ni, and Mo with different relative weights.
- the hardmetal compositions described here were in part developed based on a recognition that the material composition of the binder matrix may be specially configured and tailored to provide high-performance hardmetals to meet specific needs of various applications.
- the material composition of the binder matrix has significant effects on other material properties of the resulting hardmetals, such as the elasticity, the rigidity, and the strength parameters (including the transverse rupture strength, the tensile strength, and the impact strength).
- the inventor recognized that it was desirable to provide the proper material composition for the binder matrix to better match the material composition of the hard particles and other components of the hardmetals in order to enhance the material properties and the performance of the resulting hardmetals.
- these hardmetal compositions use binder matrices that include rhenium, a nickel-based superalloy or a combination of at least one nickel-based superalloy and other binder materials.
- suitable binder materials may include, among others, rhenium (Re) or cobalt.
- a Ni-based superalloy exhibits a high material strength at a relatively high temperature.
- the resulting hardmetal formed with such a binder material can benefit from the high material strength at high temperatures of rhenium and Ni-superalloy and exhibit enhanced performance at high temperatures.
- a Ni-based superalloy also exhibits superior resistance to corrosion and oxidation, and thus, when used as a binder material, can improve the corresponding resistance of the hardmetals.
- compositions of the hardmetals described in this application may include the binder matrix material from about 3% to about 40% by volume of the total materials in the hardmetals so that the corresponding volume percentage of the hard particles is about from 97% to about 60%, respectively.
- the binder matrix material in certain implementations may be from about 4% to about 35% by volume out of the volume of the total hardmetal materials. More preferably, some compositions of the hardmetals may have from about 5% to about 30% of the binder matrix material by volume out of the volume of the total hardmetal materials.
- the weight percentage of the binder matrix material in the total weight of the resulting hardmetals may be derived from the specific compositions of the hardmetals.
- the binder matrices may be formed primarily by a nickel-based superalloy, and by various combinations of the nickel-based superalloy with other elements such as Re, Co, Ni, Fe, Mo, and Cr.
- a Ni-based superalloy of interest may comprise, in addition to Ni, elements Co, Cr, Al, Ti, Mo, W, and other elements such as Ta, Nb, B, Zr and C.
- Ni-based superalloys may include the following constituent metals in weight percentage of the total weight of the superalloy: Ni from about 30% to about 70%, Cr from about 10% to about 30%, Co from about 0% to about 25%, a total of Al and Ti from about 4% to about 12%, Mo from about 0% to about 10%, W from about 0% to about 10%, Ta from about 0% to about 10%, Nb from about 0% to about 5%, and Hf from about 0% to about 5%.
- Ni-based superalloys may also include either or both of Re and Hf, e.g., Re from 0% to about 10%, and Hf from 0% to about 5%.
- Ni-based superalloy with Re may be used in applications under high temperatures.
- a Ni-based supper alloy may further include other elements, such as B, Zr, and C, in small amounts.
- TaC and NbC have similar properties to a certain extent and may be used to partially or completely substitute or replace each other in hardmetal compositions in some implementations. Either one or both of HfC and NbC also may be used to substitute or replace a part or all of TaC in hardmetal designs.
- WC, TiC, TaC may be produced individually in a form of a mixture together or may be produced in a form of a solid solution.
- the mixture may be selected from at least one from a group consisting of (1) a mixture of WC, TiC, and TaC, (2) a mixture of WC, TiC, and NbC, (3) a mixture of WC, TiC, and at least one of TaC and NbC, and (4) a mixture of WC, TiC, and at least one of HfC and NbC.
- a solid solution of multiple carbides may exhibit better properties and performances than a mixture of several carbides.
- hard particles may be selected from at least one from a group consisting of (1) a solid solution of WC, TiC, and TaC, (2) a solid solution of WC, TiC, and NbC, (3) a solid solution of WC, TiC, and at least one of TaC and NbC, and (4) a solid solution of WC, TiC, and at least one of HfC and NbC.
- the nickel-based superalloy as a binder material may be in a ⁇ - ⁇ ′ phase where the ⁇ ′ phase with a FCC structure mixes with the ⁇ phase.
- the strength increases with temperature within a certain extent.
- Another desirable property of such a Ni-based superalloy is its high resistance to oxidation and corrosion.
- the nickel-based superalloy may be used to either partially or entirely replace Co in various Co-based binder compositions.
- the inclusion of both of rhenium and a nickel-based superalloy in a binder matrix of a hardmetal can significantly improve the performance of the resulting hardmetal by benefiting from the superior performance at high temperatures from presence of Re while utilizing the relatively low-sintering temperature of the Ni-based superalloy to maintain a reasonably low sintering temperature for ease of fabrication.
- the relatively low content of Re in such binder compositions allows for reduced cost of the binder materials so that such materials be economically feasible.
- Such a nickel-based superalloy may have a percentage weight from several percent to 100% with respect to the total weight of all material components in the binder matrix based on the specific composition of the binder matrix.
- a typical nickel-based superalloy may primarily comprise nickel and other metal components in a ⁇ - ⁇ ′ phase strengthened state so that it exhibits an enhanced strength which increases as temperature rises.
- Various nickel-based superalloys may have a melting point lower than the common binder material cobalt, such as alloys under the trade names Rene-95, Udimet-700, Udimet-720 from Special Metals which comprise primarily Ni in combination with Co, Cr, Al, Ti, Mo, Nb, W, B, and Zr.
- cobalt such as alloys under the trade names Rene-95, Udimet-700, Udimet-720 from Special Metals which comprise primarily Ni in combination with Co, Cr, Al, Ti, Mo, Nb, W, B, and Zr.
- the nickel-based superalloy can be used in the binder to provide a high material strength and to improve the material hardness of the resulting hardmetals, at high temperatures near or above 500° C.
- Tests of some fabricated samples have demonstrated that the material hardness and strength for hardmetals with a Ni-based superalloy in the binder can improve significantly, e.g., by at least 10%, at low operating temperatures in comparison with similar material compositions without Ni-based superalloy in the binder.
- the following table show measured hardness parameters of samples P65 and P46A with Ni-based superalloy in the binder in comparison with samples P49 and P47A with pure Co as the binder, where the compositions of the samples are listed in Table 4.
- hardmetal samples with Ni-based superalloy in the binder can exhibit a material hardness that is significantly higher than that of similar hardmetal samples without having a Ni-based superalloy in the binder.
- Ni-based superalloy as a binder material can also improve the resistance to corrosion of the resulting hardmetals or cermets in comparison with hardmetals or cermets using the conventional cobalt as the binder.
- a nickel-based superalloy may be used alone or in combination with other elements to form a desired binder matrix.
- Other elements that may be combined with the nickel-based superalloy to form a binder matrix include but are not limited to, another nickel-based superalloy, other non-nickel-based alloys, Re, Co, Ni, Fe, Mo, and Cr.
- Rhenium as a binder material may be used to provide strong bonding of hard particles and in particular can produce a high melting point for the resulting hardmetal material.
- the melting point of rhenium is about 3180° C., much higher than the melting point of 1495° C. of the commonly-used cobalt as a binder material. This feature of rhenium partially contributes to the enhanced performance of hardmetals with binders using Re, e.g., the enhanced hardness and strength of the resulting hardmetals at high temperatures. Re also has other desired properties as a binder material.
- the hardness, the transverse rapture strength, the fracture toughness, and the melting point of the hardmetals with Re in their binder matrices can be increased significantly in comparison with similar hardmetals without Re in the binder matrices.
- a hardness Hv over 2600 Kg/mm 2 has been achieved in exemplary WC-based hardmetals with Re in the binder matrices.
- the melting point of some exemplary WC-based hardmetals, i.e., the sintering temperature has shown to be greater than 2200° C.
- the sintering temperature for WC-based hardmetals with Co in the binders in Table 2.1 in the cited Brookes is below 1500° C.
- a hardmetal with a high sintering temperature allows the material to operate at a high temperature below the sintering temperature.
- tools based on such Re-containing hardmetal materials may operate at high speeds to reduce the processing time and the overall throughput of the processing.
- Re as a binder material in hardmetals
- the desirable high-temperature property of Re generally leads to a high sintering temperature for fabrication.
- the oven or furnace for the conventional sintering process needs to operate at or above the high sintering temperature.
- Ovens or furnaces capable of operating at such high temperatures, e.g., above 2200° C. can be expensive and may not be widely available for commercial use.
- U.S. Pat. No. 5,476,531 discloses a use of a rapid omnidirectional compaction (ROC) method to reduce the processing temperature in manufacturing WC-based hardmetals with pure Re as the binder material from 6% to 18% of the total weight of each hardmetal. This ROC process, however, is still expensive and is generally not suitable for commercial fabrication.
- ROC rapid omnidirectional compaction
- hardmetal compositions and the composition methods described here may provide or allow for a more practical fabrication process for fabricating hardmetals with either Re or mixtures of Re with other binder materials in the binder matrices.
- this two-step process makes it possible to fabricate hardmetals where Re is at or more than 25% of the total weight of the binder matrix in the resulting hardmetal.
- Such hardmetals with equal to or more than 25% Re may be used to achieve a high material hardness and a material strength at high temperatures.
- Ni-based superalloy has exceptionally strength and oxidation resistance under 1000° C.
- a mixture of a Ni-based superalloy and Re where Re is the dominant material in the binder may be used to improve the strength and oxidation resistance of the resulting hardmetal using such a mixture as the binder.
- the addition of Re into a binder primarily comprised of a Ni-based superalloy can increase the melting range of the resulting hardmetal, and improve the high temperature strength and creep resistance of the Ni-based superalloy binder.
- the percentage weight of the rhenium in the binder matrix should be between a several percent to essentially 100% of the total weight of the binder matrix in a hardmetal.
- the percentage weight of rhenium in the binder matrix should be at or above 5%.
- the percentage weight of rhenium in the binder matrix may be at or above 10% of the binder matrix.
- the percentage weight of rhenium in the binder matrix may be at or above 25% of the total weight of the binder matrix in the resulting hardmetal.
- Hardmetals with such a high concentration of Re may be fabricated at relatively low temperatures with a two-step process described in this application.
- a hardmetal composition includes dispersed hard particles having a first material, and a binder matrix having a second, different material that includes rhenium, where the hard particles are spatially dispersed in the binder matrix in a substantially uniform manner.
- the binder matrix may be a mixture of Re and other binder materials to reduce the total content of Re to in part reduce the overall cost of the raw materials and in part to explore the presence of other binder materials to enhance the performance of the binder matrix.
- binder matrices having mixtures of Re and other binder materials include, mixtures of Re and at least one Ni-based superalloy, mixtures of Re, Co and at least one Ni-based superalloy, mixtures of Re and Co, and others.
- WC-based compositions are referred to as “hardmetals” and the TiC-based compositions are referred to as “cermets.”
- cermets TiC particles bound by a mixture of Ni and Mo or a mixture of N 1 and Mo 2 C are cermets.
- Cermets as described here further include hard particles formed by mixtures of TiC and TiN, of TiC, TiN, WC, TaC, and NbC with the binder matrices formed by the mixture of Ni and Mo or the mixture of N 1 and Mo 2 C.
- three different weight percentage ranges for the given binder material in the are listed.
- the binder may be a mixture of a Ni-based superalloy and cobalt, and the hard particles may a mixture of WC, TiC, TaC, and NbC.
- the binder may be from about 2% to about 40% of the total weight of the hardmetal. This range may be set to from about 3% to about 35% in some applications and may be further limited to a smaller range from about 4% to about 30% in other applications.
- Fabrication of hardmetals with Re or a nickel-based superalloy in binder matrices may be carried out as follows. First, a powder with desired hard particles such as one or more carbides or carbonitrides is prepared. This powder may include a mixture of different carbides or a mixture of carbides and nitrides. The powder is mixed with a suitable binder matrix material that includes Re or a nickel-based superalloy. In addition, a pressing lubricant, e.g., a wax, may be added to the mixture.
- a pressing lubricant e.g., a wax
- the mixture of the hard particles, the binder matrix material, and the lubricant is mixed through a milling or attriting process by milling or attriting over a desired period, e.g., hours, to fully mix the materials so that each hard particle is coated with the binder matrix material to facilitate the binding of the hard particles in the subsequent processes.
- the hard particles should also be coated with the lubricant material to lubricate the materials to facilitate the mixing process and to reduce or eliminate oxidation of the hard particles.
- pressing, pre-sintering, shaping, and final sintering are subsequently performed to the milled mixture to form the resulting hardmetal.
- the sintering process is a process for converting a powder material into a continuous mass by heating to a temperature that is below the melting temperature of the hard particles and may be performed after preliminary compacting by pressure. During this process, the binder material is densified to form a continuous binder matrix to bind hard particles therein. One or more additional coatings may be further formed on a surface of the resulting hardmetal to enhance the performance of the hardmetal.
- FIG. 1 is a flowchart for this implementation of the fabrication process.
- the manufacture process for cemented carbides includes wet milling in solvent, vacuum drying, pressing, and liquid-phase sintering in vacuum.
- the temperature of the liquid-phase sintering is between melting point of the binder material (e.g., Co at 1495° C.) and the eutectic temperature of the mixture of hardmetal (e.g., WC—Co at 1320° C.).
- the sintering temperature of cemented carbide is in a range of 1360 to 1480° C.
- manufacture process is same as conventional cemented carbide process.
- the principle of liquid phase sintering in vacuum is applied in here.
- the sintering temperature is slightly higher than the eutectic temperature of binder alloy and carbide.
- the sintering condition of P17 (25% of Re in binder alloy, by weight) is at 1700° C. for one hour in vacuum.
- FIG. 2 shows a two-step fabrication process based on a solid-state phase sintering for fabricating various hardmetals described in this application.
- hardmetals that can be fabricated with this two-step sintering method include hardmetals with a high concentration of Re in the binder matrix that would otherwise require the liquid-phase sintering at high temperatures.
- This two-step process may be implemented at relatively low temperatures, e.g., under 2200° C., to utilize commercially feasible ovens and to produce the hardmetals at reasonably low costs.
- the liquid phase sintering is eliminated in this two-step process because the liquid phase sintering may not be practical due to the generally high eutectic temperatures of the binder alloy and carbide. As discussed above, sintering at such high temperatures requires ovens operating at high temperatures which may not be commercially feasible.
- the first step of this two-step process is a vacuum sintering where the mixture materials for the binder matrix and the hard particles are sintered in vacuum.
- the mixture is initially processed by, e.g., wet milling, drying, and pressing, as performed in conventional processes for fabricating cemented carbides.
- This first step of sintering is performed at a temperature below the eutectic temperature of the binder alloy and the hard particle materials to remove or eliminate the interconnected porosity.
- the second step is a solid phase sintering at a temperature below the eutectic temperature and under a pressured condition to remove and eliminate the remaining porosities and voids left in the sintered mixture after the first step.
- a hot isostatic pressing (HIP) process may be used as this second step sintering. Both heat and pressure are applied to the material during the sintering to reduce the processing temperature which would otherwise be higher in absence of the pressure.
- a gas medium such as an inert gas may be used to apply and transmit the pressure to the sintered mixture.
- the pressure may be at or over 1000 bar.
- Application of pressure in the HIP process lowers the required processing temperature and allows for use of conventional ovens or furnaces.
- the temperatures of solid phase sintering and HIPping for achieving fully condensed materials are generally significantly lower than the temperatures for liquid phase sintering.
- the sample P62 which uses pure Re as the binder may be fully densified by vacuum sintering at 2200° C.
- ultra fine hard particles with a particulate dimension less than 0.5 micron can reduce the sintering temperature for fully densifying the hardmetals (fine particles are several microns in size).
- the use of such ultra fine WC allows for sintering temperatures to be low, e.g., around 2000° C. This two-step process is less expensive than the ROC method and may be used to commercial production.
- TABLE 2 provides a list of code names (lot numbers) for some of the constituent materials used to form the exemplary hardmetals, where H1 represents rhenium, and L1, L2, and L3 represent three exemplary commercial nickel-based superalloys.
- H1 represents rhenium
- L1, L2, and L3 represent three exemplary commercial nickel-based superalloys.
- TABLE 3 further lists compositions of the above three exemplary nickel-based superalloys, Udimet720 (U720), Rene'95 (R-95), and Udimet700 (U700), respectively.
- TABLE 4 lists compositions of exemplary hardmetals, both with and without rhenium or a nickel-based superalloy in the binder matrices.
- the material composition for Lot P17 primarily includes 88 grams of T32 (WC), 3 grams of 132 (TiC), 3 grams of A31 (TaC), 1.5 grams of H1 (Re) and 4.5 grams of L2 (R-95) as binder, and 2 grams of a wax as lubricant.
- Lot P58 represents a hardmetal with a nickel-based superalloy L2 as the only binder material without Re. These hardmetals were fabricated and tested to illustrate the effects of either or both of rhenium and a nickel-based superalloy as binder materials on various properties of the resulting hardmetals.
- TABLES 5-8 further provide summary information of compositions and properties of different sample lots as defined above.
- FIGS. 3 through 8 show measurements of selected hardmetal samples of this application.
- FIGS. 3 and 4 show measured toughness and hardness parameters of some exemplary hardmetals for the steel cutting grades.
- FIGS. 5 and 6 show measured toughness and hardness parameters of some exemplary hardmetals for the non-ferrous cutting grades. Measurements were performed before and after the solid-phase sintering HIP process and the data suggests that the HIP process significantly improves both the toughness and the hardness of the materials.
- FIG. 7 shows measurements of the hardness as a function of temperature for some samples. As a comparison, FIGS. 7 and 8 also show measurements of commercial C 2 and C 6 carbides under the same testing conditions, where FIG. 7 shows the measured hardness and FIG.
- I32 TiC from AEE Ti ⁇ 302 I21 TiB 2 from AEE, Ti ⁇ 201, 1-5 ⁇ m A31 TaC from AEE, TA ⁇ 301 Y31 Mo 2 C from AEE, MO ⁇ 301 D31 VC from AEE, VA ⁇ 301 B1 Co from AEE, CO ⁇ 101 K1 Ni from AEE, Ni ⁇ 101 K2 Ni from AEE, Ni ⁇ 102 I13 TiN from Cerac, T ⁇ 1153 C21 ZrB2 from Cerac, Z ⁇ 1031 Y6 Mo from AEE Mo + 100, 1-2 ⁇ m L6 Al from AEE Al ⁇ 100, 1-5 ⁇ m R31 B 4 C from AEE Bo ⁇ 301, 3 ⁇ m T3.8 WC Particle size 0.8 ⁇ m, Alldyne T3.4 WC Particle size 0.4 ⁇ m, OMG T3.2 WC Particle size 0.2 ⁇ m, OMG
- the exemplary categories of hardmetal compositions are described below to illustrate the above general designs of the various hardmetal compositions to include either of Re and Nickel-based superalloy, or both.
- the exemplary categories of hardmetal compositions are defined based on the compositions of the binder matrices for the resulting hardmetals or cermets.
- the first category uses a binder matrix having pure Re
- the second category uses a binder matrix having a Re—Co alloy
- the third category uses a binder matrix having a Ni-based superalloy
- the fourth category uses a binder matrix having an alloy having a Ni-based superalloy in combination with of Re with or without Co.
- hard and refractory particles used in hardmetals of interest may include, but are not limited to, Carbides, Nitrides, Carbonitrides, Borides, and Silicides.
- Carbides include WC, TiC, TaC, HfC, NbC, Mo 2 C, Cr 2 C 3 , VC, ZrC, B 4 C, and SiC.
- Nitrides include TiN, ZrN, HfN, VN, NbN, TaN, and BN.
- Examples of Carbonitrides include Ti(C,N), Ta(C,N), Nb(C,N), Hf(C,N), Zr(C,N), and V(C,N).
- Examples of Borides include TiB 2 , ZrB 2 , HfB 2 , TaB 2 , VB 2 , MoB 2 , WB, and W 2 B.
- examples of Silicides are TaSi 2 , WSi 2 , NbSi 2 , and MoSi 2 .
- the above-identified four categories of hardmetals or cermets can also use these and other hard and refractory particles.
- the Re may be approximately from 5% to 40% by volume of all material compositions used in a hardmetal or cermet.
- the sample with a lot No. P62 in TABLE 4 has 10% of pure Re, 70% of WC, 15% of TiC, and 5% of TaC by volume. This composition approximately corresponds to 14.48% of Re, 75.43% of WC, 5.09% of TiC and 5.0% of TaC by weight.
- the Specimen P62-4 was vacuum sintered at 2100° C. for about one hour and 2158° C. for about one hour. The density of this material is about 14.51 g/cc, where the calculated density is 14.50 g/cc.
- the average hardness Hv is 2627 ⁇ 35 Kg/mm 2 for 10 measurements taken at the room temperature under a load of 10 Kg.
- the measured surface fracture toughness K sc is about 7.4 ⁇ 10 6 Pa ⁇ m 1/2 estimated by Palmvist crack length at a load of 10 Kg.
- P66 in TABLE 4 This sample has about 20% of Re, 60% of WC, 15% of TiC, and 5% of TaC by volume in composition. In the weight percentage, this sample has about 27.92% of Re, 62.35% of WC, 4.91% of TiC, and 4.82% of TaC.
- the Specimen P66-4 was first processed with a vacuum sintering process at about 2200° C. for one hour and was then sintered in the solid-phase with a HIP process to remove porosities and voids.
- the density of the resulting hardmetal is about 14.40 g/cc compared to the calculated density of 15.04 g/cc.
- the average hardness Hv is about 2402 ⁇ 44 Kg/mm 2 for 7 different measurements taken at the room temperature under a load of 10 Kg.
- the surface fracture toughness K sc is about 8.1 ⁇ 10 6 Pa ⁇ m 1/2 .
- sample P66 and other compositions described here with a high concentration of Re with a weight percentage greater than 25% may be used for various applications at high operating temperatures and may be manufactured by using the two-step process based on solid-phase sintering.
- the microstructures and properties of Re bound multiples types of hard refractory particles may provide advantages over Re-bound WC material.
- Re bound WC—TiC—TaC may have better crater resistance in steel cutting than Re bound WC material.
- Another example is materials formed by refractory particles of Mo 2 C and TiC bound in a Re binder.
- the Re—Co alloy may be about from 5 to 40 Vol % of all material compositions used in the composition.
- the Re-to-Co ratio in the binder may vary from 0.01 to 0.99 approximately.
- Inclusion of Re can improve the mechanical properties of the resulting hardmetals, such as hardness, strength and toughness special at high temperature compared to Co bounded hardmetal. The higher Re content is the better high temperature properties are for most materials using such a binder matrix.
- the sample P31 in TABLE 4 is one example within this category with 2.5% of Re, 7.5% of Co, and 90% of WC by volume, and 3.44% of Re, 4.40% of Co and 92.12% of WC by weight.
- the Specimen P31-1 was vacuum sintered at 1725 C for about one hour. slight under sintering with some porosities and voids.
- the density of the resulting hardmetal is about 15.16 g/cc (calculated density at 15.27 g/cc).
- the average hardness Hv is about 1889 ⁇ 18 Kg/mm 2 at the room temperature under 10 Kg and the surface fracture toughness K sc is about 7.7 ⁇ 10 6 Pa ⁇ m 1/2 .
- the Specimen P31-1 was treated with a hot isostatic press (HIP) process at about 160° C./15 Ksi for about one hour after sintering.
- HIP hot isostatic press
- the HIP reduces or substantially eliminates the porosities and voids in the compound to increase the material density.
- the measured density is about 15.25 g/cc (calculated density at 15.27 g/cc).
- the measured hardness Hv is about 1887 ⁇ 12 Kg/mm 2 at the room temperature under 10 Kg.
- the surface fracture toughness K sc is about 7.6 ⁇ 10 6 Pa ⁇ m 1/2 .
- P32 in TABLE 4 with 5.0% of Re, 5.0% of Co, and 90% of WC in volume (6.75% of Re, 2.88% of Co and 90.38% of WC in weight).
- the Specimen P32-4 was vacuum sintered at 1800 C for about one hour.
- the measured density is about 15.58 g/cc in comparison with the calculated density at 15.57 g/cc.
- the measured hardness Hv is about 2065 Kg/mm 2 at the room temperature under 10 Kg.
- the surface fracture toughness K sc is about 5.9 ⁇ 10 6 Pa ⁇ m 1/2 .
- the Specimen P32-4 was also HIP at 1600 C/15 Ksi for about one hour after Sintering.
- the measured density is about 15.57 g/cc (calculated density at 15.57 g/cc).
- the average hardness Hv is about 2010 ⁇ 12 Kg/mm 2 at the room temperature under 10 Kg.
- the surface fracture toughness K sc is about 5.8 ⁇ 10 6 Pa ⁇ m 1/2 .
- the third example is P33 in TABLE 4 which has 7.5% of Re, 2.5% of Co, and 90% of WC by volume and 9.93% of Re, 1.41% of Co and 88.66% of WC by weight.
- the Specimen P33-7 was vacuum sintered at 1950 C for about one hour and was under sintering with porosities and voids.
- the measured density is about 15.38 g/cc (calculated density at 15.87 g/cc).
- the measured hardness Hv is about 2081 Kg/mm 2 at the room temperature under a force of 10 Kg.
- the surface fracture toughness K sc is about 5.6 ⁇ 10 6 Pa ⁇ m 1/2 .
- the Specimen P33-7 was HIP at 1600 C/15 Ksi for about one hour after Sintering.
- the average hardness Hv is measured at about 2039 ⁇ 18 Kg/mm 2 at the room temperature under 10 Kg.
- the surface fracture toughness K sc is about 6.5 ⁇ 10 6 Pa ⁇ m 1/2 .
- the samples P55, P56, P56A, and P57 in TABLE 4 are also examples for the category with a Re—Co alloy as the binder matrix. These samples have about 1.8% of Re, 7.2% of Co, 0.6% of VC except that P57 has no VC, and finally WC in balance. These different compositions are made to study the effects of hardmetal grain size on Hv and Ksc. TABLE 5 lists the results.
- Ni-based superalloys are a family of high temperature alloys with ⁇ ′ strengthening. Three different strength alloys, Rene'95, Udimet 720, and Udimet 700 are used as examples to demonstrate binder strength effects on mechanical properties of hardmetals.
- the Ni-based superalloys have a high strength specially at elevated temperatures. Also, these alloys have good environmental resistance such as resistance to corrosion and oxidation at elevated temperature. Therefore, Ni-based superalloys can be used to increase the hardness of Ni-based superalloy bound hardmetals when compared to Cobalt bound hardmetals. Notably, the tensile strengths of the Ni-based superalloys are much stronger than the common binder material cobalt as shown by TABLE 6. This further shows that Ni-based superalloys are good binder materials for hardmetals.
- P58 in TABLE 4 which has 7.5% of Rene'95, 0.6% of VC, and 91.9% of WC in weight and compares to cobalt bound P54 in TABLE 4 (8% of Co, 0.6% of VC, and 91.4% of WC).
- the hardness of P58 is significant higher than P54 as shown in TABLE 7.
- the fourth category is Ni-based superalloy plus Re as binder, e.g., approximately from 5% to 40% by volume of all materials in the resulting hardmetal or cermet. Because addition of Re increases the melting point of binder alloy of Ni-based superalloy plus Re, the processing temperature of hardmetal with Ni-based superalloy plus Re binder increases as the Re content increases. Several hardmetals with different Re concentrations are listed in TABLE 8. TABLE 9 further shows the measured properties of the hardmetals in TABLE 8.
- Ni-based superalloy plus Re and Co as binder which is also about 5% to 40% by volume.
- Exemplary compositions of hardmetals bound by Ni-based superalloy plus Re and Co are list in TABLE 10.
- Ni-based superalloys not only exhibit excellent strengths at elevated temperatures but also possess outstanding resistances to oxidation and corrosion at high temperatures.
- Ni-based superalloys have complex microstructures and strengthening mechanisms. In general, the strengthening of Ni-based superalloys is primarily due to precipitation strengthening of ⁇ - ⁇ ′ and solid-solution strengthening. The measurements the selected samples demonstrate that Ni-based superalloys can be used as a high-performance binder materials for hardmetals.
- TABLE 11 lists compositions of selected samples by their weight percentages of the total weight of the hardmetals.
- the WC particles in the samples are 0.2 ⁇ m in size.
- TABLE 12 lists the conditions for the two-step process performed and measured densities, hardness parameters, and toughness parameters of the samples.
- the sample P54 uses the conventional binder consisting of Co.
- the Ni-superalloy R-95 is used in the sample P58 to replace Co as the binder in the sample P54.
- the Hv increases from 2090 of P54 to 2246 of P58.
- the mixture of Re and Co is used to replace Co as binder and the corresponding Hv increases from 2090 of P54 to 2133 of P56.
- the samples P72, P73, P74 have the same Re content but different amounts of Co and R95.
- the mixtures of Re, Co, and R95 are used in samples P73 and P74 to replace the binder having a mixture of Re and Co as the binder in the sample 72.
- the hardness Hv increases from 2041 (P72) to 2217 (P73) and 2223 (P74).
- TABLE 13 lists the tested samples.
- the WC particles with two different particle sizes of 2 ⁇ m and 0.2 ⁇ m were used.
- TABLE 14 lists the conditions for the two-step process performed and the measured densities, hardness parameters, and toughness parameters of the selected samples.
- TABLE 15 further shows measured hardness parameters under various temperatures for the selected samples, where the Knoop hardness H k were measured under a load of 1 Kg for 15 seconds on a Nikon QM hot hardness tester and R is a ratio of H k at an elevated testing temperature over H k at 25° C.
- the hot hardness specimens of C2 and C6 carbides were prepared from inserts SNU434 which were purchased from MSC Co. (Melville, N.Y.).
- the inclusion of Re in the binder matrices of the hardmetals increases the melting point of binder alloys that include Co—Re, Ni superalloy-Re, Ni superalloy-Re—Co.
- the melting point of the sample P63 is much higher than the temperature of 2200° C. used for the solid-phase sintering process.
- Hot hardness values of such hardmetals with Re in the binders e.g., P17 to P63
- the above measurements reveal that an increase in the concentration of Re in the binder increases the hardness at high temperatures.
- the sample P62A with pure Re as the binder has the highest hardness.
- the sample P63 with a binder composition of 94% of Re and 6% of the Ni-based superalloy R95 has the second highest hardness.
- the samples P40A (71.9% Re-29.1% R95), P49 (69.9% Re-30.1% R95), P51 (88.5% Re-11.5% R95), and P50 (71.9% Re-28.1% R95) are the next group in their hardness.
- the sample P48 with 62.5% of Re and 37.5% of R95 in its binder has the lowest hardness at high temperatures among the tested materials in part because its Re content is the lowest.
- a hardmetal or cermet may include TiC and TiN bonded in a binder matrix having Ni and Mo or Mo 2 C.
- the binder Ni of cermet can be fully or partially replaced by Re, by Re plus Co, by Ni-based superalloy, by Re plus Ni-based superalloy, and by Re plus Co and Ni-based superalloy.
- P38 and P39 are a typical Ni bound cermet.
- the sample P34 is Rene95 bound Cermet.
- compositions for hardmetals or cermets may be used for a variety of applications.
- a material may be used to form a wear part in a tool that cuts, grinds, or drills a target object by using the wear part to remove the material of the target object.
- a tool may include a support part made of a different material, such as a steel. The wear part is then engaged to the support part as an insert.
- the tool may be designed to include multiple inserts engaged to the support part.
- some mining drills may include multiple button bits made of a hardmetal material. Examples of such a tool includes a drill, a cutter such as a knife, a saw, a grinder, a drill.
- hardmetals descried here may be used to form the entire head of a tool as the wear part for cutting, drilling or other machining operations.
- the hardmetal particles may also be used to form abrasive grits for polishing or grinding various materials.
- such hardmetals may also be used to construct housing and exterior surfaces or layers for various devices to meet specific needs of the operations of the devices or the environmental conditions under which the devices operate.
- the hardmetals described here may be used to manufacture cutting tools for machining of metal, composite, plastic and wood.
- the cutting tools may include indexable inserts for turning, milling, boring and drilling, drills, end mills, reamers, taps, hobs and milling cutters. Since the temperature of the cutting edge of such tools may be higher than 500° C. during machining, the hardmetal compositions for high-temperature operating conditions described above may have special advantages when used in such cutting tools, e.g., extended tool life and improved productivity by such tools by increasing the cutting speed.
- the hardmetals described here may be used to manufacture tools for wire drawing, extrusion, forging and cold heading. Also as mold and Punch for powder process. In addition, such hardmetals may be used as wear-resistant material for rock drilling and mining.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Powder Metallurgy (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
- Ceramic Products (AREA)
Abstract
Description
- This application is a divisional application of and claims priority to U.S. patent application Ser. No. 10/941,967, filed Sep. 14, 2004, which is a divisional application of U.S. patent application Ser. No. 10/453,085, filed Jun. 2, 2003, now U.S. Pat. No. 6,911,063, which claims the benefit of U.S. Provisional Application No. 60/439,838, filed Jan. 13, 2003, and U.S. Provisional Application No. 60/449,305 filed Feb. 20, 2003. The disclosures of the prior applications are considered part of (and are incorporated by reference in) the disclosure of this application.
- This application relates to hardmetal compositions, their fabrication techniques, and associated applications.
- Hardmetals include various composite materials and are specially designed to be hard and refractory, and exhibit strong resistance to wear. Examples of widely-used hardmetals include sintered or cemented carbides or carbonitrides, or a combination of such materials. Some hardmetals, called cermets, have compositions that may include processed ceramic particles (e.g., TiC) bonded with binder metal particles. Certain compositions of hardmetals have been documented in the technical literature. For example, a comprehensive compilation of hardmetal compositions is published in Brookes' World Dictionary and Handbook of Hardmetals, sixth edition, International Carbide Data, United Kingdom (1996).
- Hardmetals may be used in a variety of applications. Exemplary applications include cutting tools for cutting metals, stones, and other hard materials, wire-drawing dies, knives, mining tools for cutting coals and various ores and rocks, and drilling tools for oil and other drilling applications. In addition, such hardmetals also may be used to construct housing and exterior surfaces or layers for various devices to meet specific needs of the operations of the devices or the environmental conditions under which the devices operate.
- Many hardmetals may be formed by first dispersing hard, refractory particles of carbides or carbonitrides in a binder matrix and then pressing and sintering the mixture. The sintering process allows the binder matrix to bind the particles and to condense the mixture to form the resulting hardmetals. The hard particles primarily contribute to the hard and refractory properties of the resulting hardmetals.
- The hardmetal materials described below include materials comprising hard particles having a first material, and a binder matrix having a second, different material. The hard particles are spatially dispersed in the binder matrix in a substantially uniform manner. The first material for the hard particles may include, for example, materials based on tungsten carbide, materials based on titanium carbide, and materials based on a mixture of tungsten carbide and titanium carbide. The second material for the binder matrix may include, among others, rhenium, a mixture of rhenium and cobalt, a nickel-based superalloy, a mixture of a nickel-based superalloy and rhenium, a mixture of a nickel-based superalloy, rhenium and cobalt, and these materials mixed with other materials. The nickel-based superalloy may be in the γ-γ′ metallurgic phase.
- In various implementations, for example, the volume of the second material may be from about 3% to about 40% of a total volume of the material. For some applications, the binder matrix may comprise rhenium in an amount at or greater than 25% of a total weight of the binder matrix in the material. In other applications, the second material may include a Ni-based superalloy. The Ni-based superalloy may include Ni and other elements such as Re for certain applications.
- Fabrication of the hardmetal materials of this application may be carried out by, according to one implementation, sintering the material mixture under a vacuum condition and performing a solid-phase sintering under a pressure applied through a gas medium.
- Advantages arising from these hardmetal materials and composition methods may include one or more of the following: superior hardness in general, enhanced hardness at high temperatures, and improved resistance to corrosion and oxidation.
- These and other features, implementations, and advantages are now described in detail with respect to the drawings, the detailed description, and the claims.
-
FIG. 1 shows one exemplary fabrication flow in making a hardmetal according to one implementation. -
FIG. 2 shows an exemplary two-step sintering process for processing hardmetals in a solid state. -
FIGS. 3 , 4, 5, 6, 7, and 8 show various measured properties of selected exemplary hardmetals. - Compositions of hardmetals are important in that they directly affect the technical performance of the hardmetals in their intended applications, and processing conditions and equipment used during fabrication of such hardmetals. The hardmetal compositions also can directly affect the cost of the raw materials for the hardmetals, and the costs associated with the fabrication processes. For these and other reasons, extensive efforts have been made in the hardmetal industry to develop technically superior and economically feasible compositions for hardmetals. This application describes, among other features, material compositions for hardmetals with selected binder matrix materials that, together, provide performance advantages.
- Material compositions for hardmetals of interest include various hard particles and various binder matrix materials. In general, the hard particles may be formed from carbides of the metals in columns IVB (e.g., TiC, ZrC, HfC), VB (e.g., VC, NbC, TaC), and VIB (e.g., Cr3C2, Mo2C, WC) in the Periodic Table of Elements. In addition, nitrides formed by metals elements in columns IVB (e.g., TiN, ZrN, HfN) and VB (e.g., VN, NbN, and TaN) in the Periodic Table of Elements may also be used. For example, one material composition for hard particles that is widely used for many hardmetals is a tungsten carbide, e.g., the mono tungsten carbide (WC). Various nitrides may be mixed with carbides to form the hard particles. Two or more of the above and other carbides and nitrides may be combined to form WC-based hardmetals or WC-free hardmetals. Examples of mixtures of different carbides include but are not limited to a mixture of WC and TiC, and a mixture of WC, TiC, and TaC.
- The material composition of the binder matrix, in addition to providing a matrix for bonding the hard particles together, can significantly affect the hard and refractory properties of the resulting hardmetals. In general, the binder matrix may include one or more transition metals in the eighth column of the Periodic Table of Elements, such as cobalt (Co), nickel (Ni), and iron (Fe), and the metals in the 6B column such as molybdenum (Mo) and chromium (Cr). Two or more of such and other binder metals may be mixed together to form desired binder matrices for bonding suitable hard particles. Some binder matrices, for example, use combinations of Co, Ni, and Mo with different relative weights.
- The hardmetal compositions described here were in part developed based on a recognition that the material composition of the binder matrix may be specially configured and tailored to provide high-performance hardmetals to meet specific needs of various applications. In particular, the material composition of the binder matrix has significant effects on other material properties of the resulting hardmetals, such as the elasticity, the rigidity, and the strength parameters (including the transverse rupture strength, the tensile strength, and the impact strength). Hence, the inventor recognized that it was desirable to provide the proper material composition for the binder matrix to better match the material composition of the hard particles and other components of the hardmetals in order to enhance the material properties and the performance of the resulting hardmetals.
- More specifically, these hardmetal compositions use binder matrices that include rhenium, a nickel-based superalloy or a combination of at least one nickel-based superalloy and other binder materials. Other suitable binder materials may include, among others, rhenium (Re) or cobalt. A Ni-based superalloy exhibits a high material strength at a relatively high temperature. The resulting hardmetal formed with such a binder material can benefit from the high material strength at high temperatures of rhenium and Ni-superalloy and exhibit enhanced performance at high temperatures. In addition, a Ni-based superalloy also exhibits superior resistance to corrosion and oxidation, and thus, when used as a binder material, can improve the corresponding resistance of the hardmetals.
- The compositions of the hardmetals described in this application may include the binder matrix material from about 3% to about 40% by volume of the total materials in the hardmetals so that the corresponding volume percentage of the hard particles is about from 97% to about 60%, respectively. Within the above volume percentage range, the binder matrix material in certain implementations may be from about 4% to about 35% by volume out of the volume of the total hardmetal materials. More preferably, some compositions of the hardmetals may have from about 5% to about 30% of the binder matrix material by volume out of the volume of the total hardmetal materials. The weight percentage of the binder matrix material in the total weight of the resulting hardmetals may be derived from the specific compositions of the hardmetals.
- In various implementations, the binder matrices may be formed primarily by a nickel-based superalloy, and by various combinations of the nickel-based superalloy with other elements such as Re, Co, Ni, Fe, Mo, and Cr. A Ni-based superalloy of interest may comprise, in addition to Ni, elements Co, Cr, Al, Ti, Mo, W, and other elements such as Ta, Nb, B, Zr and C. For example, Ni-based superalloys may include the following constituent metals in weight percentage of the total weight of the superalloy: Ni from about 30% to about 70%, Cr from about 10% to about 30%, Co from about 0% to about 25%, a total of Al and Ti from about 4% to about 12%, Mo from about 0% to about 10%, W from about 0% to about 10%, Ta from about 0% to about 10%, Nb from about 0% to about 5%, and Hf from about 0% to about 5%. Ni-based superalloys may also include either or both of Re and Hf, e.g., Re from 0% to about 10%, and Hf from 0% to about 5%. Ni-based superalloy with Re may be used in applications under high temperatures. A Ni-based supper alloy may further include other elements, such as B, Zr, and C, in small amounts.
- TaC and NbC have similar properties to a certain extent and may be used to partially or completely substitute or replace each other in hardmetal compositions in some implementations. Either one or both of HfC and NbC also may be used to substitute or replace a part or all of TaC in hardmetal designs. WC, TiC, TaC may be produced individually in a form of a mixture together or may be produced in a form of a solid solution. When a mixture is used, the mixture may be selected from at least one from a group consisting of (1) a mixture of WC, TiC, and TaC, (2) a mixture of WC, TiC, and NbC, (3) a mixture of WC, TiC, and at least one of TaC and NbC, and (4) a mixture of WC, TiC, and at least one of HfC and NbC. A solid solution of multiple carbides may exhibit better properties and performances than a mixture of several carbides. Hence, hard particles may be selected from at least one from a group consisting of (1) a solid solution of WC, TiC, and TaC, (2) a solid solution of WC, TiC, and NbC, (3) a solid solution of WC, TiC, and at least one of TaC and NbC, and (4) a solid solution of WC, TiC, and at least one of HfC and NbC.
- The nickel-based superalloy as a binder material may be in a γ-γ′ phase where the γ′ phase with a FCC structure mixes with the γ phase. The strength increases with temperature within a certain extent. Another desirable property of such a Ni-based superalloy is its high resistance to oxidation and corrosion. The nickel-based superalloy may be used to either partially or entirely replace Co in various Co-based binder compositions. As demonstrated by examples disclosed in this application, the inclusion of both of rhenium and a nickel-based superalloy in a binder matrix of a hardmetal can significantly improve the performance of the resulting hardmetal by benefiting from the superior performance at high temperatures from presence of Re while utilizing the relatively low-sintering temperature of the Ni-based superalloy to maintain a reasonably low sintering temperature for ease of fabrication. In addition, the relatively low content of Re in such binder compositions allows for reduced cost of the binder materials so that such materials be economically feasible.
- Such a nickel-based superalloy may have a percentage weight from several percent to 100% with respect to the total weight of all material components in the binder matrix based on the specific composition of the binder matrix. A typical nickel-based superalloy may primarily comprise nickel and other metal components in a γ-γ′ phase strengthened state so that it exhibits an enhanced strength which increases as temperature rises.
- Various nickel-based superalloys may have a melting point lower than the common binder material cobalt, such as alloys under the trade names Rene-95, Udimet-700, Udimet-720 from Special Metals which comprise primarily Ni in combination with Co, Cr, Al, Ti, Mo, Nb, W, B, and Zr. Hence, using such a nickel-based superalloy alone as a binder material may not increase the melting point of the resulting hardmetals in comparison with hardmetals using binders with Co.
- However, in one implementation, the nickel-based superalloy can be used in the binder to provide a high material strength and to improve the material hardness of the resulting hardmetals, at high temperatures near or above 500° C. Tests of some fabricated samples have demonstrated that the material hardness and strength for hardmetals with a Ni-based superalloy in the binder can improve significantly, e.g., by at least 10%, at low operating temperatures in comparison with similar material compositions without Ni-based superalloy in the binder. The following table show measured hardness parameters of samples P65 and P46A with Ni-based superalloy in the binder in comparison with samples P49 and P47A with pure Co as the binder, where the compositions of the samples are listed in Table 4.
-
Effects of Ni-based Superalloy (NS) in Binder Sample Hv at Room Ksc at room Code Co or NS Temperature temperature Name Binder (Kg/mm2) (×106 Pa · m1/2) Comparison P49 Co: 10 2186 6.5 volume % P65 NS: 10 2532 6.7 Hv is about 16% volume % greater than that of P49 P47A Co: 15 2160 6.4 volume % P46A NS: 15 2364 6.4 Hv is about 10% volume % greater than that of P47A - Notably, at high operating temperatures above 500° C., hardmetal samples with Ni-based superalloy in the binder can exhibit a material hardness that is significantly higher than that of similar hardmetal samples without having a Ni-based superalloy in the binder. In addition, Ni-based superalloy as a binder material can also improve the resistance to corrosion of the resulting hardmetals or cermets in comparison with hardmetals or cermets using the conventional cobalt as the binder.
- A nickel-based superalloy may be used alone or in combination with other elements to form a desired binder matrix. Other elements that may be combined with the nickel-based superalloy to form a binder matrix include but are not limited to, another nickel-based superalloy, other non-nickel-based alloys, Re, Co, Ni, Fe, Mo, and Cr.
- Rhenium as a binder material may be used to provide strong bonding of hard particles and in particular can produce a high melting point for the resulting hardmetal material. The melting point of rhenium is about 3180° C., much higher than the melting point of 1495° C. of the commonly-used cobalt as a binder material. This feature of rhenium partially contributes to the enhanced performance of hardmetals with binders using Re, e.g., the enhanced hardness and strength of the resulting hardmetals at high temperatures. Re also has other desired properties as a binder material. For example, the hardness, the transverse rapture strength, the fracture toughness, and the melting point of the hardmetals with Re in their binder matrices can be increased significantly in comparison with similar hardmetals without Re in the binder matrices. A hardness Hv over 2600 Kg/mm2 has been achieved in exemplary WC-based hardmetals with Re in the binder matrices. The melting point of some exemplary WC-based hardmetals, i.e., the sintering temperature, has shown to be greater than 2200° C. In comparison, the sintering temperature for WC-based hardmetals with Co in the binders in Table 2.1 in the cited Brookes is below 1500° C. A hardmetal with a high sintering temperature allows the material to operate at a high temperature below the sintering temperature. For example, tools based on such Re-containing hardmetal materials may operate at high speeds to reduce the processing time and the overall throughput of the processing.
- The use of Re as a binder material in hardmetals, however, may present limitations in practice. For example, the desirable high-temperature property of Re generally leads to a high sintering temperature for fabrication. Thus, the oven or furnace for the conventional sintering process needs to operate at or above the high sintering temperature. Ovens or furnaces capable of operating at such high temperatures, e.g., above 2200° C., can be expensive and may not be widely available for commercial use. U.S. Pat. No. 5,476,531 discloses a use of a rapid omnidirectional compaction (ROC) method to reduce the processing temperature in manufacturing WC-based hardmetals with pure Re as the binder material from 6% to 18% of the total weight of each hardmetal. This ROC process, however, is still expensive and is generally not suitable for commercial fabrication.
- One potential advantage of the hardmetal compositions and the composition methods described here is that they may provide or allow for a more practical fabrication process for fabricating hardmetals with either Re or mixtures of Re with other binder materials in the binder matrices. In particular, this two-step process makes it possible to fabricate hardmetals where Re is at or more than 25% of the total weight of the binder matrix in the resulting hardmetal. Such hardmetals with equal to or more than 25% Re may be used to achieve a high material hardness and a material strength at high temperatures.
- Another limitation of using pure Re as a binder material for hardmetals is that Re oxidizes severely in air at or above about 350° C. This poor oxidation resistance may dramatically reduce the use of pure Re as binder for any application above about 300° C. Since Ni-based superalloy has exceptionally strength and oxidation resistance under 1000° C., a mixture of a Ni-based superalloy and Re where Re is the dominant material in the binder may be used to improve the strength and oxidation resistance of the resulting hardmetal using such a mixture as the binder. On the other hand, the addition of Re into a binder primarily comprised of a Ni-based superalloy can increase the melting range of the resulting hardmetal, and improve the high temperature strength and creep resistance of the Ni-based superalloy binder.
- In general, the percentage weight of the rhenium in the binder matrix should be between a several percent to essentially 100% of the total weight of the binder matrix in a hardmetal. Preferably, the percentage weight of rhenium in the binder matrix should be at or above 5%. In particular, the percentage weight of rhenium in the binder matrix may be at or above 10% of the binder matrix. In some implementations, the percentage weight of rhenium in the binder matrix may be at or above 25% of the total weight of the binder matrix in the resulting hardmetal. Hardmetals with such a high concentration of Re may be fabricated at relatively low temperatures with a two-step process described in this application.
- Since rhenium is generally more expensive than other materials used in hardmetals, cost should be considered in designing binder matrices that include rhenium. Some of the examples given below reflect this consideration. In general, according to one implementation, a hardmetal composition includes dispersed hard particles having a first material, and a binder matrix having a second, different material that includes rhenium, where the hard particles are spatially dispersed in the binder matrix in a substantially uniform manner. The binder matrix may be a mixture of Re and other binder materials to reduce the total content of Re to in part reduce the overall cost of the raw materials and in part to explore the presence of other binder materials to enhance the performance of the binder matrix. Examples of binder matrices having mixtures of Re and other binder materials include, mixtures of Re and at least one Ni-based superalloy, mixtures of Re, Co and at least one Ni-based superalloy, mixtures of Re and Co, and others.
- TABLE 1 lists some examples of hardmetal compositions of interest. In this table, WC-based compositions are referred to as “hardmetals” and the TiC-based compositions are referred to as “cermets.” Traditionally, TiC particles bound by a mixture of Ni and Mo or a mixture of N1 and Mo2C are cermets. Cermets as described here further include hard particles formed by mixtures of TiC and TiN, of TiC, TiN, WC, TaC, and NbC with the binder matrices formed by the mixture of Ni and Mo or the mixture of N1 and Mo2C. For each hardmetal composition, three different weight percentage ranges for the given binder material in the are listed. As an example, the binder may be a mixture of a Ni-based superalloy and cobalt, and the hard particles may a mixture of WC, TiC, TaC, and NbC. In this composition, the binder may be from about 2% to about 40% of the total weight of the hardmetal. This range may be set to from about 3% to about 35% in some applications and may be further limited to a smaller range from about 4% to about 30% in other applications.
-
TABLE 1 (NS: Ni-based superalloy) Composition Binder for 1st Binder 2nd Binder 3rd Binder Composition Hard Particles Wt. % Range Wt. % Range Wt. % Range Hardmetals Re WC 4 to 40 5 to 35 6 to 30 WC—TiC—TaC—NbC 4 to 40 5 to 35 6 to 30 NS WC 2 to 30 3 to 25 4 to 20 WC—TiC—TaC—NbC 2 to 30 3 to 25 4 to 20 NS—Re WC 2 to 40 3 to 35 4 to 30 WC—TiC—TaC—NbC 2 to 40 3 to 35 4 to 30 Re—Co WC 2 to 40 3 to 35 4 to 30 WC—TiC—TaC—NbC 2 to 40 3 to 35 4 to 30 NS—Re—Co WC 2 to 40 3 to 35 4 to 30 WC—TiC—TaC—NbC 2 to 40 3 to 35 4 to 30 Cermets NS Mo2C—TiC 5 to 40 6 to 35 8 to 40 Mo2C—TiC—TiN— 5 to 40 6 to 35 8 to 40 WC—TaC—NbC Re Mo2C—TiC 10 to 55 12 to 50 15 to 45 Mo2C—TiC—TiN— 10 to 55 12 to 50 15 to 45 WC—TaC—NbC NS—Re Mo2C—TiC 5 to 55 6 to 50 8 to 45 Mo2C—TiC—TiN— 5 to 55 6 to 50 8 to 45 WC—TaC—NbC - Fabrication of hardmetals with Re or a nickel-based superalloy in binder matrices may be carried out as follows. First, a powder with desired hard particles such as one or more carbides or carbonitrides is prepared. This powder may include a mixture of different carbides or a mixture of carbides and nitrides. The powder is mixed with a suitable binder matrix material that includes Re or a nickel-based superalloy. In addition, a pressing lubricant, e.g., a wax, may be added to the mixture.
- The mixture of the hard particles, the binder matrix material, and the lubricant is mixed through a milling or attriting process by milling or attriting over a desired period, e.g., hours, to fully mix the materials so that each hard particle is coated with the binder matrix material to facilitate the binding of the hard particles in the subsequent processes. The hard particles should also be coated with the lubricant material to lubricate the materials to facilitate the mixing process and to reduce or eliminate oxidation of the hard particles. Next, pressing, pre-sintering, shaping, and final sintering are subsequently performed to the milled mixture to form the resulting hardmetal. The sintering process is a process for converting a powder material into a continuous mass by heating to a temperature that is below the melting temperature of the hard particles and may be performed after preliminary compacting by pressure. During this process, the binder material is densified to form a continuous binder matrix to bind hard particles therein. One or more additional coatings may be further formed on a surface of the resulting hardmetal to enhance the performance of the hardmetal.
FIG. 1 is a flowchart for this implementation of the fabrication process. - In one implementation, the manufacture process for cemented carbides includes wet milling in solvent, vacuum drying, pressing, and liquid-phase sintering in vacuum. The temperature of the liquid-phase sintering is between melting point of the binder material (e.g., Co at 1495° C.) and the eutectic temperature of the mixture of hardmetal (e.g., WC—Co at 1320° C.). In general, the sintering temperature of cemented carbide is in a range of 1360 to 1480° C. For new materials with low concentration of Re or a Ni-based superalloy in binder alloy, manufacture process is same as conventional cemented carbide process. The principle of liquid phase sintering in vacuum is applied in here. The sintering temperature is slightly higher than the eutectic temperature of binder alloy and carbide. For example, the sintering condition of P17 (25% of Re in binder alloy, by weight) is at 1700° C. for one hour in vacuum.
-
FIG. 2 shows a two-step fabrication process based on a solid-state phase sintering for fabricating various hardmetals described in this application. Examples of hardmetals that can be fabricated with this two-step sintering method include hardmetals with a high concentration of Re in the binder matrix that would otherwise require the liquid-phase sintering at high temperatures. This two-step process may be implemented at relatively low temperatures, e.g., under 2200° C., to utilize commercially feasible ovens and to produce the hardmetals at reasonably low costs. The liquid phase sintering is eliminated in this two-step process because the liquid phase sintering may not be practical due to the generally high eutectic temperatures of the binder alloy and carbide. As discussed above, sintering at such high temperatures requires ovens operating at high temperatures which may not be commercially feasible. - The first step of this two-step process is a vacuum sintering where the mixture materials for the binder matrix and the hard particles are sintered in vacuum. The mixture is initially processed by, e.g., wet milling, drying, and pressing, as performed in conventional processes for fabricating cemented carbides. This first step of sintering is performed at a temperature below the eutectic temperature of the binder alloy and the hard particle materials to remove or eliminate the interconnected porosity. The second step is a solid phase sintering at a temperature below the eutectic temperature and under a pressured condition to remove and eliminate the remaining porosities and voids left in the sintered mixture after the first step. A hot isostatic pressing (HIP) process may be used as this second step sintering. Both heat and pressure are applied to the material during the sintering to reduce the processing temperature which would otherwise be higher in absence of the pressure. A gas medium such as an inert gas may be used to apply and transmit the pressure to the sintered mixture. The pressure may be at or over 1000 bar. Application of pressure in the HIP process lowers the required processing temperature and allows for use of conventional ovens or furnaces. The temperatures of solid phase sintering and HIPping for achieving fully condensed materials are generally significantly lower than the temperatures for liquid phase sintering. For example, the sample P62 which uses pure Re as the binder may be fully densified by vacuum sintering at 2200° C. for one to two hours and then HIPping at about 2000° C. under a pressure of 30,000 PSI in the inert gas such as Ar for about one hour. Notably, the use of ultra fine hard particles with a particulate dimension less than 0.5 micron can reduce the sintering temperature for fully densifying the hardmetals (fine particles are several microns in size). For example, in making the samples P62 and P63, the use of such ultra fine WC allows for sintering temperatures to be low, e.g., around 2000° C. This two-step process is less expensive than the ROC method and may be used to commercial production.
- The following sections describe exemplary hardmetal compositions and their properties based on various binder matrix materials that include at least rhenium or a nickel-based superalloy.
- TABLE 2 provides a list of code names (lot numbers) for some of the constituent materials used to form the exemplary hardmetals, where H1 represents rhenium, and L1, L2, and L3 represent three exemplary commercial nickel-based superalloys. TABLE 3 further lists compositions of the above three exemplary nickel-based superalloys, Udimet720 (U720), Rene'95 (R-95), and Udimet700 (U700), respectively. TABLE 4 lists compositions of exemplary hardmetals, both with and without rhenium or a nickel-based superalloy in the binder matrices. For example, the material composition for Lot P17 primarily includes 88 grams of T32 (WC), 3 grams of 132 (TiC), 3 grams of A31 (TaC), 1.5 grams of H1 (Re) and 4.5 grams of L2 (R-95) as binder, and 2 grams of a wax as lubricant. Lot P58 represents a hardmetal with a nickel-based superalloy L2 as the only binder material without Re. These hardmetals were fabricated and tested to illustrate the effects of either or both of rhenium and a nickel-based superalloy as binder materials on various properties of the resulting hardmetals. TABLES 5-8 further provide summary information of compositions and properties of different sample lots as defined above.
-
FIGS. 3 through 8 show measurements of selected hardmetal samples of this application.FIGS. 3 and 4 show measured toughness and hardness parameters of some exemplary hardmetals for the steel cutting grades.FIGS. 5 and 6 show measured toughness and hardness parameters of some exemplary hardmetals for the non-ferrous cutting grades. Measurements were performed before and after the solid-phase sintering HIP process and the data suggests that the HIP process significantly improves both the toughness and the hardness of the materials.FIG. 7 shows measurements of the hardness as a function of temperature for some samples. As a comparison,FIGS. 7 and 8 also show measurements of commercial C2 and C6 carbides under the same testing conditions, whereFIG. 7 shows the measured hardness andFIG. 8 shows measured change in hardness from the value at the room temperature (RT). Clearly, the hardmetal samples based on the compositions described here outperform the commercial grade materials in terms of the hardness at high temperatures. These results demonstrate that the superior performance of binder matrices with either or both of Re and a nickel-based superalloy as binder materials in comparison with Co-based binder matrix materials. -
TABLE 2 Powder Code Composition Note T32 WC Particle size 1.5 μm, from Alldyne T35 WC Particle size 15 μm, from Alldyne Y20 Mo Particle size 1.7-2.2 μm, from Alldyne L3 U-700 −325 Mesh, special metal Udimet 700 L1 U-720 −325 Mesh, Special Metal, Udimet 720 L2 Re-95 −325 Mesh, Special Metal, Rene 95 H1 Re −325 Mesh, Rhenium Alloy Inc. I32 TiC from AEE, Ti − 302 I21 TiB2 from AEE, Ti − 201, 1-5 μm A31 TaC from AEE, TA − 301 Y31 Mo2C from AEE, MO − 301 D31 VC from AEE, VA − 301 B1 Co from AEE, CO − 101 K1 Ni from AEE, Ni − 101 K2 Ni from AEE, Ni − 102 I13 TiN from Cerac, T − 1153 C21 ZrB2 from Cerac, Z − 1031 Y6 Mo from AEE Mo + 100, 1-2 μm L6 Al from AEE Al − 100, 1-5 μm R31 B4C from AEE Bo − 301, 3 μmT3.8 WC Particle size 0.8 μm, Alldyne T3.4 WC Particle size 0.4 μm, OMG T3.2 WC Particle size 0.2 μm, OMG -
TABLE 3 Ni Co Cr Al Ti Mo Nb W Zr B C V R95 61.982 8.04 13.16 3.54 2.53 3.55 3.55 3.54 0.049 0.059 U700 54.331 17.34 15.35 4.04 3.65 5.17 .028 .008 .04 .019 .019 .005 U720 56.334 15.32 16.38 3.06 5.04 3.06 0.01 1.30 .035 .015 .012 .004 -
TABLE 4 Lot No Composition (units in grams) P17 H1 = 1.5, L2 = 4.5, I32 = 3, A31 = 3, T32 = 88, Wax = 2 P18 H1 = 3, L2 = 3, I32 = 3, A31 = 3, T32 = 88, Wax = 2 P19 H1 = 1.5, L3 = 4.5, I32 = 3, A31 = 3, T32 = 88, Wax = 2 P20 H1 = 3, L3 = 3, I32 = 3, A31 = 3, T32 = 88, Wax = 2 P25 H1 = 3.75, L2 = 2.25, I32 = 3, A31 = 3, T32 = 88, Wax = 2 P25A H1 = 3.75, L2 = 2.25, I32 = 3, A31 = 3, T32 = 88, Wax = 2 P31 H1 = 3.44, B1 = 4.4, T32 = 92.16, Wax = 2 P32 H1 = 6.75, B1 = 2.88, T32 = 90.37, Wax = 2 P33 H1 = 9.93, B1 = 1.41, T32 = 88.66, Wax = 2 P34 L2 = 14.47, I32 = 69.44, Y31 = 16.09 P35 H1 = 8.77, L2 = 10.27, I32 = 65.73, Y31 = 15.23 P36 H1 = 16.66, L2 = 6.50, I32 = 62.4, Y31 = 14.56 P37 H1 = 23.80, L2 = 3.09, I32 = 59.38, Y31 = 13.76 P38 K1 = 15.51, I32 = 68.60, Y31 = 15.89 P39 K2 = 15.51, I32 = 68.60, Y31 = 15.89 P40 H1 = 7.57, L2 = 2.96, I32 = 5.32, A31 = 5.23, T32 = 78.92, Wax = 2 P40A H1 = 7.57, L2 = 2.96, I32 = 5.32, A31 = 5.23, T32 = 78.92, Wax = 2 P41 H1 = 11.1, L2 = 1.45, I32 = 5.20, A31 = 5.11, T32 = 77.14, Wax = 2 P41A H1 = 11.1, L2 = 1.45, I32 = 5.20, A31 = 5.11, T32 = 77.14, Wax = 2 P42 H1 = 9.32, L2 = 3.64, I32 = 6.55, A31 = 6.44, I21 = 0.40, R31 = 4.25, T32 = 69.40, P43 H1 = 9.04, L2 = 3.53, I32 = 6.35, A31 = 6.24, I21 = 7.39, R31 = 0.22, T32 = 67.24, P44 H1 = 8.96, L2 = 3.50, I32 = 14.69, A31 = 6.19, T32 = 66.67, Wax = 2 P45 H1 = 9.37, L2 = 3.66, I32 = 15.37, A31 = 6.47, Y31 = 6.51, T32 = 58.61, Wax = 2 P46 H1 = 11.40, L2 = 4.45, I32 = 5.34, A31 = 5.25, T32 = 73.55, Wax = 2 P46A H1 = 11.40, L2 = 4.45, I32 = 5.34, A31 = 5.25, T32 = 73.55, Wax = 2 P47 H1 = 11.35, B1 = 4.88, I32 = 5.32, A31 = 5.23, T32 = 73.22, Wax = 2 P47A H1 = 11.35, B1 = 4.88, I32 = 5.32, A31 = 5.23, T32 = 73.22, Wax = 2 P48 H1 = 3.75, L2 = 2.25, I32 = 5, A31 = 5, T32 = 84, Wax = 2 P49 H1 = 7.55, B1 = 3.25, I32 = 5.31, A31 = 5.21, T32 = 78.68, Wax = 2 P50 H1 = 4.83, L2 = 1.89, I32 = 5.31, A31 = 5.22, T32 = 82.75, Wax = 2 P51 H1 = 7.15, L2 = 0.93, I32 = 5.23, A31 = 5.14, T32 = 81.55, Wax = 2 P52 B1 = 8, D31 = 0.6, T3.8 = 91.4, Wax = 2 P53 B1 = 8, D31 = 0.6, T3.4 = 91.4, Wax = 2 P54 B1 = 8, D31 = 0.6, T3.2 = 91.4, Wax = 2 P55 H1 = 1.8, B1 = 7.2, D31 = 0.6, T3.4 = 90.4, Wax = 2 P56 H1 = 1.8, B1 = 7.2, D31 = 0.6, T3.2 = 90.4, Wax = 2 P56A H1 = 1.8, B1 = 7.2, D31 = 0.6, T3.2 = 90.4, Wax = 2 P57 H1 = 1.8, B1 = 7.2, T3.2 = 91, Wax = 2 P58 L2 = 7.5, D31 = 0.6, T3.2 = 91.9, Wax = 2 P59 H1 = 0.4, B1 = 3, L2 = 4.5, D31 = 0.6, T3.2 = 91.5, Wax = 2 P62 H1 = 14.48, I32 = 5.09, A31 = 5.00, T3.2 = 75.43, Wax = 2 P62A H1 = 14.48, I32 = 5.09, A31 = 5.00, T3.2 = 75.43, Wax = 2 P63 H1 = 12.47, L2 = 0.86, I32 = 5.16, A31 = 5.07, T3.2 = 76.45, Wax = 2 P65 H1 = 7.57, L2 = 2.96, I32 = 5.32, A31 = 5.23, T3.2 = 78.92, Wax = 2 P65A H1 = 7.57, L2 = 2.96, I32 = 5.32, A31 = 5.23, T3.2 = 78.92, Wax = 2 P66 H1 = 27.92, I32 = 4.91, A31 = 4.82, T3.2 = 62.35, Wax = 2 P67 H1 = 24.37, L3 = 1.62, I32 = 5.04, A31 = 4.95, T32 = 32.01, T33 = 32.01, Wax = 2 P69 L2 = 7.5, D31 = 0.4, T3.2 = 92.1, Wax = 2 P70 L1 = 7.4, D31 = 0.3, T3.2 = 92.3, Wax = 2 P71 L3 = 7.2, D31 = 0.3, T3.2 = 92.5, Wax = 2 P72 H1 = 1.8, B1 = 7.2, D31 = 0.3, T3.2 = 90.7, Wax = 2 P73 H1 = 1.8, B1 = 4.8, L2 = 2.7, D31 = 0.3, T3.2 = 90.4, Wax = 2 P74 H1 = 1.8, B1 = 3, L2 = 4.5, D31 = 0.3, T3.2 = 90.4, Wax = 2 P75 H1 = 0.8, B1 = 3, L2 = 4.5, D31 = 0.3, T3.2 = 91.4, Wax = 2 P76 H1 = 0.8, B1 = 3, L1 = 4.5, D31 = 0.3, T3.2 = 91.4, Wax = 2 P77 H1 = 0.8, B1 = 3, L3 = 4.5, D31 = 0.3, T3.2 = 91.4, Wax = 2 P78 H1 = 0.8, B1 = 4.5, L1 = 3, D31 = 0.3, T3.2 = 91.4, Wax = 2 P79 H1 = 0.8, B1 = 4.5, L3 = 3.1, D31 = 0.3, T3.2 = 91.3, Wax = 2 - Several exemplary categories of hardmetal compositions are described below to illustrate the above general designs of the various hardmetal compositions to include either of Re and Nickel-based superalloy, or both. The exemplary categories of hardmetal compositions are defined based on the compositions of the binder matrices for the resulting hardmetals or cermets. The first category uses a binder matrix having pure Re, the second category uses a binder matrix having a Re—Co alloy, the third category uses a binder matrix having a Ni-based superalloy, and the fourth category uses a binder matrix having an alloy having a Ni-based superalloy in combination with of Re with or without Co.
- In general, hard and refractory particles used in hardmetals of interest may include, but are not limited to, Carbides, Nitrides, Carbonitrides, Borides, and Silicides. Some examples of Carbides include WC, TiC, TaC, HfC, NbC, Mo2C, Cr2C3, VC, ZrC, B4C, and SiC. Examples of Nitrides include TiN, ZrN, HfN, VN, NbN, TaN, and BN. Examples of Carbonitrides include Ti(C,N), Ta(C,N), Nb(C,N), Hf(C,N), Zr(C,N), and V(C,N). Examples of Borides include TiB2, ZrB2, HfB2, TaB2, VB2, MoB2, WB, and W2B. In addition, examples of Silicides are TaSi2, WSi2, NbSi2, and MoSi2. The above-identified four categories of hardmetals or cermets can also use these and other hard and refractory particles.
- In the first category of hardmetals based on the pure Re alloy binder matrix, the Re may be approximately from 5% to 40% by volume of all material compositions used in a hardmetal or cermet. For example, the sample with a lot No. P62 in TABLE 4 has 10% of pure Re, 70% of WC, 15% of TiC, and 5% of TaC by volume. This composition approximately corresponds to 14.48% of Re, 75.43% of WC, 5.09% of TiC and 5.0% of TaC by weight. In fabrication, the Specimen P62-4 was vacuum sintered at 2100° C. for about one hour and 2158° C. for about one hour. The density of this material is about 14.51 g/cc, where the calculated density is 14.50 g/cc. The average hardness Hv is 2627±35 Kg/mm2 for 10 measurements taken at the room temperature under a load of 10 Kg. The measured surface fracture toughness Ksc is about 7.4×106 Pa·m1/2 estimated by Palmvist crack length at a load of 10 Kg.
- Another example under this category is P66 in TABLE 4. This sample has about 20% of Re, 60% of WC, 15% of TiC, and 5% of TaC by volume in composition. In the weight percentage, this sample has about 27.92% of Re, 62.35% of WC, 4.91% of TiC, and 4.82% of TaC. The Specimen P66-4 was first processed with a vacuum sintering process at about 2200° C. for one hour and was then sintered in the solid-phase with a HIP process to remove porosities and voids. The density of the resulting hardmetal is about 14.40 g/cc compared to the calculated density of 15.04 g/cc. The average hardness Hv is about 2402±44 Kg/mm2 for 7 different measurements taken at the room temperature under a load of 10 Kg. The surface fracture toughness Ksc is about 8.1×106 Pa·m1/2.
- The sample P66 and other compositions described here with a high concentration of Re with a weight percentage greater than 25%, as the sole binder material or one of two or more different binder materials in the binder, may be used for various applications at high operating temperatures and may be manufactured by using the two-step process based on solid-phase sintering.
- The microstructures and properties of Re bound multiples types of hard refractory particles, such as carbides, nitrides, carbonnitrides, suicides, and bobides, may provide advantages over Re-bound WC material. For example, Re bound WC—TiC—TaC may have better crater resistance in steel cutting than Re bound WC material. Another example is materials formed by refractory particles of Mo2C and TiC bound in a Re binder.
- For the second category with a Re—Co alloy as the binder matrix, the Re—Co alloy may be about from 5 to 40 Vol % of all material compositions used in the composition. In some implementations, the Re-to-Co ratio in the binder may vary from 0.01 to 0.99 approximately. Inclusion of Re can improve the mechanical properties of the resulting hardmetals, such as hardness, strength and toughness special at high temperature compared to Co bounded hardmetal. The higher Re content is the better high temperature properties are for most materials using such a binder matrix.
- The sample P31 in TABLE 4 is one example within this category with 2.5% of Re, 7.5% of Co, and 90% of WC by volume, and 3.44% of Re, 4.40% of Co and 92.12% of WC by weight. In fabrication, the Specimen P31-1 was vacuum sintered at 1725 C for about one hour. slight under sintering with some porosities and voids. The density of the resulting hardmetal is about 15.16 g/cc (calculated density at 15.27 g/cc). The average hardness Hv is about 1889±18 Kg/mm2 at the room temperature under 10 Kg and the surface fracture toughness Ksc is about 7.7×106 Pa·m1/2. In addition, the Specimen P31-1 was treated with a hot isostatic press (HIP) process at about 160° C./15 Ksi for about one hour after sintering. The HIP reduces or substantially eliminates the porosities and voids in the compound to increase the material density. After HIP, the measured density is about 15.25 g/cc (calculated density at 15.27 g/cc). The measured hardness Hv is about 1887±12 Kg/mm2 at the room temperature under 10 Kg. The surface fracture toughness Ksc is about 7.6×106 Pa·m1/2.
- Another example in this category is P32 in TABLE 4 with 5.0% of Re, 5.0% of Co, and 90% of WC in volume (6.75% of Re, 2.88% of Co and 90.38% of WC in weight). The Specimen P32-4 was vacuum sintered at 1800 C for about one hour. The measured density is about 15.58 g/cc in comparison with the calculated density at 15.57 g/cc. The measured hardness Hv is about 2065 Kg/mm2 at the room temperature under 10 Kg. The surface fracture toughness Ksc is about 5.9×106 Pa·m1/2. The Specimen P32-4 was also HIP at 1600 C/15 Ksi for about one hour after Sintering. The measured density is about 15.57 g/cc (calculated density at 15.57 g/cc). The average hardness Hv is about 2010±12 Kg/mm2 at the room temperature under 10 Kg. The surface fracture toughness Ksc is about 5.8×106 Pa·m1/2.
- The third example is P33 in TABLE 4 which has 7.5% of Re, 2.5% of Co, and 90% of WC by volume and 9.93% of Re, 1.41% of Co and 88.66% of WC by weight. In fabrication, the Specimen P33-7 was vacuum sintered at 1950 C for about one hour and was under sintering with porosities and voids. The measured density is about 15.38 g/cc (calculated density at 15.87 g/cc). The measured hardness Hv is about 2081 Kg/mm2 at the room temperature under a force of 10 Kg. The surface fracture toughness Ksc is about 5.6×106 Pa·m1/2. The Specimen P33-7 was HIP at 1600 C/15 Ksi for about one hour after Sintering. The measured density is about 15.82 g/cc (calculated density=15.87 g/cc). The average hardness Hv is measured at about 2039±18 Kg/mm2 at the room temperature under 10 Kg. The surface fracture toughness Ksc is about 6.5×106 Pa·m1/2.
-
TABLE 5 Re—Co alloy bound hardmetals Density Temperature g/cc Hv ° C. Calcu- Meas- Kg/ Ksc ×106 Grain Sinter HIP lated ured mm2 Pa · m1/2 size P55-1 1350 1300 14.77 14.79 2047 8.6 Ultra-fine P56-5 1360 1300 14.77 14.72 2133 8.6 Ultra-fine P56A-4 1350 1300 14.77 14.71 2108 8.5 Ultra-fine P57-1 1350 1300 14.91 14.93 1747 12.3 Fine - The samples P55, P56, P56A, and P57 in TABLE 4 are also examples for the category with a Re—Co alloy as the binder matrix. These samples have about 1.8% of Re, 7.2% of Co, 0.6% of VC except that P57 has no VC, and finally WC in balance. These different compositions are made to study the effects of hardmetal grain size on Hv and Ksc. TABLE 5 lists the results.
-
TABLE 6 Properties of Ni-based superalloys, Ni, Re, and Co Test Temp. C. R-95 U-700 U720 Nickel Rhenium Cobalt Density 21 8.2 7.9 8.1 8.9 21 8.9 (g/c.c.) Melting 1255 1205 1210 1450 3180 1495 Point (° C.) Elastic 21 30.3 32.4 32.2 207 460 211 Modulus (Gpa) Ultimate 21 1620 1410 1570 317 1069 234 Tensile 760 1170 1035 1455 Strength 800 620 (Mpa) 870 690 1150 1200 414 0.2% 21 1310 965 1195 60 Yield 760 1100 825 1050 Strength 800 (Mpa) 870 635 1200 Tensile 21 15 17 13 30 >15 Elongation 760 15 20 9 (%) 800 5 870 27 1200 2 Oxidation Excellent Excellent Excellent Good Poor Good Resistance - The third category is based on binder matrices with Ni-based superalloys from 5 to 40% in volume of all materials in the resulting hardmetal. Ni-based superalloys are a family of high temperature alloys with γ′ strengthening. Three different strength alloys, Rene'95, Udimet 720, and Udimet 700 are used as examples to demonstrate binder strength effects on mechanical properties of hardmetals. The Ni-based superalloys have a high strength specially at elevated temperatures. Also, these alloys have good environmental resistance such as resistance to corrosion and oxidation at elevated temperature. Therefore, Ni-based superalloys can be used to increase the hardness of Ni-based superalloy bound hardmetals when compared to Cobalt bound hardmetals. Notably, the tensile strengths of the Ni-based superalloys are much stronger than the common binder material cobalt as shown by TABLE 6. This further shows that Ni-based superalloys are good binder materials for hardmetals.
- One example for this category is P58 in TABLE 4 which has 7.5% of Rene'95, 0.6% of VC, and 91.9% of WC in weight and compares to cobalt bound P54 in TABLE 4 (8% of Co, 0.6% of VC, and 91.4% of WC). The hardness of P58 is significant higher than P54 as shown in TABLE 7.
-
TABLE 7 Comparison of P54 and P58 Hv, Ksc ×106 Sintering HIP Kg/mm2 Pa · m1/2 P54-1 1350 C./1 hr 1305° C. 2094 8.8 P54-2 1380 C./1 hr 15 KSI 2071 7.8 P54-3 1420 C./1 hr under Ar 2107 8.5 P58-1 1350, 1380, 1400, 1420, 1 hour 2322 7.0 1450, 1475 for 1 hour at each temperature P58-3 1450 C./1 hr 2272 7.4 P58-5 1500 C./1 hr 2259 7.2 P58-7 1550 C./1 hr 2246 7.3 - The fourth category is Ni-based superalloy plus Re as binder, e.g., approximately from 5% to 40% by volume of all materials in the resulting hardmetal or cermet. Because addition of Re increases the melting point of binder alloy of Ni-based superalloy plus Re, the processing temperature of hardmetal with Ni-based superalloy plus Re binder increases as the Re content increases. Several hardmetals with different Re concentrations are listed in TABLE 8. TABLE 9 further shows the measured properties of the hardmetals in TABLE 8.
-
TABLE 8 Hardmetal with Ni-based superalloy plus Re binder Sintering Composition, weight % Re to Binder Temperature Re Rene95 U-700 U-720 WC TiC TaC Ratio ° C. P17 1.5 4.5 88 3 3 25% 1600~1750 P18 3 3.0 88 3 3 50% 1600~1775 P25 3.75 2.25 88 3 3 62.5% 1650~1825 P48 3.75 2.25 84 5 5 62.5% 1650~1825 P50 4.83 1.89 82.75 5.31 5.22 71.9% 1675~1850 P40 7.57 2.96 78.92 5.32 5.23 71.9% 1675~1850 P46 11.40 4.45 73.55 5.34 5.24 71.9% 1675~1850 P51 7.15 0.93 81.55 5.23 5.14 88.5% 1700~1900 P41 11.10 1.45 77.14 5.20 5.11 88.5% 1700~1900 P63 12.47 0.86 76.45 5.16 5.07 93.6% 1850~2100 P19 1.5 4.5 88 3 3 25% 1600~1750 P20 3 3 88 3 3 50% 1600~1775 P67 24.37 1.62 64.02 5.04 4.95 93.6% 1950~2300 -
TABLE 9 Properties of hardmetals bound by Ni-based superalloy and Re Temperature, C. Density, g/cc Hv Ksc ×106 Sinter HIP Calculated Measured Kg/mm2 Pa · m1/2 P17 1700 14.15 14.18 2120 6.8 P17 1700 1600 14.15 14.21 2092 7.2 P18 1700 14.38 14.47 2168 5.9 P18 1700 1600 14.38 14.42 2142 6.1 P25 1750 14.49 14.41 2271 6.1 P25 1750 1600 14.49 14.48 2193 6.5 P48 1800 1600 13.91 13.99 2208 6.3 P50 1800 1600 13.9 13.78 2321 6.5 P40 1800 13.86 13.82 2343 P40 1800 1600 13.86 13.86 2321 6.3 P46 1800 13.81 13.88 2282 7.1 P46 1800 1725 13.81 13.82 2326 6.7 P51 1800 1600 14.11 13.97 2309 6.6 P41 1800 1600 14.18 14.63 2321 6.5 P63 2000 14.31 14.37 2557 7.9 P19 1700 14.11 14.11 2059 7.6 P19 1700 1600 14.11 2012 8.0 P20 1725 14.35 14.52 2221 6.4 P20 1725 1600 14.35 14.35 2151 7.0 P67 2200 14.65 14.21 2113 8.1 P67 2200 1725 14.65 14.34 2210 7.1 - Another example under the fourth category uses a Ni-based superalloy plus Re and Co as binder which is also about 5% to 40% by volume. Exemplary compositions of hardmetals bound by Ni-based superalloy plus Re and Co are list in TABLE 10.
-
TABLE 10 Composition of hardmetals bound by Ni-based superalloy plus Re and Co Composition, weight % Re Co Rene95 U-720 U-700 WC VC P73 1.8 4.8 2.7 90.4 0.3 P74 1.8 3 4.5 90.4 0.3 P75 0.8 3 4.5 91.4 0.3 P76 0.8 3 4.5 91.4 0.3 P77 0.8 3 4.5 91.4 0.3 P78 0.8 4.5 3 91.4 0.3 P79 0.8 4.5 3.1 91.3 0.3 - Measurements on selected samples have been performed to study properties of the binder matrices with Ni-based superalloys. In general, Ni-based superalloys not only exhibit excellent strengths at elevated temperatures but also possess outstanding resistances to oxidation and corrosion at high temperatures. Ni-based superalloys have complex microstructures and strengthening mechanisms. In general, the strengthening of Ni-based superalloys is primarily due to precipitation strengthening of γ-γ′ and solid-solution strengthening. The measurements the selected samples demonstrate that Ni-based superalloys can be used as a high-performance binder materials for hardmetals.
- TABLE 11 lists compositions of selected samples by their weight percentages of the total weight of the hardmetals. The WC particles in the samples are 0.2 μm in size. TABLE 12 lists the conditions for the two-step process performed and measured densities, hardness parameters, and toughness parameters of the samples. The Palmqvist fracture toughness Ksc is calculated from the total crack length of Palmqvist crack which is produced by the Vicker Indentor: Ksc=0.087*(Hv*W)1/2. See, e.g., Warren and H. Matzke, Proceedings Of the International Conference On the Science of Hard Materials, Jackson, Wyo., Aug. 23-28, 1981. Hardness Hv and Crack Length are measured at a load of 10 Kg for 15 seconds. During each measurement, eight indentations were made on each specimen and the average value was used in computation of the listed data.
-
TABLE 11 Weight % Re in Vol % Re Co R-95 WC VC Binder Binder P54 0 8 0 91.4 0.6 0 13.13 P58 0 0 7.5 91.9 0.6 0 13.25 P56 1.8 7.2 0 90.4 0.6 20 13.20 P72 1.8 7.2 0 90.7 0.3 20 13.18 P73 1.8 4.8 2.7 90.4 0.3 20 14.00 P74 1.8 3 4.5 90.4 0.3 20 14.24 -
TABLE 12 Palmqvist Cal. Measu. Toughness Sample Sinter HIP Density Density Hardness, Hv Ksc, ×106 Code Condition Condition g/c.c. g/c.c. Kg/mm2 Pa · m1/2 P54-5 1360° C./1 hr 14.63 14.58 2062 ± 35 8.9 ± 0.2 1360° C./1 hr 1305° C./15 KSI/1 hr 14.55 2090 ± 22 8.5 ± 0.2 P58-7 1550° C./1 hr 14.50 14.40 2064 ± 12 7.9 ± 0.2 1550° C./1 hr 1305° C./15 KSI/1 hr 14.49 2246 ± 23 7.3 ± 0.1 P56-5 1360° C./1 hr 14.77 14.71 2064 ± 23 8.2 ± 0.1 1360° C./1 hr 1305° C./15 KSI/1 hr 14.72 2133 ± 34 8.6 ± 0.2 P72-6 1475° C./1 hr 14.83 14.77 2036 ± 34 8.5 ± 0.6 1475° C./1 hr 1305° C./15 KSI/1 hr 14.91 2041 ± 30 9.1 ± 0.4 P73-6 1475° C./1 hr 14.73 14.70 2195 ± 23 7.7 ± 0.1 1475° C./1 hr 1305° C./15 KSI/1 hr 14.72 2217 ± 25 8.1 ± 0.2 P74-5 1500° C./1 hr and 14.69 14.69 2173 ± 30 7.4 ± 0.3 1520° C./1 hr 1500° C./1 hr and 1305° C./15 KSI/1 hr 14.74 2223 ± 34 7.7 ± 0.1 1520° C./1 hr - Among the tested samples, the sample P54 uses the conventional binder consisting of Co. The Ni-superalloy R-95 is used in the sample P58 to replace Co as the binder in the sample P54. As a result, the Hv increases from 2090 of P54 to 2246 of P58. In the sample P56, the mixture of Re and Co is used to replace Co as binder and the corresponding Hv increases from 2090 of P54 to 2133 of P56. The samples P72, P73, P74 have the same Re content but different amounts of Co and R95. The mixtures of Re, Co, and R95 are used in samples P73 and P74 to replace the binder having a mixture of Re and Co as the binder in the sample 72. The hardness Hv increases from 2041 (P72) to 2217 (P73) and 2223 (P74).
-
TABLE 13 Weight % WC WC Re in Vol. % Re R-95 Co TiC TaC (2 μm) (0.2 μm) Binder Binder P17 1.5 4.5 0 3 3 88 0 25 8.78 P18 3 3 0 3 3 88 0 50 7.31 P25 3.75 2.25 0 3 3 88 0 62.5 6.57 P48 3.75 2.25 0 5 5 84 0 62.5 6.3 P50 4.83 1.89 0 5.31 5.22 82.75 0 71.9 6.4 P51 7.15 0.93 0 5.23 5.14 81.55 0 88.5 6.4 P49 7.55 0 3.25 5.31 5.21 78.68 0 69.9 10 P40A 7.57 2.96 0 5.32 5.23 78.92 0 71.9 10 P63 12.47 0.86 0 5.16 5.07 0 76.45 93.6 10 P62A 14.48 0 0 5.09 5.00 0 75.43 100 10 P66 27.92 0 0 4.91 4.82 0 62.35 100 20 - Measurements on selected samples have also been performed to further study properties of the binder matrices with Re in the binder matrices. TABLE 13 lists the tested samples. The WC particles with two different particle sizes of 2 μm and 0.2 μm were used. TABLE 14 lists the conditions for the two-step process performed and the measured densities, hardness parameters, and toughness parameters of the selected samples.
-
TABLE 14 Cal. Measu. Palmqvist Sample Sinter HIP Density Density Hardness, Hv Toughness** Code Condition Condition g/c.c. g/c.c. Kg/mm2 Ksc, MPam0.5 P17-5 1800° C./1 hr 1600° C./15 KSI/1 hr 14.15 14.21 2092 ± 3 7.2 ± 0.1 P18-3 1800° C./1 hr 1600° C./15 KSI/1 hr 14.38 14.59 2028 ± 88 6.8 ± 0.3 P25-3 1750° C./1 hr 1600° C./15 KSI/1 hr 14.49 14.48 2193 ± 8 6.5 ± 0.1 P48-1 1800° C./1 hr 1600° C./15 KSI/1 hr 13.91 13.99 2208 ± 12 6.3 ± 0.4 P50-4 1800° C./1 hr 1600° C./15 KSI/1 hr 13.9 13.8 2294 ± 20 6.3 ± 0.1 P51-1 1800° C./1 hr 1600° C./15 KSI/1 hr 14.11 13.97 2309 ± 6 6.6 ± 0.1 P40A-1 1800° C./1 hr 1600° C./15 KSI/1 hr 13.86 13.86 2321 ± 10 6.3 ± 0.1 P49-1 1800° C./1 hr 1600° C./15 KSI/1 hr 13.91 13.92 2186 ± 29 6.5 ± 0.2 P62A-6 2200° C./1 hr 1725° C./30 KSI/1 hr 14.5 14.41 2688 ± 22 6.7 ± 0.1 P63-5 2200° C./1 hr 1725° C./30 KSI/1 hr 14.31 14.37 2562 ± 31 6.7 ± 0.2 P66-4 2200° C./1 hr 15.04 14.40 2402 ± 44 8.2 ± 0.4 P66-4 2200° C./1 hr 1725° C./30 KSI/1 hr 15.04 14.52 P66-4 2200° C./1 hr 1725° C./30 KSI/1 hr + 15.04 14.53 2438 ± 47 6.9 ± 0.2 1950° C./30 KSI/1 hr P66-5 2200° C./1 hr 15.04 14.33 2092 ± 23 7.3 ± 0.3 P66-5 2200° C./1 hr 1725° C./30 KSI/1 hr 15.04 14.63 P66-5 2200° C./1 hr 1725° C./30 KSI/1 hr + 15.04 14.66 2207 ± 17 7.1 ± 0.2 1850° C./30 KSI/1 hr - TABLE 15 further shows measured hardness parameters under various temperatures for the selected samples, where the Knoop hardness Hk were measured under a load of 1 Kg for 15 seconds on a Nikon QM hot hardness tester and R is a ratio of Hk at an elevated testing temperature over Hk at 25° C. The hot hardness specimens of C2 and C6 carbides were prepared from inserts SNU434 which were purchased from MSC Co. (Melville, N.Y.).
-
TABLE 15 (each measured value at a given temperature is an averaged value of 3 different measurements) Testing Temperature, ° C. Lot No. 25 400 500 600 700 800 900 Hv @25° P17-5 Hk, Kg/mm2 1880 ± 10 1720 ± 17 1653 ± 25 1553 ± 29 1527 ± 6 2092 ± 3 R, % 100 91 88 83 81 P18-3 Hk, Kg/mm2 1773 ± 32 1513 ± 12 1467 ± 21 1440 ± 10 1340 ± 16 2028 ± 88 R, % 100 85 83 81 76 P25-3 Hk, Kg/mm2 1968 ± 45 1813 ± 12 1710 ± 0 1593 ± 5 2193 ± 8 R, % 100 92 87 81 P40A-1 Hk, Kg/mm2 2000 ± 35 1700 ± 17 1663 ± 12 1583 ± 21 1540 ± 35 2321 ± 10 R, % 100 85 83 79 77 P48-1 Hk, Kg/mm2 1925 ± 25 1613 ± 15 1533 ± 29 1477 ± 6 1377 ± 15 2208 ± 12 R, % 100 84 80 77 72 P49-1 Hk, Kg/mm2 2023 ± 32 1750 ± 0 1633 ± 6 1600 ± 17 2186 ± 29 R, % 100 87 81 79 P50-4 Hk, Kg/mm2 2057 ± 25 1857 ± 15 1780 ± 20 1713 ± 6 1627 ± 40 2294 ± 20 R, % 100 90 87 83 79 P51-1 Hk, Kg/mm2 2050 ± 26 1797 ± 6 1743 ± 35 1693 ± 15 1607 ± 15 2309 ± 6 R, % 100 88 85 83 78 P62A-6 Hk, Kg/mm2 2228 ± 29 2063 ± 25 1960 ± 76 1750 ± 0 2688 ± 22 R, % 100 93 88 79 P63-5 Hk, Kg/mm2 1887 ± 6 1707 ± 35 1667 ± 15 1633 ± 6 1603 ± 25 2562 ± 31 R, % 100 C2 Carbide Hk, Kg/mm2 1503 ± 38 988 ± 9 711 ± 0 584 ± 27 1685 ± 16 R, % 100 66 47 39 C6 Carbide Hk, Kg/mm2 1423 ± 23 1127 ± 25 1090 ± 10 1033 ± 23 928 ± 18 1576 ± 11 R, % 100 79 77 73 65 - The inclusion of Re in the binder matrices of the hardmetals increases the melting point of binder alloys that include Co—Re, Ni superalloy-Re, Ni superalloy-Re—Co. For example, the melting point of the sample P63 is much higher than the temperature of 2200° C. used for the solid-phase sintering process. Hot hardness values of such hardmetals with Re in the binders (e.g., P17 to P63) are much higher than conventional Co bound hardmetals (C2 and C6 carbides). In particular, the above measurements reveal that an increase in the concentration of Re in the binder increases the hardness at high temperatures. Among the tested samples, the sample P62A with pure Re as the binder has the highest hardness. The sample P63 with a binder composition of 94% of Re and 6% of the Ni-based superalloy R95 has the second highest hardness. The samples P40A (71.9% Re-29.1% R95), P49 (69.9% Re-30.1% R95), P51 (88.5% Re-11.5% R95), and P50 (71.9% Re-28.1% R95) are the next group in their hardness. The sample P48 with 62.5% of Re and 37.5% of R95 in its binder has the lowest hardness at high temperatures among the tested materials in part because its Re content is the lowest.
- In yet another category, a hardmetal or cermet may include TiC and TiN bonded in a binder matrix having Ni and Mo or Mo2C. The binder Ni of cermet can be fully or partially replaced by Re, by Re plus Co, by Ni-based superalloy, by Re plus Ni-based superalloy, and by Re plus Co and Ni-based superalloy. For example, P38 and P39 are a typical Ni bound cermet. The sample P34 is Rene95 bound Cermet. The P35, P36, P37, and P45 are Re plus Rene95 bound cermet. Compositions of P34, 35, 36, 37, 38, 39, and 45 are list in TABLE 16.
-
TABLE 16 Composition of P34 to P39 Weight % Re Rene95 Ni 1 Ni 2TiC Mo2C WC TaC P34 14.47 69.44 16.09 P35 8.77 10.27 65.37 15.23 P36 16.6 6.50 62.40 14.46 P37 23.8 3.09 59.38 13.76 P38 15.51 68.60 15.89 P39 15.51 68.60 15.89 P45 9.37 3.66 15.37 6.51 58.6 6.47 - The above compositions for hardmetals or cermets may be used for a variety of applications. For example, such a material may be used to form a wear part in a tool that cuts, grinds, or drills a target object by using the wear part to remove the material of the target object. Such a tool may include a support part made of a different material, such as a steel. The wear part is then engaged to the support part as an insert. The tool may be designed to include multiple inserts engaged to the support part. For example, some mining drills may include multiple button bits made of a hardmetal material. Examples of such a tool includes a drill, a cutter such as a knife, a saw, a grinder, a drill. Alternatively, hardmetals descried here may be used to form the entire head of a tool as the wear part for cutting, drilling or other machining operations. The hardmetal particles may also be used to form abrasive grits for polishing or grinding various materials. In addition, such hardmetals may also be used to construct housing and exterior surfaces or layers for various devices to meet specific needs of the operations of the devices or the environmental conditions under which the devices operate.
- More specifically, the hardmetals described here may be used to manufacture cutting tools for machining of metal, composite, plastic and wood. The cutting tools may include indexable inserts for turning, milling, boring and drilling, drills, end mills, reamers, taps, hobs and milling cutters. Since the temperature of the cutting edge of such tools may be higher than 500° C. during machining, the hardmetal compositions for high-temperature operating conditions described above may have special advantages when used in such cutting tools, e.g., extended tool life and improved productivity by such tools by increasing the cutting speed.
- The hardmetals described here may be used to manufacture tools for wire drawing, extrusion, forging and cold heading. Also as mold and Punch for powder process. In addition, such hardmetals may be used as wear-resistant material for rock drilling and mining.
- Only a few implementations and examples are disclosed. However, it is understood that variations and enhancements may be made without departing from the spirit of and are intended to be encompassed by the following claims.
Claims (17)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/099,737 US20080257107A1 (en) | 2003-01-13 | 2008-04-08 | Compositions of Hardmetal Materials with Novel Binders |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US43983803P | 2003-01-13 | 2003-01-13 | |
US44930503P | 2003-02-20 | 2003-02-20 | |
US10/453,085 US6911063B2 (en) | 2003-01-13 | 2003-06-02 | Compositions and fabrication methods for hardmetals |
US10/941,967 US7354548B2 (en) | 2003-01-13 | 2004-09-14 | Fabrication of hardmetals having binders with rhenium or Ni-based superalloy |
US12/099,737 US20080257107A1 (en) | 2003-01-13 | 2008-04-08 | Compositions of Hardmetal Materials with Novel Binders |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/941,967 Division US7354548B2 (en) | 2003-01-13 | 2004-09-14 | Fabrication of hardmetals having binders with rhenium or Ni-based superalloy |
Publications (1)
Publication Number | Publication Date |
---|---|
US20080257107A1 true US20080257107A1 (en) | 2008-10-23 |
Family
ID=32686102
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/453,085 Expired - Lifetime US6911063B2 (en) | 2003-01-13 | 2003-06-02 | Compositions and fabrication methods for hardmetals |
US10/941,967 Expired - Lifetime US7354548B2 (en) | 2003-01-13 | 2004-09-14 | Fabrication of hardmetals having binders with rhenium or Ni-based superalloy |
US12/099,737 Abandoned US20080257107A1 (en) | 2003-01-13 | 2008-04-08 | Compositions of Hardmetal Materials with Novel Binders |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/453,085 Expired - Lifetime US6911063B2 (en) | 2003-01-13 | 2003-06-02 | Compositions and fabrication methods for hardmetals |
US10/941,967 Expired - Lifetime US7354548B2 (en) | 2003-01-13 | 2004-09-14 | Fabrication of hardmetals having binders with rhenium or Ni-based superalloy |
Country Status (11)
Country | Link |
---|---|
US (3) | US6911063B2 (en) |
EP (1) | EP1466025A4 (en) |
JP (2) | JP2006513119A (en) |
KR (1) | KR100857493B1 (en) |
CN (2) | CN1995427B (en) |
AU (1) | AU2003248862A1 (en) |
BR (1) | BR0313898A (en) |
CA (1) | CA2454098C (en) |
IL (2) | IL160248A0 (en) |
TW (1) | TWI279445B (en) |
WO (1) | WO2004065645A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100180514A1 (en) * | 2003-01-13 | 2010-07-22 | Genius Metal, Inc. | High-Performance Hardmetal Materials |
US20120152620A1 (en) * | 2009-07-01 | 2012-06-21 | Atlas Copco Rock Drills Ab | Device and method for protecting the rock drilling machine from corrosion |
CN103981419A (en) * | 2014-04-09 | 2014-08-13 | 宁波东联密封件有限公司 | High-strength titanium carbonitride metal ceramic sealing material and preparation method thereof |
CN105568107A (en) * | 2016-01-29 | 2016-05-11 | 柳州市安龙机械设备有限公司 | Manufacturing method for high wire roll ring |
US9340852B2 (en) | 2011-09-26 | 2016-05-17 | National Tsing Hua University | Elevated refractory alloy with ambient-temperature and low-temperature ductility and method thereof |
RU2689456C2 (en) * | 2014-12-30 | 2019-05-28 | Сандвик Хиперион АБ | Corrosion-resistant cemented carbide for operation with fluids |
CN111424203A (en) * | 2020-03-09 | 2020-07-17 | 株洲鑫品硬质合金股份有限公司 | Ultra-fine grain hard alloy and preparation method thereof |
Families Citing this family (91)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6911063B2 (en) * | 2003-01-13 | 2005-06-28 | Genius Metal, Inc. | Compositions and fabrication methods for hardmetals |
US20070034048A1 (en) * | 2003-01-13 | 2007-02-15 | Liu Shaiw-Rong S | Hardmetal materials for high-temperature applications |
WO2006001791A1 (en) * | 2004-06-10 | 2006-01-05 | Allomet Corporation | Method for consolidating tough coated hard powders |
US7857188B2 (en) * | 2005-03-15 | 2010-12-28 | Worldwide Strategy Holding Limited | High-performance friction stir welding tools |
US9422616B2 (en) * | 2005-08-12 | 2016-08-23 | Kennametal Inc. | Abrasion-resistant weld overlay |
AU2006280936A1 (en) * | 2005-08-19 | 2007-02-22 | Worldwide Strategy Holdings Limited | Hardmetal materials for high-temperature applications |
CA2641029A1 (en) * | 2006-01-31 | 2007-08-09 | Genius Metal, Inc. | High-performance friction stir welding tools |
US8608822B2 (en) | 2006-03-31 | 2013-12-17 | Robert G. Lee | Composite system |
US7687023B1 (en) * | 2006-03-31 | 2010-03-30 | Lee Robert G | Titanium carbide alloy |
US8936751B2 (en) | 2006-03-31 | 2015-01-20 | Robert G. Lee | Composite system |
JP2008087088A (en) * | 2006-09-29 | 2008-04-17 | Denso Corp | Cutting tool and manufacturing method of the same |
US10137502B1 (en) * | 2006-10-20 | 2018-11-27 | Utron Kinetics, LLC | Near net shape combustion driven compaction process and refractory composite material for high temperature applications |
JP4796477B2 (en) * | 2006-11-08 | 2011-10-19 | 山伸工業株式会社 | Steel pipe soil cement pile construction method and composite pile construction method |
US7841259B2 (en) | 2006-12-27 | 2010-11-30 | Baker Hughes Incorporated | Methods of forming bit bodies |
DE102007004937B4 (en) * | 2007-01-26 | 2008-10-23 | H.C. Starck Gmbh | metal formulations |
US8512882B2 (en) | 2007-02-19 | 2013-08-20 | TDY Industries, LLC | Carbide cutting insert |
WO2009032989A1 (en) * | 2007-09-06 | 2009-03-12 | Shaiw-Rong Scott Liu | Kinetic energy penetrator |
TWI347978B (en) * | 2007-09-19 | 2011-09-01 | Ind Tech Res Inst | Ultra-hard composite material and method for manufacturing the same |
US8361178B2 (en) * | 2008-04-21 | 2013-01-29 | Smith International, Inc. | Tungsten rhenium compounds and composites and methods for forming the same |
SE533070C2 (en) * | 2008-11-10 | 2010-06-22 | Seco Tools Ab | Ways to make cutting tools |
US8440314B2 (en) | 2009-08-25 | 2013-05-14 | TDY Industries, LLC | Coated cutting tools having a platinum group metal concentration gradient and related processes |
US8100318B1 (en) * | 2010-02-11 | 2012-01-24 | The United States Of America As Represented By The Secretary Of The Air Force | Joining of tungsten alloys |
NZ599937A (en) * | 2010-03-29 | 2014-09-26 | Robert G Lee | Titanium-based composite system containing hard powder |
CN101912888B (en) * | 2010-07-15 | 2012-08-22 | 江阴东大新材料研究院 | Manufacturing method of die core of wire-drawing die |
EP2465960B1 (en) | 2010-12-17 | 2014-10-08 | Sandvik Intellectual Property AB | Cermet body and a method of making a cermet body |
CN102274923B (en) * | 2011-08-04 | 2013-08-28 | 广东新劲刚新材料科技股份有限公司 | Method for in situ synthesis of tungsten carbide-based hard alloy coating on surface of cast |
US20130052236A1 (en) * | 2011-08-30 | 2013-02-28 | Mast Biosurgery | Composite polylactic acid/alginate surgical barrier |
US20130105231A1 (en) * | 2011-11-01 | 2013-05-02 | Tdy Industries, Inc. | Earth boring cutting inserts and earth boring bits including the same |
ES2675907T3 (en) * | 2011-11-11 | 2018-07-13 | Sandvik Intellectual Property Ab | Friction and agitation welding tool made from tungsten carbide cemented with nickel and with a surface coating of Al2O3 |
US8936114B2 (en) * | 2012-01-13 | 2015-01-20 | Halliburton Energy Services, Inc. | Composites comprising clustered reinforcing agents, methods of production, and methods of use |
EP2757424B1 (en) * | 2013-01-17 | 2018-05-16 | Omega SA | Part for clockwork |
GB201302345D0 (en) * | 2013-02-11 | 2013-03-27 | Element Six Gmbh | Cemented carbide material and method of making same |
CN103849789A (en) * | 2014-03-19 | 2014-06-11 | 江苏新亚特钢锻造有限公司 | Multielement coupled bionic remanufactured wear-resistant material for grinding roller, and preparation method thereof |
CN104278186B (en) * | 2014-10-16 | 2016-07-06 | 成都工具研究所有限公司 | Carbide blade for automobile cast iron process |
CN104593626B (en) * | 2015-01-07 | 2016-08-24 | 陕西理工学院 | Ni-Fe base high temperature coheres the preparation method of phase cemented carbide |
US10144065B2 (en) | 2015-01-07 | 2018-12-04 | Kennametal Inc. | Methods of making sintered articles |
CN104911431A (en) * | 2015-06-26 | 2015-09-16 | 河源正信硬质合金有限公司 | High-toughness ultra-wear-resistant hard alloy and manufacturing method thereof |
CN104988373B (en) * | 2015-08-06 | 2017-08-08 | 广东工业大学 | A kind of case-hardened gradient hard alloy and preparation method thereof |
CN105154746A (en) * | 2015-09-07 | 2015-12-16 | 南京腾达五金制品有限公司 | High temperature resistant alloy cutter head and preparation method thereof |
US9759261B2 (en) | 2015-11-18 | 2017-09-12 | Honeywell International Inc. | Methods for manufacturing high temperature bearing components and rolling element bearings |
TW201726582A (en) * | 2016-01-29 | 2017-08-01 | 國立清華大學 | Composites |
CN105734387B (en) * | 2016-03-17 | 2018-02-23 | 中南大学 | A kind of TiB2Based ceramic metal and preparation method thereof |
CN105950939A (en) * | 2016-06-04 | 2016-09-21 | 醴陵市凯维陶瓷有限公司 | Metal ceramic material and preparation method thereof |
CN105970061A (en) * | 2016-06-23 | 2016-09-28 | 王莹 | High-strength carbide-base metal ceramic lining plate and preparation method thereof |
CN106064240A (en) * | 2016-07-12 | 2016-11-02 | 张倩楠 | A kind of resistance to grinding column of manganese steel and manufacture method thereof |
CN106086575B (en) * | 2016-08-26 | 2017-10-20 | 洛阳金鹭硬质合金工具有限公司 | A kind of steel bonded carbide and preparation method thereof |
CN106238224B (en) * | 2016-09-07 | 2017-09-26 | 洛阳豫鹭矿业有限责任公司 | A kind of nozzle for mineral floating equipment |
CN106544566B (en) * | 2016-10-28 | 2018-03-06 | 四川科力特硬质合金股份有限公司 | A kind of corrosion-resistant and high-temperature resistant hard alloy and preparation method thereof |
CN106591671A (en) * | 2016-12-12 | 2017-04-26 | 威海职业学院 | TiC-Ti-Ni porous ceramic material and preparation method thereof |
CN106521213A (en) * | 2016-12-26 | 2017-03-22 | 苏州新锐合金工具股份有限公司 | Static pressure forming method for Ti(C, N) base metal ceramic material |
CN106893915B (en) * | 2017-01-22 | 2018-12-04 | 苏州新锐合金工具股份有限公司 | It is a kind of to squeeze the porous effective sintered-carbide die material of microchannel aluminium alloy flat |
CN106591678A (en) * | 2017-02-09 | 2017-04-26 | 江苏汇诚机械制造有限公司 | Preparation method of chromium-nickel-molybdenum alloy-cast-iron-based TiC/TiN steel-bonded carbide |
CN106801183A (en) * | 2017-02-09 | 2017-06-06 | 江苏汇诚机械制造有限公司 | A kind of preparation method of monikrom cast iron base TiN steel bonded carbide |
CN106591679A (en) * | 2017-02-09 | 2017-04-26 | 江苏汇诚机械制造有限公司 | Preparation method for high-toughness modified high-manganese steel-based TiC/TiN steel-bonded hard alloy |
CN106591674A (en) * | 2017-02-09 | 2017-04-26 | 江苏汇诚机械制造有限公司 | Preparation method for high-strength high-toughness heat-resistant TiN steel-bonded hard alloy |
CN106591711A (en) * | 2017-02-09 | 2017-04-26 | 江苏汇诚机械制造有限公司 | Preparation method for high strength and toughness modified high manganese steel based TiN steel bonded cemented carbide |
US11065863B2 (en) * | 2017-02-20 | 2021-07-20 | Kennametal Inc. | Cemented carbide powders for additive manufacturing |
CN106747465B (en) * | 2017-02-27 | 2020-02-11 | 太原理工大学 | HfC particle dispersion toughening and reinforcing TiN-based ceramic cutter material and preparation method thereof |
CN107099688B (en) * | 2017-04-27 | 2018-09-18 | 陕西理工大学 | Large volume fraction laves high temperature coheres the preparation method of hard alloy |
CN109136603B (en) * | 2017-06-16 | 2020-09-29 | 荆门市格林美新材料有限公司 | Preparation method of aluminum-doped hard alloy |
GB2565063B (en) | 2017-07-28 | 2020-05-27 | Oxmet Tech Limited | A nickel-based alloy |
TWI652352B (en) * | 2017-09-21 | 2019-03-01 | 國立清華大學 | Eutectic porcelain gold material |
US10662716B2 (en) | 2017-10-06 | 2020-05-26 | Kennametal Inc. | Thin-walled earth boring tools and methods of making the same |
CN108165858B (en) * | 2017-11-15 | 2022-03-25 | 常德永 | High-temperature sensitive nano material and preparation method thereof |
CN107805809A (en) * | 2017-11-21 | 2018-03-16 | 江苏雨燕模业科技有限公司 | A kind of automobile die surface coating renovation technique |
US11998987B2 (en) | 2017-12-05 | 2024-06-04 | Kennametal Inc. | Additive manufacturing techniques and applications thereof |
CN107775006A (en) * | 2017-12-12 | 2018-03-09 | 鑫京瑞钨钢(厦门)有限公司 | A kind of gradient hard alloy DRILL POINT DIES |
CN108277413A (en) * | 2018-02-28 | 2018-07-13 | 湖南天益高技术材料制造有限公司 | A kind of 3D glass heats bender high temperature resistant soaking plate and its manufacturing process |
CN108300922A (en) * | 2018-02-28 | 2018-07-20 | 湖南天益高技术材料制造有限公司 | A kind of 3D glass heats bender soaking plate and its production method |
CN108411178A (en) * | 2018-04-12 | 2018-08-17 | 明光市天淼新能源科技有限公司 | A kind of cemented carbide material |
CN109355542A (en) * | 2018-11-13 | 2019-02-19 | 武汉新科冶金设备制造有限公司 | Blast furnace opening drill bit ceramet bit material and preparation method thereof |
CN113573828B (en) | 2019-03-25 | 2024-03-01 | 肯纳金属公司 | Additive manufacturing technology and application thereof |
CN110165045B (en) * | 2019-04-08 | 2021-05-25 | 中国科学院物理研究所 | W-B alloy material and spin-orbit torque-based spin electronic device |
CN110484886B (en) * | 2019-09-12 | 2021-09-17 | 南京达迈科技实业有限公司 | Nickel-rhenium alloy rotary tubular target containing trace rare earth elements and preparation method |
CN110777289B (en) * | 2019-11-29 | 2021-04-23 | 湘潭大学 | Preparation method of metal ceramic composite material resistant to molten aluminum corrosion |
CN110846549B (en) * | 2019-11-29 | 2021-04-13 | 湘潭大学 | Metal ceramic composite material resistant to corrosion of molten aluminum |
GB201918892D0 (en) * | 2019-12-19 | 2020-02-05 | Element Six Uk Ltd | Friction stir welding using a PCBN-based tool containing superalloys |
CN111911648B (en) * | 2020-06-08 | 2022-10-14 | 温州加利利阀门制造有限公司 | Valve ball and processing method thereof |
CN111763865A (en) * | 2020-07-14 | 2020-10-13 | 株洲钻石切削刀具股份有限公司 | Rhenium-containing hard alloy and preparation method and application thereof |
CN111705251A (en) * | 2020-07-21 | 2020-09-25 | 广东正信硬质材料技术研发有限公司 | Method for improving toughness of hard alloy |
CN111809092A (en) * | 2020-07-21 | 2020-10-23 | 广东正信硬质材料技术研发有限公司 | Hard alloy extrusion die material and preparation method thereof |
CN111945051A (en) * | 2020-08-21 | 2020-11-17 | 盐城市欧特威机械科技有限公司 | Manufacturing process of bicrystal hard alloy for cutting tooth of coal mining heading machine |
CN115074591A (en) * | 2021-03-16 | 2022-09-20 | 湖南工业大学 | Niobium-chromium-based ultrafine-grained hard alloy and preparation method thereof |
CN113881922B (en) * | 2021-09-18 | 2023-08-18 | 上海理工大学 | Method for preparing high-density W-Ti alloy sputtering target material at low temperature |
MX2024006049A (en) * | 2021-11-20 | 2024-06-04 | Hyperion Materials & Tech Inc | Improved cemented carbides. |
CN114894568A (en) * | 2022-04-20 | 2022-08-12 | 中国科学院金属研究所 | Preparation and detection method of plate-shaped tensile sample of hard alpha inclusion material in titanium alloy |
CN114959400A (en) * | 2022-04-21 | 2022-08-30 | 广东翔鹭钨业股份有限公司 | WC-Co hard alloy with high toughness and high hardness and preparation method thereof |
CN115368128A (en) * | 2022-08-08 | 2022-11-22 | 江苏科技大学 | Preparation method of ZnO varistor material |
AT526477A1 (en) | 2022-09-09 | 2024-03-15 | Boehlerit Gmbh & Co Kg | Carbide object |
CN116334491B (en) * | 2023-03-28 | 2024-06-21 | 如皋市宏茂重型锻压有限公司 | Die steel and heat treatment process for improving toughness of die steel |
CN116752024A (en) * | 2023-08-21 | 2023-09-15 | 包头市新盛粉末冶金制品科技有限公司 | Tungsten carbide super wear-resistant hard alloy and preparation method and application thereof |
Citations (58)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2823988A (en) * | 1955-09-15 | 1958-02-18 | Sintercast Corp America | Composite matter |
US3342794A (en) * | 1963-06-03 | 1967-09-19 | Phillips Petroleum Co | Polymerization reaction cleanup |
US3409416A (en) * | 1966-08-29 | 1968-11-05 | Du Pont | Nitride-refractory metal compositions |
US3409418A (en) * | 1966-11-09 | 1968-11-05 | Du Pont | Dense products of vanadium or zirconium nitride with iron, nickel or cobalt |
US3672849A (en) * | 1969-07-07 | 1972-06-27 | Wall Colmonoy Corp | Cermet-type alloy coating on metal base |
US3814635A (en) * | 1973-01-17 | 1974-06-04 | Int Nickel Co | Production of powder alloy products |
US3865586A (en) * | 1972-11-17 | 1975-02-11 | Int Nickel Co | Method of producing refractory compound containing metal articles by high energy milling the individual powders together and consolidating them |
US3916497A (en) * | 1973-02-16 | 1975-11-04 | Mitsubishi Metal Corp | Heat resistant and wear resistant alloy |
US4013453A (en) * | 1975-07-11 | 1977-03-22 | Eutectic Corporation | Flame spray powder for wear resistant alloy coating containing tungsten carbide |
US4067742A (en) * | 1976-04-01 | 1978-01-10 | Nasa | Thermal shock and erosion resistant tantalum carbide ceramic material |
US4194910A (en) * | 1978-06-23 | 1980-03-25 | Chromalloy American Corporation | Sintered P/M products containing pre-alloyed titanium carbide additives |
US4246027A (en) * | 1979-03-23 | 1981-01-20 | Director-General Of The Agency Of Industrial Science And Technology | High-density sintered bodies with high mechanical strengths |
US4249913A (en) * | 1979-05-21 | 1981-02-10 | United Technologies Corporation | Alumina coated silicon carbide abrasive |
US4265662A (en) * | 1977-12-29 | 1981-05-05 | Sumitomo Electric Industries, Ltd. | Hard alloy containing molybdenum and tungsten |
US4284430A (en) * | 1979-04-27 | 1981-08-18 | General Electric Company | Cyclic oxidation resistant transverse ductile fiber reinforced eutectic nickel-base superalloys |
US4330333A (en) * | 1980-08-29 | 1982-05-18 | The Valeron Corporation | High titanium nitride cutting material |
US4463352A (en) * | 1982-07-06 | 1984-07-31 | Honeywell Inc. | Fault tolerant, self-powered data reporting system |
US4574607A (en) * | 1983-02-03 | 1986-03-11 | Kyocera Corporation | Can end seaming tool |
US4589937A (en) * | 1982-09-22 | 1986-05-20 | General Electric Company | Carbide reinforced nickel-base superalloy eutectics having improved resistance to surface carbide formation |
US4729526A (en) * | 1985-11-02 | 1988-03-08 | Josef Becker | Sleeve type lap creel having a changeable axial length |
US4735656A (en) * | 1986-12-29 | 1988-04-05 | United Technologies Corporation | Abrasive material, especially for turbine blade tips |
US4744943A (en) * | 1986-12-08 | 1988-05-17 | The Dow Chemical Company | Process for the densification of material preforms |
US4861735A (en) * | 1986-10-29 | 1989-08-29 | Imperial Chemical Industries Plc | Production of ceramic materials |
US4963183A (en) * | 1989-03-03 | 1990-10-16 | Gte Valenite Corporation | Corrosion resistant cemented carbide |
US5213612A (en) * | 1991-10-17 | 1993-05-25 | General Electric Company | Method of forming porous bodies of molybdenum or tungsten |
US5273712A (en) * | 1989-08-10 | 1993-12-28 | Siemens Aktiengesellschaft | Highly corrosion and/or oxidation-resistant protective coating containing rhenium |
US5328763A (en) * | 1993-02-03 | 1994-07-12 | Kennametal Inc. | Spray powder for hardfacing and part with hardfacing |
US5462901A (en) * | 1993-05-21 | 1995-10-31 | Kabushiki Kaisha Kobe Seiko Sho | Cermet sintered body |
US5470371A (en) * | 1992-03-12 | 1995-11-28 | General Electric Company | Dispersion strengthened alloy containing in-situ-formed dispersoids and articles and methods of manufacture |
US5476531A (en) * | 1992-02-20 | 1995-12-19 | The Dow Chemical Company | Rhenium-bound tungsten carbide composites |
US5647920A (en) * | 1989-12-27 | 1997-07-15 | Toshiba Kikai Kabushiki Kaisha | Process for preparation of corrosion-resistant and wear-resistant alloy |
US5778301A (en) * | 1994-05-20 | 1998-07-07 | Hong; Joonpyo | Cemented carbide |
US5780116A (en) * | 1990-08-24 | 1998-07-14 | United Technologies Corporation | Method for producing an abradable seal |
US5802955A (en) * | 1995-03-03 | 1998-09-08 | Kennametal Inc. | Corrosion resistant cermet wear parts |
US6024776A (en) * | 1997-08-27 | 2000-02-15 | Kennametal Inc. | Cermet having a binder with improved plasticity |
US6124040A (en) * | 1993-11-30 | 2000-09-26 | Widia Gmbh | Composite and process for the production thereof |
US6214247B1 (en) * | 1998-06-10 | 2001-04-10 | Tdy Industries, Inc. | Substrate treatment method |
US6346132B1 (en) * | 1997-09-18 | 2002-02-12 | Daimlerchrysler Ag | High-strength, high-damping metal material and method of making the same |
US6355086B2 (en) * | 1997-08-12 | 2002-03-12 | Rolls-Royce Corporation | Method and apparatus for making components by direct laser processing |
US6368377B1 (en) * | 1999-02-23 | 2002-04-09 | Kennametal Pc Inc. | Tungsten carbide nickel-chromium alloy hard member and tools using the same |
US20020078794A1 (en) * | 2000-09-06 | 2002-06-27 | Jorg Bredthauer | Ultra-coarse, monocrystalline tungsten carbide and a process for the preparation thereof, and hardmetal produced therefrom |
US6432855B1 (en) * | 1999-06-07 | 2002-08-13 | Iowa State University Reseach Foundation, Inc,. | Superabrasive boride and a method of preparing the same by mechanical alloying and hot pressing |
US20020194955A1 (en) * | 2000-03-09 | 2002-12-26 | Smith International, Inc. | Polycrystalline diamond carbide composites |
US6514456B1 (en) * | 1999-10-12 | 2003-02-04 | Plansee Tizit Aktiengesellschaft | Cutting metal alloy for shaping by electrical discharge machining methods |
US20030207142A1 (en) * | 2002-05-03 | 2003-11-06 | Honeywell International, Inc | Use of powder metal sintering/diffusion bonding to enable applying silicon carbide or rhenium alloys to face seal rotors |
US20030206824A1 (en) * | 2002-05-03 | 2003-11-06 | Adams Robbie J. | Oxidation and wear resistant rhenium metal matrix composites |
US6648206B2 (en) * | 2000-05-08 | 2003-11-18 | Tracey W. Nelson | Friction stir welding using a superabrasive tool |
US6663688B2 (en) * | 2001-06-28 | 2003-12-16 | Woka Schweisstechnik Gmbh | Sintered material of spheroidal sintered particles and process for producing thereof |
US20040134309A1 (en) * | 2003-01-13 | 2004-07-15 | Liu Shaiw-Rong Scott | Compositions and fabrication methods for hardmetals |
US6776328B2 (en) * | 2002-09-17 | 2004-08-17 | The Boeing Company | Radiation assisted friction welding |
US20040238599A1 (en) * | 2003-05-30 | 2004-12-02 | General Electric Company | Apparatus and method for friction stir welding of high strength materials, and articles made therefrom |
US20050117984A1 (en) * | 2001-12-05 | 2005-06-02 | Eason Jimmy W. | Consolidated hard materials, methods of manufacture and applications |
US20050129565A1 (en) * | 2003-12-15 | 2005-06-16 | Ohriner Evan K. | Tungsten alloy high temperature tool materials |
US20050191482A1 (en) * | 2003-01-13 | 2005-09-01 | Liu Shaiw-Rong S. | High-performance hardmetal materials |
US20050249978A1 (en) * | 2004-04-02 | 2005-11-10 | Xian Yao | Gradient polycrystalline cubic boron nitride materials and tools incorporating such materials |
US20070034048A1 (en) * | 2003-01-13 | 2007-02-15 | Liu Shaiw-Rong S | Hardmetal materials for high-temperature applications |
US20070119276A1 (en) * | 2005-03-15 | 2007-05-31 | Liu Shaiw-Rong S | High-Performance Friction Stir Welding Tools |
US7357292B2 (en) * | 2005-02-01 | 2008-04-15 | Battelle Energy Alliance, Llc | Friction stir welding tool |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US638377A (en) * | 1899-07-20 | 1899-12-05 | Jerome Burt | Cheese-cutter. |
AT348264B (en) * | 1976-05-04 | 1979-02-12 | Eurotungstene | HARD METALS AND METHOD FOR PRODUCING THEM |
SE434776B (en) * | 1979-01-30 | 1984-08-13 | Smeds Stig E | PRACTICE WITH TEMPERATURE SENSORS IN THE CHEMICAL ORGANIZATION |
ATE11574T1 (en) * | 1980-07-19 | 1985-02-15 | Kernforschungszentrum Karlsruhe Gmbh | HARD ALLOY CONSISTING OF ONE OR MORE HARD MATERIALS AND A BINDER METAL ALLOY, AND PROCESS FOR MAKING SUCH ALLOY. |
JPS61194146A (en) * | 1985-02-23 | 1986-08-28 | Hitachi Choko Kk | Cermet wire for dot printer |
JPS61201752A (en) * | 1985-03-01 | 1986-09-06 | Daido Steel Co Ltd | Manufacture of particle-dispersed alloy |
US4639352A (en) * | 1985-05-29 | 1987-01-27 | Sumitomo Electric Industries, Ltd. | Hard alloy containing molybdenum |
JPH02111823A (en) * | 1988-10-19 | 1990-04-24 | Sumitomo Electric Ind Ltd | Production of high melting point metal bonded cermet |
JP4366803B2 (en) * | 2000-01-11 | 2009-11-18 | 三菱マテリアル株式会社 | Cemented carbide extruded material, method for producing the same, and cutting tool |
JP4193958B2 (en) * | 2000-04-26 | 2008-12-10 | 東洋鋼鈑株式会社 | Molten metal member having excellent corrosion resistance against molten metal and method for producing the same |
JP2002180175A (en) * | 2000-12-14 | 2002-06-26 | Fuji Dies Kk | Sintered alloy excellent in high temperature property and die for hot forming using the alloy |
JP2002322505A (en) * | 2001-02-23 | 2002-11-08 | Sumitomo Titanium Corp | Cylindrical porous body |
-
2003
- 2003-06-02 US US10/453,085 patent/US6911063B2/en not_active Expired - Lifetime
- 2003-07-08 EP EP03808236A patent/EP1466025A4/en not_active Withdrawn
- 2003-07-08 CN CN2007100841384A patent/CN1995427B/en not_active Expired - Fee Related
- 2003-07-08 CN CNB038010224A patent/CN1309852C/en not_active Expired - Fee Related
- 2003-07-08 JP JP2004544169A patent/JP2006513119A/en active Pending
- 2003-07-08 KR KR1020057006112A patent/KR100857493B1/en not_active IP Right Cessation
- 2003-07-08 WO PCT/US2003/021332 patent/WO2004065645A1/en active Application Filing
- 2003-07-08 BR BR0313898-4A patent/BR0313898A/en not_active IP Right Cessation
- 2003-07-08 AU AU2003248862A patent/AU2003248862A1/en not_active Abandoned
- 2003-07-08 CA CA2454098A patent/CA2454098C/en not_active Expired - Fee Related
- 2003-07-08 IL IL16024803A patent/IL160248A0/en unknown
-
2004
- 2004-01-07 TW TW093100326A patent/TWI279445B/en not_active IP Right Cessation
- 2004-02-05 IL IL160248A patent/IL160248A/en not_active IP Right Cessation
- 2004-09-14 US US10/941,967 patent/US7354548B2/en not_active Expired - Lifetime
-
2008
- 2008-04-08 US US12/099,737 patent/US20080257107A1/en not_active Abandoned
-
2009
- 2009-12-24 JP JP2009293126A patent/JP2010156048A/en active Pending
Patent Citations (61)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2823988A (en) * | 1955-09-15 | 1958-02-18 | Sintercast Corp America | Composite matter |
US3342794A (en) * | 1963-06-03 | 1967-09-19 | Phillips Petroleum Co | Polymerization reaction cleanup |
US3409416A (en) * | 1966-08-29 | 1968-11-05 | Du Pont | Nitride-refractory metal compositions |
US3409418A (en) * | 1966-11-09 | 1968-11-05 | Du Pont | Dense products of vanadium or zirconium nitride with iron, nickel or cobalt |
US3672849A (en) * | 1969-07-07 | 1972-06-27 | Wall Colmonoy Corp | Cermet-type alloy coating on metal base |
US3865586A (en) * | 1972-11-17 | 1975-02-11 | Int Nickel Co | Method of producing refractory compound containing metal articles by high energy milling the individual powders together and consolidating them |
US3814635A (en) * | 1973-01-17 | 1974-06-04 | Int Nickel Co | Production of powder alloy products |
US3916497A (en) * | 1973-02-16 | 1975-11-04 | Mitsubishi Metal Corp | Heat resistant and wear resistant alloy |
US4013453A (en) * | 1975-07-11 | 1977-03-22 | Eutectic Corporation | Flame spray powder for wear resistant alloy coating containing tungsten carbide |
US4067742A (en) * | 1976-04-01 | 1978-01-10 | Nasa | Thermal shock and erosion resistant tantalum carbide ceramic material |
US4265662A (en) * | 1977-12-29 | 1981-05-05 | Sumitomo Electric Industries, Ltd. | Hard alloy containing molybdenum and tungsten |
US4194910A (en) * | 1978-06-23 | 1980-03-25 | Chromalloy American Corporation | Sintered P/M products containing pre-alloyed titanium carbide additives |
US4246027A (en) * | 1979-03-23 | 1981-01-20 | Director-General Of The Agency Of Industrial Science And Technology | High-density sintered bodies with high mechanical strengths |
US4284430A (en) * | 1979-04-27 | 1981-08-18 | General Electric Company | Cyclic oxidation resistant transverse ductile fiber reinforced eutectic nickel-base superalloys |
US4249913A (en) * | 1979-05-21 | 1981-02-10 | United Technologies Corporation | Alumina coated silicon carbide abrasive |
US4330333A (en) * | 1980-08-29 | 1982-05-18 | The Valeron Corporation | High titanium nitride cutting material |
US4463352A (en) * | 1982-07-06 | 1984-07-31 | Honeywell Inc. | Fault tolerant, self-powered data reporting system |
US4589937A (en) * | 1982-09-22 | 1986-05-20 | General Electric Company | Carbide reinforced nickel-base superalloy eutectics having improved resistance to surface carbide formation |
US4574607A (en) * | 1983-02-03 | 1986-03-11 | Kyocera Corporation | Can end seaming tool |
US4729526A (en) * | 1985-11-02 | 1988-03-08 | Josef Becker | Sleeve type lap creel having a changeable axial length |
US4861735A (en) * | 1986-10-29 | 1989-08-29 | Imperial Chemical Industries Plc | Production of ceramic materials |
US4744943A (en) * | 1986-12-08 | 1988-05-17 | The Dow Chemical Company | Process for the densification of material preforms |
US4735656A (en) * | 1986-12-29 | 1988-04-05 | United Technologies Corporation | Abrasive material, especially for turbine blade tips |
US4963183A (en) * | 1989-03-03 | 1990-10-16 | Gte Valenite Corporation | Corrosion resistant cemented carbide |
US5273712A (en) * | 1989-08-10 | 1993-12-28 | Siemens Aktiengesellschaft | Highly corrosion and/or oxidation-resistant protective coating containing rhenium |
US5647920A (en) * | 1989-12-27 | 1997-07-15 | Toshiba Kikai Kabushiki Kaisha | Process for preparation of corrosion-resistant and wear-resistant alloy |
US5780116A (en) * | 1990-08-24 | 1998-07-14 | United Technologies Corporation | Method for producing an abradable seal |
US5213612A (en) * | 1991-10-17 | 1993-05-25 | General Electric Company | Method of forming porous bodies of molybdenum or tungsten |
US5476531A (en) * | 1992-02-20 | 1995-12-19 | The Dow Chemical Company | Rhenium-bound tungsten carbide composites |
US5470371A (en) * | 1992-03-12 | 1995-11-28 | General Electric Company | Dispersion strengthened alloy containing in-situ-formed dispersoids and articles and methods of manufacture |
US5328763A (en) * | 1993-02-03 | 1994-07-12 | Kennametal Inc. | Spray powder for hardfacing and part with hardfacing |
US5462901A (en) * | 1993-05-21 | 1995-10-31 | Kabushiki Kaisha Kobe Seiko Sho | Cermet sintered body |
US6124040A (en) * | 1993-11-30 | 2000-09-26 | Widia Gmbh | Composite and process for the production thereof |
US5778301A (en) * | 1994-05-20 | 1998-07-07 | Hong; Joonpyo | Cemented carbide |
US5802955A (en) * | 1995-03-03 | 1998-09-08 | Kennametal Inc. | Corrosion resistant cermet wear parts |
US6355086B2 (en) * | 1997-08-12 | 2002-03-12 | Rolls-Royce Corporation | Method and apparatus for making components by direct laser processing |
US6024776A (en) * | 1997-08-27 | 2000-02-15 | Kennametal Inc. | Cermet having a binder with improved plasticity |
US6346132B1 (en) * | 1997-09-18 | 2002-02-12 | Daimlerchrysler Ag | High-strength, high-damping metal material and method of making the same |
US6214247B1 (en) * | 1998-06-10 | 2001-04-10 | Tdy Industries, Inc. | Substrate treatment method |
US6368377B1 (en) * | 1999-02-23 | 2002-04-09 | Kennametal Pc Inc. | Tungsten carbide nickel-chromium alloy hard member and tools using the same |
US6432855B1 (en) * | 1999-06-07 | 2002-08-13 | Iowa State University Reseach Foundation, Inc,. | Superabrasive boride and a method of preparing the same by mechanical alloying and hot pressing |
US6514456B1 (en) * | 1999-10-12 | 2003-02-04 | Plansee Tizit Aktiengesellschaft | Cutting metal alloy for shaping by electrical discharge machining methods |
US20020194955A1 (en) * | 2000-03-09 | 2002-12-26 | Smith International, Inc. | Polycrystalline diamond carbide composites |
US20040134972A1 (en) * | 2000-05-08 | 2004-07-15 | Nelson Tracy W. | Friction stir welding using a superabrasive tool |
US6648206B2 (en) * | 2000-05-08 | 2003-11-18 | Tracey W. Nelson | Friction stir welding using a superabrasive tool |
US6779704B2 (en) * | 2000-05-08 | 2004-08-24 | Tracy W. Nelson | Friction stir welding of metal matrix composites, ferrous alloys, non-ferrous alloys, and superalloys using a superabrasive tool |
US20020078794A1 (en) * | 2000-09-06 | 2002-06-27 | Jorg Bredthauer | Ultra-coarse, monocrystalline tungsten carbide and a process for the preparation thereof, and hardmetal produced therefrom |
US6663688B2 (en) * | 2001-06-28 | 2003-12-16 | Woka Schweisstechnik Gmbh | Sintered material of spheroidal sintered particles and process for producing thereof |
US20050117984A1 (en) * | 2001-12-05 | 2005-06-02 | Eason Jimmy W. | Consolidated hard materials, methods of manufacture and applications |
US20030206824A1 (en) * | 2002-05-03 | 2003-11-06 | Adams Robbie J. | Oxidation and wear resistant rhenium metal matrix composites |
US6773663B2 (en) * | 2002-05-03 | 2004-08-10 | Honeywell International, Inc. | Oxidation and wear resistant rhenium metal matrix composites |
US20030207142A1 (en) * | 2002-05-03 | 2003-11-06 | Honeywell International, Inc | Use of powder metal sintering/diffusion bonding to enable applying silicon carbide or rhenium alloys to face seal rotors |
US6776328B2 (en) * | 2002-09-17 | 2004-08-17 | The Boeing Company | Radiation assisted friction welding |
US20040134309A1 (en) * | 2003-01-13 | 2004-07-15 | Liu Shaiw-Rong Scott | Compositions and fabrication methods for hardmetals |
US20050191482A1 (en) * | 2003-01-13 | 2005-09-01 | Liu Shaiw-Rong S. | High-performance hardmetal materials |
US20070034048A1 (en) * | 2003-01-13 | 2007-02-15 | Liu Shaiw-Rong S | Hardmetal materials for high-temperature applications |
US20040238599A1 (en) * | 2003-05-30 | 2004-12-02 | General Electric Company | Apparatus and method for friction stir welding of high strength materials, and articles made therefrom |
US20050129565A1 (en) * | 2003-12-15 | 2005-06-16 | Ohriner Evan K. | Tungsten alloy high temperature tool materials |
US20050249978A1 (en) * | 2004-04-02 | 2005-11-10 | Xian Yao | Gradient polycrystalline cubic boron nitride materials and tools incorporating such materials |
US7357292B2 (en) * | 2005-02-01 | 2008-04-15 | Battelle Energy Alliance, Llc | Friction stir welding tool |
US20070119276A1 (en) * | 2005-03-15 | 2007-05-31 | Liu Shaiw-Rong S | High-Performance Friction Stir Welding Tools |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100180514A1 (en) * | 2003-01-13 | 2010-07-22 | Genius Metal, Inc. | High-Performance Hardmetal Materials |
US20120152620A1 (en) * | 2009-07-01 | 2012-06-21 | Atlas Copco Rock Drills Ab | Device and method for protecting the rock drilling machine from corrosion |
US9352461B2 (en) * | 2009-07-01 | 2016-05-31 | Atlas Copco Rock Drills Ab | Device and method for protecting the rock drilling machine from corrosion |
US9340852B2 (en) | 2011-09-26 | 2016-05-17 | National Tsing Hua University | Elevated refractory alloy with ambient-temperature and low-temperature ductility and method thereof |
CN103981419A (en) * | 2014-04-09 | 2014-08-13 | 宁波东联密封件有限公司 | High-strength titanium carbonitride metal ceramic sealing material and preparation method thereof |
RU2689456C2 (en) * | 2014-12-30 | 2019-05-28 | Сандвик Хиперион АБ | Corrosion-resistant cemented carbide for operation with fluids |
CN105568107A (en) * | 2016-01-29 | 2016-05-11 | 柳州市安龙机械设备有限公司 | Manufacturing method for high wire roll ring |
CN111424203A (en) * | 2020-03-09 | 2020-07-17 | 株洲鑫品硬质合金股份有限公司 | Ultra-fine grain hard alloy and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
US20040134309A1 (en) | 2004-07-15 |
JP2010156048A (en) | 2010-07-15 |
CN1995427A (en) | 2007-07-11 |
US7354548B2 (en) | 2008-04-08 |
KR100857493B1 (en) | 2008-09-09 |
WO2004065645A1 (en) | 2004-08-05 |
KR20050095762A (en) | 2005-09-30 |
CA2454098C (en) | 2010-10-26 |
CA2454098A1 (en) | 2004-07-13 |
IL160248A0 (en) | 2004-09-27 |
US6911063B2 (en) | 2005-06-28 |
EP1466025A4 (en) | 2005-07-27 |
BR0313898A (en) | 2005-07-19 |
TWI279445B (en) | 2007-04-21 |
IL160248A (en) | 2011-04-28 |
TW200426225A (en) | 2004-12-01 |
JP2006513119A (en) | 2006-04-20 |
US20080008616A1 (en) | 2008-01-10 |
EP1466025A1 (en) | 2004-10-13 |
CN1995427B (en) | 2010-09-29 |
AU2003248862A1 (en) | 2004-08-13 |
CN1309852C (en) | 2007-04-11 |
CN1592795A (en) | 2005-03-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6911063B2 (en) | Compositions and fabrication methods for hardmetals | |
US7645315B2 (en) | High-performance hardmetal materials | |
WO2007022514A2 (en) | Hardmetal materials for high-temperature applications | |
US7857188B2 (en) | High-performance friction stir welding tools | |
EP1982001A2 (en) | High-performance friction stir welding tools | |
EP2347024B1 (en) | A hard-metal | |
US20070034048A1 (en) | Hardmetal materials for high-temperature applications | |
CN101415518A (en) | High-performance friction stir welding tools | |
JP4351453B2 (en) | Cemented carbide and drill using the same | |
JP2001277008A (en) | Cermet for cutting tool and its manufacturing method | |
JP2003277873A (en) | Supper hard alloy | |
SE461916B (en) | Carbonitride-based alloy for cutting tools and method for producing this alloy |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: GENIUS METAL, INC., CALIFORNIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:LIU, SHAIW-RONG SCOTT;REEL/FRAME:021041/0596 Effective date: 20030602 |
|
AS | Assignment |
Owner name: WORLDWIDE STRATEGY HOLDINGS LIMITED, HONG KONG Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:GENIUS METAL, INC.;REEL/FRAME:021994/0315 Effective date: 20081212 Owner name: GENIUS METAL, INC., CALIFORNIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:GENIUS METAL, INC.;REEL/FRAME:021994/0315 Effective date: 20081212 |
|
AS | Assignment |
Owner name: WORLDWIDE STRATEGY HOLDINGS LIMITED, HONG KONG Free format text: CORRECTIVE ASSIGNMENT TO CORRECT THE ASSIGNEE PREVIOUSLY RECORDED ON REEL 021994 FRAME 0315;ASSIGNOR:GENIUS METAL, INC.;REEL/FRAME:022551/0808 Effective date: 20081212 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |