EP1420076A1 - Alliage dur et poudre composite contenant du carbure à base de W comme produit de départ - Google Patents
Alliage dur et poudre composite contenant du carbure à base de W comme produit de départ Download PDFInfo
- Publication number
- EP1420076A1 EP1420076A1 EP03024424A EP03024424A EP1420076A1 EP 1420076 A1 EP1420076 A1 EP 1420076A1 EP 03024424 A EP03024424 A EP 03024424A EP 03024424 A EP03024424 A EP 03024424A EP 1420076 A1 EP1420076 A1 EP 1420076A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hard alloy
- specific element
- amount
- carbide
- group
- 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.)
- Withdrawn
Links
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 75
- 239000000956 alloy Substances 0.000 title claims abstract description 75
- 239000000843 powder Substances 0.000 title claims description 49
- 239000002131 composite material Substances 0.000 title description 12
- 239000007858 starting material Substances 0.000 title description 7
- 239000013078 crystal Substances 0.000 claims abstract description 35
- 239000011651 chromium Substances 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 239000010936 titanium Substances 0.000 claims abstract description 28
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 27
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 24
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 23
- 239000011572 manganese Substances 0.000 claims abstract description 22
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 20
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 20
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 20
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 19
- 239000010955 niobium Substances 0.000 claims abstract description 19
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 18
- 239000006104 solid solution Substances 0.000 claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 16
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 11
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 11
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 11
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 11
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 11
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims abstract description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011733 molybdenum Substances 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000004767 nitrides Chemical class 0.000 claims abstract description 4
- 230000000737 periodic effect Effects 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 19
- 229910052721 tungsten Inorganic materials 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000001976 improved effect Effects 0.000 description 15
- 238000005260 corrosion Methods 0.000 description 14
- 230000007797 corrosion Effects 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- 239000011812 mixed powder Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 8
- 150000001247 metal acetylides Chemical class 0.000 description 8
- 229910003470 tongbaite Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910003460 diamond Inorganic materials 0.000 description 4
- 239000010432 diamond Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910003178 Mo2C Inorganic materials 0.000 description 3
- 229910001080 W alloy Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910000599 Cr alloy Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 2
- 230000008094 contradictory effect Effects 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910001339 C alloy Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical class O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910020515 Co—W Inorganic materials 0.000 description 1
- 229910002551 Fe-Mn Inorganic materials 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910009001 W2C Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003966 growth inhibitor Substances 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229910000048 titanium hydride Inorganic materials 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—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
- C22C29/02—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
Definitions
- the present invention relates to a hard alloy to be used for cutting tools, wear resistant tools, corrosion resistant and wear resistant parts, etc., and particularly to a hard alloy in which characteristics such as hardness, toughness, strength, wear resistance, fracture resistance, plastic deformation resistance, thermal crack resistance, antioxidation property, corrosion resistance, etc., by adding specific element(s) to crystal of hexagonal tungsten carbide which is a primary hard phase as a solid solution, and to a W-based composite carbide powder which becomes a starting material thereof.
- a hard alloy produced by mixing, in addition to WC and Co, other powder of carbides such as TiC, TaC, VC, Cr 3 C 2 , etc., subjecting to molding under pressure, and sintering under heating has been used for various kinds of uses such as cutting tools, wear resistant tools and parts. Also, by adjusting grain size of WC, a Co amount, a kind and amount of a carbide to be added, and the like, alloy characteristics such as hardness, strength, toughness, heat resistance, oxidation resistance, corrosion resistance, etc. required for the respective uses are obtained.
- TiC is added to steel cutting tools in which wear due to a reaction or welding becomes a problem
- TaC and/or ZrC is/are added to hot-working mold or steel cutting tools in which plastic deformation at high temperatures becomes a problem
- VC and/or Cr 3 C 2 is/are added to a drill to which hardness and strength are required as a grain growth inhibitor of WC
- Cr 3 C 2 and/or Mo 2 C is/are added to wear resistant parts in which corrosion becomes a problem.
- Japanese Provisional Patent Publication No. 7-54001 there is disclosed a preparation method of fine complex carbide powder for preparation of a tungsten carbide-based hard alloy in which mixed powder comprising tungsten oxide, cobalt oxide, carbon, and further carbides of V, Cr, Ta and/or Nb each having an average particle diameter of about 1 ⁇ m or lower is subjected to reduction treatment and carbonization treatment both at'700 to 1200°C.
- powder comprising a transition metal carbide and Group VIII metal and a process for preparing the same, which comprises heating a precursor mixed powder which becomes a metal selected from iron, cobalt and nickel and a transition metal carbide of a metal selected from tungsten, titanium, tantalum, molybdenum, zirconium, hafnium, vanadium, niobium and chromium at 1173 to 1773K (900 to 1500°C).
- a precursor mixed powder which becomes a metal selected from iron, cobalt and nickel and a transition metal carbide of a metal selected from tungsten, titanium, tantalum, molybdenum, zirconium, hafnium, vanadium, niobium and chromium at 1173 to 1773K (900 to 1500°C).
- a complex carbide containing a tungsten carbide obtained by heating a mixed powder comprising tungsten oxide and chromium oxide or metallic chromium in hydrogen atmosphere at 700 to 1100°C to obtain a solid solution or a intermetallic compound, mixing carbon powder thereto, and carbonizing in hydrogen and vacuum at a temperature of 1300 to 1700°C, and 0.5 to 2.0% by weight of metal chromium based on the amount of the tungsten carbide, and a process for preparing the same.
- transition metal or its carbide is uniformly and finely dispersed, so that when they are used as a hard alloy, characteristics such as hardness, strength, toughness, etc. can be improved but a heating temperature is low so that an amount of the transition metal dissolved in tungsten carbide is extremely little, whereby there is no improvement in characteristics of the tungsten carbide itself.
- a heating temperature is low so that an amount of the transition metal dissolved in tungsten carbide is extremely little, whereby there is no improvement in characteristics of the tungsten carbide itself.
- This is to subject a (W, Mo)C solid solution which has conventionally been well known to nitriding synthesis by heating to 500 to 2000°C in a nitrogen atmosphere at a pressure of 10 atm or higher.
- the (W, Mo)(CN) powder disclosed in this publication has a wide range of an amount of Mo as a solid solution and when it is employed for a hard alloy, an effect of making particles fine by the nitrogen can be expected.
- an amount of Mo to be dissolved as a solid solution is large, there are problems that decreases in hardness, strength, wear resistance, plastic deformation property and oxidation resistance are remarkable.
- Hei.11-6025 there are disclosed a hard alloy comprising 3 to 25% by weight of Co and Ni in total, 10 to 30% by weight of Cr in terms of chromium carbide based on the amount of Co and Ni, and the reminder being tungsten carbide and inevitable impurities, a coated alloy using the hard alloy as a matrix and coated cutting tools.
- a Cr content, a Co/Ni ratio and grain size of WC are limited to optimum ranges when they are used as cutting tools, and Cr is dissolved in a metal binder phase, but is not dissolved in WC as a solid solution, so that there is a problem that an effect of Cr added cannot sufficiently be shown.
- an iron-based hard alloy comprising a binder phase which comprises Fe containing 0.35 to 3.0% by weight of C, 3.0 to 30.0% by weight of Mn, and 3.0 to 25.0% by weight of Cr.
- a hard alloy using titanium compound powder as a starting material which powder has a coated film on the surface thereof, comprising at least one substance selected from the group consisting of Groups 4a, 5a, 6a metal except for titanium, their carbide, nitride and carbonitride, and rhenium metal and iridium metal.
- the hard alloys containing Mn or Re metal disclosed in these publications are to improve strength, toughness, corrosion resistance, heat resistance, etc. of the hard alloy by adding these metals as a solid solution to a metal binder phase, but these metals are not dissolved in WC, so that an effect of adding Mn or Re is little and if an amount of these metals to be added is large, the metal binder phase becomes brittle whereby there are problems that strength and toughness are lowered.
- the present invention is to solve the above-mentioned problems, and specifically, an object of the present invention is to provide a hard alloy in which contradicting alloy characteristics of the hard alloy are simultaneously improved by dissolving specific element(s) such as Ti, Zr, V, Ta, Cr, Mn, etc. into crystalline of WC as a solid solution whereby hardness, toughness, oxidation resistance, corrosion resistance, etc. of the WC itself are improved, and to provide W-based composite carbide powder which becomes a starting material of the hard alloy.
- specific element(s) such as Ti, Zr, V, Ta, Cr, Mn, etc.
- the present inventors have studied to improve contradicting characteristics of hard alloy at the same time for a long period of time, and as a result, they have found that to improve characteristics of WC itself is effective, various characteristics of the alloy can be improved when specific element(s) is/are dissolved in the crystal of WC, metals belonging to Group IVB (Ti, Zr, Hf), VB (V, Nb, Ta) or VIB (Cr, Mo) of the Periodic Table (except for W), and Mn and Re are the most effective as the specific element(s), and WC dissolved the specific element(s) therein can be obtained by subjecting a mixed powder of W, C and an oxide of the specific element(s) to heat treatment, whereby they have accomplished the present invention.
- specific element(s) is/are dissolved in the crystal of WC
- the hard alloy of the present invention comprises 5 to 50% by volume of a metallic binder phase comprising at least one element selected from cobalt, nickel and iron as a main component, 0 to 40% by volume of a cubic crystal compound comprising at least one compound selected from a carbide, nitride and mutual solid solution of a metal of Group IVB (Ti, Zr, Hf), VB (V, Nb, Ta), VIB (Cr, Mo) of the Periodic Table, and the reminder being hexagonal tungsten carbide and inevitable impurities, wherein at least one specific element(s) selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, manganese and rhenium is dissolved in the crystal of the hexagonal tungsten carbide as a solid solution in an amount of 0.1 to 3.0% by weight based on the amount of the tungsten carbide.
- a metallic binder phase comprising at least one element
- the hexagonal tungsten carbide in the hard alloy of the present invention is a material in which at least one of the specific element(s) selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, Mn and Re is dissolved in the crystal of WC as a solid solution.
- An amount of the specific element(s) to be dissolved in WC as a solid solution is defined to be 0.1 to 3.0% by weight, since if it is added in an amount of less than 0.1% by weight, improved effects in hardness, toughness, oxidation resistance, corrosion resistance, etc. are little, whereas Ti, Zr, Hf, V, Nb or Ta is extremely difficult to be dissolved in WC in an amount exceeding 3.0% by weight, and even when Cr, Mo, Mn or Re can be dissolved in WC in an amount exceeding 3.0% by weight, it accompanies with lowering in hardness or oxidation resistance, or formation of brittle sub-carbide material.
- the amount is preferably 0.3 to 2% by weight.
- the specific element(s) dissolved in WC crystal has slightly different characteristics to be provided to the hard alloy depending on the kind thereof.
- Ti, Zr, Hf and V improve hardness, wear resistance, welding resistance, oxidation resistance, etc.
- Nb and Ta improve toughness, fracture resistance, heat resistance, etc.
- Cr improves toughness, oxidation resistance and corrosion resistance
- Mo, Mn and Re improve hardness, toughness, heat resistance, etc.
- the specific element(s) is/are at least one selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium and tantalum, and a content of a cubic crystal compound mentioned hereinbelow is 1% by volume or less, since strength and toughness are particularly high.
- the specific element(s) is chromium, and 0.1 to 10% by weight of chromium is contained based on the total amount of the hard alloy, since chromium is also dissolved in the metal binder phase as a solid solution, so that improved effects of hardness, toughness, heat resistance, corrosion resistance, oxidation resistance, etc. are more remarkable.
- the specific element(s) is/are manganese and/or rhenium, and 0.1 to 10% by weight of manganese and/or rhenium is/are contained in the total amount of the hard alloy, since it is/they are also dissolved in the binder phase, whereby improved effects of hardness, toughness, heat resistance, etc. are more remarkable.
- the metal binder phase of the hard alloy according to the present invention comprises an alloy containing iron group metal (Fe, Co, Ni) as a main component and 30% by weight or less of W is dissolved therein. More specifically, the binder phase may be mentioned, for example, Co-W alloy, CoRe alloy, Co-W-Cr alloy, Ni-Mo alloy, Ni-Cr-W alloy, Co-Ni-Cr-W alloy, Fe-Ni-W alloy, Fe-Mo-Cr alloy, Fe-Mn alloy, and the like.
- An amount of the metal binder phase is defined to be 5 to 50% by volume, since if it is less than 5% by volume, micro pores are remained in the alloy, so that hardness, strength, toughness or fracture resistance is lowered, while if it exceeds 50% by volume, hardness or wear resistance is lowered.
- the cubic crystal compound which is an optional component of the hard alloy according to the present invention may be specifically mentioned, for example, VC, NbC, TaC, (W,Ti)C, (W, Zr) C, (W, Ti, Ta) C, (W, Ti, Re) C, TiN, ZrN, HfN, (W,Ti,Ta)-(C,N), (W,Ti,Mo)(C,N), and the like.
- the hard alloy of the present invention may contain Cr 7 C 3 , Mo 2 C, etc. which do not belong to the cubic crystal compound with a small amount. If the content of the cubic crystal compound in the hard alloy exceeds 40% by volume, an amount of WC to which the specific element(s) is/are dissolved is relatively lowered, so that an improved effect thereof becomes a little.
- the W-based composite carbide powder of the present invention comprises complex carbide powder which contains tungsten, carbon, and at least one specific element(s) selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, manganese and rhenium, wherein said complex carbide powder contains 80% by volume or more of hexagonal tungsten carbide, and 0.1 to 3.0% by weight of the specific element(s)is/are dissolved in the crystals of the hexagonal tungsten carbide.
- An amount of the specific element(s) to be dissolved in the W-based composite carbide powder of the present invention is defined to be 0.1 to 3.0% by weight, since if it is less than 0.1% by weight, improved effects on the WC itself such as hardness, toughness, oxidation resistance, corrosion resistance, etc. are low, and it is difficult to dissolve the specific element(s) in an amount exceeding 3.0% by weight in the WC crystal.
- the complex carbide of the present invention is represented by the chemical formula, it is a material of (W 1-x ,M x )C y wherein x and y satisfy the relationship of 0.002 ⁇ x ⁇ 0.06 and 0.95 ⁇ y ⁇ 1.00 since the specific element(s) is/are substituted for the W atom in the WC crystal, and taken into the hexagonal crystal lattice.
- M represents at least one of the specific elements.
- the W-based composite carbide powder of the present invention comprises WC in which the specific element(s) is/are dissolved as a main component, and a cubic crystal compound into which W is dissolved, and W 2 C, Cr 3 C 2 , Mo 2 C or the like into which the specific element(s) is dissolved. If an amount of the WC in which the specific element(s) is/are dissolved is less than 80% by volume, improved effects on hardness, toughness, oxidation resistance, corrosion resistance, etc. due to the specific element(s) dissolved in WC are little in the hard alloy to be produced by using the present products.
- the cubic crystal compound which may be contained in the complex carbide powder comprises W, carbon and/or nitrogen, and at least one selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium and tantalum. Specific compositions thereof may be mentioned (W 0.6 Ti 0.4 )C 0.8 , (W 0.06 Zr 0.95 )C 0.75 , (W 0.45 V 0.55 )C 0.9 , (W 0.65 Ta 0.35 )C 0.9 , (W 0.5 Ti 0.5 )(C 0.9 N 0.1 ) 0.95 , (W 0.5 Ti 0.3 Ta 0.2 )C 0.9 , and the like.
- These cubic crystal compounds are formed when the specific element(s) is/are added exceeding a limit of an amount capable of being dissolved, and to show added effects of the specific element(s) at the highest level, the presence of the cubic crystal compound is sometimes preferred.
- an amount thereof becomes 20% by volume or more, it becomes difficult to adjust a ratio of the composition for producing the hard alloy, and in particular, a problem of lowering in strength of the hard alloy arises.
- W 2 C is likely formed when the content of carbon is lower, when the powder is subjected to heat treatment at higher temperatures, when the specific element(s) is Cr or Mo, or the like, but to enlarge an amount of the element(s) to be dissolved, W 2 C is rather preferably contained in an amount of up to 5% by volume.
- the WC crystal to which the specific element(s) is/are dissolved has a lattice constant of a axis of a hexagonal crystal lattice of 0.2910 nm or longer and/or a lattice constant of c axis of the same of 0.2840 nm or longer, since dissolution of the specific element(s) in the WC crystal is complete and uniform whereby improved effects of the various kinds of characteristics become maximum.
- the hard alloy of the present invention can be produced by the conventionally employed powder metallurgy method when the W-based composite carbide powder of the present invention is used as a starting material.
- the W-based composite carbide powder can be obtained, for example, by heating a mixed powder of WC and TiH 2 , a mixed powder of W, TiN and carbon, a mixed powder of WO 3 , TiO 2 and carbon and the like in a non-oxidative atmosphere or a combined atmosphere of reducing and carburizing atmospheres at high temperatures.
- powder with a much amount of dissolution as well as a uniform dissolution degree and uniform grain size distribution can be produced.
- the W-based composite carbide powder of the present invention can be produced by subjecting a mixed powder comprising W powder, carbon powder and oxide powder of the specific element(s) each having a grain size of 1 ⁇ m or less to heat treatment at 1500 to 2000°C or so in an inert gas atmosphere or under vacuum.
- a mixed powder comprising W powder, carbon powder and oxide powder of the specific element(s) each having a grain size of 1 ⁇ m or less
- the heat treatment temperature is higher, an amount of the specific element(s) dissolved in the powder increases but the WC crystals become coarse to cause abnormal grain growth.
- Cr or Mn which has a higher vapor pressure is used as the specific element(s)
- the hexagonal tungsten carbide into which the specific element(s) is/are dissolved, which is in the W-based composite carbide powder used as a starting material has functions of improving hardness, toughness, heat resistance, corrosion resistance, oxidation resistance, etc. of the tungsten carbide itself, and the improved characteristics have functions of improving alloy characteristics or practical characteristics.
- a formulated carbon amount was adjusted by addition of C or W, so that the alloy became medium carbon alloy (center of a range of a sound phase which does not precipitate free carbon or Co 3 W 3 C, Ni 2 W 4 C) after sintering. Then, these powders were filled in a mold, and green compacts having a size of 5.5 x 9.5 x 29 mm were produced with a pressure of 196 MPa, placed on a sheet comprising alumina and carbon fiber and heated by inserting into a vacuum atmosphere furnace.
- the atmosphere was made vacuum of about 20 Pa, and thereafter, heating was carried out in the atmosphere shown in Table 4, and sintering was carried out at 1400°C for 1.0 hour to obtain hard alloys of Present products 1 to 14 and Comparative products 1 to 14.
- Present product and Comparative product with the same number were so formulated that the components of the hard alloy and grain size of WC are substantially the same.
- the resulting hard alloy sample piece was subjected to wet polishing processing with a 230 mesh diamond whetstone to produce a sample with a size of 4.0 x 8.0 x 25.0 mm, and transverse-rupture strength (hereinafter abbreviated to as "TRS") was measured by the JIS method. Also, one surface of the same sample was subjected to lap processing with a diamond past having an average particle size of 0.3 ⁇ m, hardness and fracture toughness value K1C (IM method) were measured under a load of 196N using a Vickers indenter.
- TRS transverse-rupture strength
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002309855 | 2002-10-24 | ||
| JP2002309855A JP2004142993A (ja) | 2002-10-24 | 2002-10-24 | 六方晶複合炭化物およびその製造方法 |
| JP2003027343 | 2003-02-04 | ||
| JP2003027343A JP2004238660A (ja) | 2003-02-04 | 2003-02-04 | クロム含有超硬合金 |
| JP2003055291A JP2004263251A (ja) | 2003-03-03 | 2003-03-03 | ７ａ族元素含有超硬合金 |
| JP2003055291 | 2003-03-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1420076A1 true EP1420076A1 (fr) | 2004-05-19 |
Family
ID=32110655
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP03024424A Withdrawn EP1420076A1 (fr) | 2002-10-24 | 2003-10-23 | Alliage dur et poudre composite contenant du carbure à base de W comme produit de départ |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US20040079191A1 (fr) |
| EP (1) | EP1420076A1 (fr) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012145773A1 (fr) | 2011-04-26 | 2012-11-01 | Wolfram Bergbau Und Hütten Ag | Carbure de tungstène hexagonal dopé et son procédé de fabrication |
| RU2789102C1 (ru) * | 2022-03-04 | 2023-01-30 | Федеральное государственное бюджетное учреждение науки Федеральный исследовательский центр "Кольский научный центр Российской академии наук" (ФИЦ КНЦ РАН) | Способ получения порошков тугоплавких карбидов переходных металлов пятой подгруппы |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9428822B2 (en) | 2004-04-28 | 2016-08-30 | Baker Hughes Incorporated | Earth-boring tools and components thereof including material having hard phase in a metallic binder, and metallic binder compositions for use in forming such tools and components |
| CN1796315A (zh) * | 2004-12-23 | 2006-07-05 | 鸿富锦精密工业（深圳）有限公司 | 复合结构模仁及其制备方法 |
| CN100560522C (zh) * | 2005-01-07 | 2009-11-18 | 鸿富锦精密工业（深圳）有限公司 | 复合结构模仁及其制备方法 |
| TW200624400A (en) * | 2005-01-14 | 2006-07-16 | Hon Hai Prec Ind Co Ltd | Mold for molding glass optical articles and method for making same |
| EP2571647A4 (fr) | 2010-05-20 | 2017-04-12 | Baker Hughes Incorporated | Procédés de formation d'au moins une partie d'outils de forage terrestre, et articles formés par de tels procédés |
| WO2011146760A2 (fr) * | 2010-05-20 | 2011-11-24 | Baker Hughes Incorporated | Procédés de formation d'au moins une partie d'outils de forage terrestre, et articles formés par de tels procédés |
| RU2694401C2 (ru) * | 2013-05-31 | 2019-07-12 | Сандвик Интеллекчуал Проперти Аб | Новый способ получения цементированного карбида и получаемый при его помощи продукт |
| CN103320667B (zh) * | 2013-07-18 | 2015-06-17 | 成都成量工具集团有限公司 | 一种硬质合金及其制备方法 |
| DE102017113401A1 (de) * | 2017-06-19 | 2018-12-20 | Epcos Ag | Schichtwiderstand und Dünnfilmsensor |
| CN107058841B (zh) * | 2017-06-29 | 2018-12-21 | 浙江创特新材科技有限公司 | 一种高机械强度钨合金材料及其制备方法 |
| JP7216656B2 (ja) | 2017-11-14 | 2023-02-01 | 株式会社アライドマテリアル | 炭化タングステンを含む粉末 |
| CN111670261B (zh) * | 2018-02-06 | 2021-11-26 | 三菱电机株式会社 | 电触点及使用该电触点的真空阀 |
| CN108277414A (zh) * | 2018-02-25 | 2018-07-13 | 株洲市超宇实业有限责任公司 | 一种用于3d玻璃热弯机硬质合金均热板的生产方法 |
| WO2020127684A1 (fr) * | 2018-12-20 | 2020-06-25 | Ab Sandvik Coromant | Outil de coupe revêtu |
| CN113549800A (zh) * | 2021-05-13 | 2021-10-26 | 厦门大鸿翰金属材料科技有限公司 | 一种高性能超细硬质合金及其制备方法 |
| CN113373364A (zh) * | 2021-05-26 | 2021-09-10 | 北京有研粉末新材料研究院有限公司 | 颗粒增强难熔高熵复合材料及其制备方法 |
| CN114769583B (zh) * | 2022-05-13 | 2024-02-02 | 赣南师范大学 | 一种核-壳结构复合粉末及其制备方法 |
| CN114853016B (zh) * | 2022-05-25 | 2023-08-25 | 内蒙古科技大学 | 由含铌矿物制备碳化铌钛的方法 |
| US20250027189A1 (en) * | 2023-07-17 | 2025-01-23 | Kennametal Inc. | Solid solution tungsten carbide powders and applications thereof |
| CN119040720B (zh) * | 2024-10-29 | 2025-02-07 | 赣州海盛硬质合金有限公司 | 一种高红硬性合金材料及其制备方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4216009A (en) * | 1977-07-27 | 1980-08-05 | Sumitomo Electric Industries, Ltd. | Method of making alloy and carbide powders of molybdenum and tungsten |
| US4279651A (en) * | 1977-12-29 | 1981-07-21 | Sumitomo Electric Industries, Ltd. | Sintered hard metal and the method for producing the same |
| US4300952A (en) * | 1978-02-28 | 1981-11-17 | Sandvik Aktiebolag | Cemented hard metal |
| JPS5858245A (ja) * | 1981-10-02 | 1983-04-06 | Sumitomo Electric Ind Ltd | 耐衝撃工具用硬質合金 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH621749A5 (fr) * | 1977-08-09 | 1981-02-27 | Battelle Memorial Institute | |
| US4548786A (en) * | 1983-04-28 | 1985-10-22 | General Electric Company | Coated carbide cutting tool insert |
| US4963183A (en) * | 1989-03-03 | 1990-10-16 | Gte Valenite Corporation | Corrosion resistant cemented carbide |
| US5918103A (en) * | 1995-06-06 | 1999-06-29 | Toshiba Tungaloy Co., Ltd. | Plate-crystalline tungsten carbide-containing hard alloy, composition for forming plate-crystalline tungsten carbide and process for preparing said hard alloy |
| JP2990655B2 (ja) * | 1996-05-21 | 1999-12-13 | 東京タングステン株式会社 | 複合炭化物粉末及びその製造方法 |
-
2003
- 2003-10-23 EP EP03024424A patent/EP1420076A1/fr not_active Withdrawn
- 2003-10-23 US US10/690,672 patent/US20040079191A1/en not_active Abandoned
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4216009A (en) * | 1977-07-27 | 1980-08-05 | Sumitomo Electric Industries, Ltd. | Method of making alloy and carbide powders of molybdenum and tungsten |
| US4279651A (en) * | 1977-12-29 | 1981-07-21 | Sumitomo Electric Industries, Ltd. | Sintered hard metal and the method for producing the same |
| US4300952A (en) * | 1978-02-28 | 1981-11-17 | Sandvik Aktiebolag | Cemented hard metal |
| JPS5858245A (ja) * | 1981-10-02 | 1983-04-06 | Sumitomo Electric Ind Ltd | 耐衝撃工具用硬質合金 |
Non-Patent Citations (1)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN vol. 0071, no. 47 (C - 173) 28 June 1983 (1983-06-28) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012145773A1 (fr) | 2011-04-26 | 2012-11-01 | Wolfram Bergbau Und Hütten Ag | Carbure de tungstène hexagonal dopé et son procédé de fabrication |
| RU2789102C1 (ru) * | 2022-03-04 | 2023-01-30 | Федеральное государственное бюджетное учреждение науки Федеральный исследовательский центр "Кольский научный центр Российской академии наук" (ФИЦ КНЦ РАН) | Способ получения порошков тугоплавких карбидов переходных металлов пятой подгруппы |
Also Published As
| Publication number | Publication date |
|---|---|
| US20040079191A1 (en) | 2004-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1420076A1 (fr) | Alliage dur et poudre composite contenant du carbure à base de W comme produit de départ | |
| US5918103A (en) | Plate-crystalline tungsten carbide-containing hard alloy, composition for forming plate-crystalline tungsten carbide and process for preparing said hard alloy | |
| EP0759480B1 (fr) | Alliage dur contenant du carbure de tungstène lamellaire, composition pour la préparation de carbure de tungstène lamellaire et procédé pour la préparation de l'alliage dur | |
| EP2010687B1 (fr) | Corps en métal dur et procédé de son production | |
| KR100436327B1 (ko) | 소결 경질 합금 | |
| JP7272353B2 (ja) | 超硬合金、切削工具および超硬合金の製造方法 | |
| CN1497053A (zh) | 硬质合金和用作原材料的基于w的复合碳化物粉末 | |
| EP3814542B1 (fr) | Carbure cémenté avec liant alternatif | |
| JP2990655B2 (ja) | 複合炭化物粉末及びその製造方法 | |
| JP4282298B2 (ja) | 超微粒超硬合金 | |
| JP2004076049A (ja) | 超微粒超硬合金 | |
| EP3205737A1 (fr) | Corps fritté dur résistant à l'oxydation à haute température exempt de métaux rares et son procédé de fabrication | |
| JPH11302767A (ja) | 機械的特性に優れた超硬合金およびその製法 | |
| JP2004142993A (ja) | 六方晶複合炭化物およびその製造方法 | |
| JP2017148895A (ja) | 耐折損性にすぐれたｗｃ基超硬合金製ドリル | |
| JPH0333771B2 (fr) | ||
| JPH06212341A (ja) | 超硬合金及びその製造方法 | |
| JPH07278719A (ja) | 微粒板状晶ｗｃ含有超硬合金およびその製造方法 | |
| JP4140928B2 (ja) | 耐摩耗性硬質焼結合金 | |
| EP4389923A1 (fr) | Outil de coupe en carbure cémenté | |
| JP2004263251A (ja) | ７ａ族元素含有超硬合金 | |
| JP2019123903A (ja) | 高熱伝導性を有する耐熱性ｗｃ基複合材料およびその製造方法 | |
| JP2004238660A (ja) | クロム含有超硬合金 | |
| JPH1136022A (ja) | 板状晶ｗｃ含有超硬合金の製法 | |
| JPH11269573A (ja) | 板状晶ｗｃ含有超硬合金の製法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
| AX | Request for extension of the european patent |
Extension state: AL LT LV MK |
|
| 17P | Request for examination filed |
Effective date: 20040723 |
|
| 17Q | First examination report despatched |
Effective date: 20040922 |
|
| AKX | Designation fees paid |
Designated state(s): AT DE SE |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
| 18D | Application deemed to be withdrawn |
Effective date: 20050202 |