EP2954082A2 - Cemented carbide material and method of making same - Google Patents
Cemented carbide material and method of making sameInfo
- Publication number
- EP2954082A2 EP2954082A2 EP14703394.8A EP14703394A EP2954082A2 EP 2954082 A2 EP2954082 A2 EP 2954082A2 EP 14703394 A EP14703394 A EP 14703394A EP 2954082 A2 EP2954082 A2 EP 2954082A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- cemented carbide
- around
- carbide material
- binder
- phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 212
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 31
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 30
- 239000011230 binding agent Substances 0.000 claims description 49
- 229910003460 diamond Inorganic materials 0.000 claims description 23
- 239000010432 diamond Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 16
- 150000001247 metal acetylides Chemical class 0.000 claims description 14
- 238000003801 milling Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 229910052735 hafnium Inorganic materials 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 229910052758 niobium Inorganic materials 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001887 electron backscatter diffraction Methods 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 8
- 238000010276 construction Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000006104 solid solution Substances 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000003966 growth inhibitor Substances 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000005065 mining Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000009527 percussion Methods 0.000 claims description 2
- GJNGXPDXRVXSEH-UHFFFAOYSA-N 4-chlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C=C1 GJNGXPDXRVXSEH-UHFFFAOYSA-N 0.000 claims 1
- 230000006835 compression Effects 0.000 claims 1
- 238000007906 compression Methods 0.000 claims 1
- 229910020706 Co—Re Inorganic materials 0.000 description 22
- 230000035882 stress Effects 0.000 description 13
- 229910009043 WC-Co Inorganic materials 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 239000002131 composite material Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- 239000003870 refractory metal Substances 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 238000007545 Vickers hardness test Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000001683 neutron diffraction Methods 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- 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
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
-
- 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
-
- 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
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F2005/001—Cutting tools, earth boring or grinding tool other than table ware
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
- B22F3/15—Hot isostatic pressing
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
- C22C2026/006—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes with additional metal compounds being carbides
Definitions
- This disclosure is related to a cemented carbide material such as for use in high-pressure components for synthesis of diamond or c-BN or fabrication of poly-crystalline diamond or c-BN and a method of making same.
- cemented carbides employed for high-pressure high-temperature (HPHT) components used for diamond synthesis and production of polycrystalline diamond (PCD), including anvils and dies, are subjected to high pressures, temperatures and loads. Such unfavorable conditions lead to their deformation and, if the deformation exceeds a certain level, the HPHT components fail. In this respect it is very important to have a cemented carbide material with a high level of Young's modulus to reduce the deformation at high pressures and consequently improve the deformation resistance and lifetime of the HPHT components.
- cemented carbide material for use in the fabrication of high- pressure high-temperature components having improved resistance to deformation as well as high fracture toughness and strength.
- a cemented carbide material comprising WC, Co and Re, wherein: the cemented carbide material comprises between around 3 to around 10 wt.% Co and between around 0.5 to around 8 wt.% Re;
- the equivalent total carbon (ETC) content of the cemented carbide material with respect to WC being between around 6.3 wt.% to around 6.9 wt.%
- the cemented carbide material being substantially free of eta-phase and free carbon.
- a polycrystalline superhard construction comprising: a substrate comprising the cemented carbide material defined above; and a body of polycrystalline superhard material bonded to the substrate along an interface.
- a cutter comprising a substrate comprising the cemented carbide material defined above bonded to a body of polycrystalline superhard material adapted for a rotary drill bit for boring into the earth.
- a PCD element for a rotary shear bit for boring into the earth, for a percussion drill bit or for a pick for mining or asphalt degradation comprising a cutter element comprising a body of superhard polycrystalline material bonded to a body of cemented carbide material as defined above.
- a drill bit or a component of a drill bit for boring into the earth comprising a PCD element as defined above.
- a method of producing the cemented carbide material defined above comprising: milling a cemented carbide mixture containing WC and carbon with Re, Co, Ni and/or Fe and optionally grain growth inhibitors comprising one or more of V, Cr, Ta, Ti, Mo, Zr, Nb and Hf or a carbide thereof; pressing the cemented carbide article from the mixture; sintering the article at a temperature of above around 1450°C in vacuum for between around 1 to 10 minutes and a pressure of Ar (HIP) for around 5 to 120 minutes; and cooling the article from sintering the temperature to approximately 1300 degrees Centigrade (°C).
- HIP pressure of Ar
- a method of recycling the cemented carbide material defined above comprising melting the carbide material in a protective atmosphere with liquid Zn, evaporating the Zn to form a resultant product; and milling the resulting product to recover Re from the product.
- a method of recycling the cemented carbide material defined above comprising subjecting the cemented carbide material to an acid leaching mixture to remove the binder phase from the cemented carbide material; and chemically recovering Co and Re from the removed binder phase.
- a method of recycling the cemented carbide material defined above comprising oxidation of the cemented carbide material to dissolve the carbide, Re and Co, and recovering the Re.
- a cemented carbide material in a high- pressure component for synthesis of diamond or c-BN, or in fabrication of polycrystalline diamond or c-BN operating at a pressure of above 5 GPa and a temperature of above 1 100°C
- the cemented carbide material comprises: a carbide of one or more metals in form of the second carbide phase, or dissolved in a binder phase in the material, said one or more metals comprising Ti, V, Cr, Mn, Zr, Nb, Mo, Hf and/or Ta; between around 0.5 to around 8 wt.% Re and between around 3 to around 10 wt.% Co; the equivalent total carbon (ETC) content of the cemented carbide material with respect to WC being between around 6.3 wt.% to around 6.9 wt.%
- the cemented carbide material being substantially free of eta-phase and free carbon.
- Figure 1 is an SEM image of a cemented carbide material according to a first example and comprising WC-Co-Re;
- Figure 2 is an EBSD image of the WC-Co-Re cemented carbide material of Figure 1 ;
- Figure 3 is an EBSD image showing the microstructure of conventional WC-Co cemented carbide material.
- ETC equivalent total carbon
- a "superhard material” is a material having a Vickers hardness of at least about 25GPa. Diamond and cubic boron nitride (cBN) material are examples of superhard materials.
- a "superhard construction” means a construction comprising polycrystalline superhard material or superhard composite material, or comprising polycrystalline superhard material and superhard composite material bonded to a cemented carbide substrate.
- polycrystalline diamond is a PCS material comprising a mass of diamond grains, a substantial portion of which are directly inter-bonded with each other and in which the content of diamond is at least about 80 volume percent of the material.
- interstices between the diamond gains may be at least partly filled with a binder material comprising a catalyst for diamond.
- interstices or "interstitial regions” are regions between the diamond grains of PCD material.
- interstices or interstitial regions may be substantially or partially filled with a material other than diamond, or they may be substantially empty.
- Embodiments of PCD material may comprise at least a region from which catalyst material has been removed from the interstices, leaving interstitial voids between the diamond grains.
- polycrystalline cubic boron nitride (PCBN) material is a PCS material comprising a mass of cBN grains dispersed within a wear resistant matrix, which may comprise ceramic or metal material, or both, and in which the content of cBN is at least about 50 volume percent of the material.
- the content of cBN grains is at least about 60 volume percent, at least about 70 volume percent or at least about 80 volume percent.
- Embodiments of superhard material may comprise grains of superhard materials dispersed within a hard matrix, wherein the hard matrix preferably comprises ceramic material as a major component, the ceramic material preferably being selected from silicon carbide, titanium nitride and titanium carbo-nitride.
- a cemented carbide material comprises a mass of grains of a hard material comprising a carbide phase and interstices between the hard grains which are filled with a binder material which constitutes the binder phase.
- the carbide phase is WC and the binder phase comprises an alloy of Co and Re with some W and C dissolved in it.
- Figure 3 shows, for comparison, a conventional cemented carbide material comprising WC as the carbide phase and Co as the binder phase.
- the cemented carbide material further comprises a carbide of one or more metals in the form of a second carbide phase or dissolved in the binder phase, the one or more metals comprising Ti, V, Cr, Mn, Zr, Nb, Mo, Hf and/or Ta.
- the cemented carbide material is substantially free of eta-phase and free carbon.
- the cemented carbide material comprises between around 0.5 to around 8 wt% Re.
- the cemented carbide material comprises between around 3 to around 10 wt.% Co.
- the cemented carbide material comprises between around 0.5 to around 6 wt.% Re.
- the WC in the cemented carbide material may, for example, have a mean grain size below around 0.6 microns.
- the equivalent total carbon (ETC) content with respect to WC lies between around 6.3 wt% to around 6.9 wt%.
- the magnetic properties of the cemented carbide material may be related to important structural and compositional characteristics and is understood to be an indication of the carbon content in the cemented carbide material.
- the most common technique for measuring the carbon content in cemented carbides is indirectly, by measuring the concentration of tungsten dissolved in the binder to which it is indirectly proportional. The higher the content of carbon dissolved in the binder the lower the concentration of tungsten dissolved in the binder.
- the magnetic saturation 4 ⁇ or magnetic moment ⁇ of a hard metal, of which cemented tungsten carbide is an example, is defined as the magnetic moment or magnetic saturation per unit weight.
- the magnetic moment, ⁇ , of pure Co is 16.1 micro-Tesla times cubic metre per kilogram ⁇ T.m 3 /kg), and the induction of saturation, also referred to as the magnetic saturation, 4 ⁇ , of pure Co is 201.9 ⁇ . ⁇ 3 ⁇ .
- the following formula may be used to relate magnetic saturation, Ms, to the concentrations of W and C in the binder:
- cemented carbide material have an associated magnetic saturation of at least around 40 percent to around 80 percent of the magnetic saturation of nominally pure Co.
- the mean grain size of carbide grains may be determined by examination of micrographs obtained using a scanning electron microscope (SEM) or light microscopy images of metallurgically prepared cross-sections of a cemented carbide material body, applying the mean linear intercept technique, for example.
- the mean size of the WC grains may be estimated indirectly by measuring the magnetic coercivity of the cemented carbide material, which indicates the mean free path of Co intermediate the grains, from which the WC grain size may be calculated using a simple formula well known in the art. This formula quantifies the inverse relationship between magnetic coercivity of a Co-cemented WC cemented carbide material and the Co mean free path, and consequently the mean WC grain size. Magnetic coercivity has an inverse relationship with MFP.
- the "mean free path" (MFP) of a composite material such as cemented carbide is a measure of the mean distance between the aggregate carbide grains cemented within the binder material.
- the mean free path characteristic of a cemented carbide material may be measured using a micrograph of a polished section of the material. For example, the micrograph may have a magnification of about 1500x.
- the MFP may be determined by measuring the distance between each intersection of a line and a grain boundary on a uniform grid.
- the matrix line segments, Lm are summed and the grain line segments, Lg, are summed.
- the mean matrix segment length using both axes is the "mean free path". Mixtures of multiple distributions of tungsten carbide particle sizes may result in a wide distribution of MFP values for the same matrix content.
- the grain sizes are expressed in terms of Equivalent Circle Diameter (ECD) according to the ISO FDIS 13067 standard.
- ECD Equivalent Circle Diameter
- the carbide phase of the cemented carbide material is formed of carbide grains having a mean grain size of at least around 0.1 ⁇ to at most around 10 ⁇ and the cemented carbide material may have an associated magnetic coercive force varying from around 2kA/m to around 70 kA/m.
- the carbide phase comprises WC and the cemented carbide material has a coercive force He in kA/m as a function of the WC mean grain size D wc in ⁇ determined on the basis of EBSD images of the carbide microstructure equal to or less than values given by the equation:
- the carbide phase comprises WC and the binder phase comprises Co and Re.
- the binder phase of the cemented carbide material may, for example, be a solid solution of Re, carbon and W and one of more of Fe, Co, and Ni.
- the binder phase comprises at least about 0.1 weight percent to at most about 5 weight percent of one or more of V, Cr, Ta, Ti, Mo, Zr, Nb and Hf in solid solution and/or in the form of carbide compounds.
- the material comprises at least about 0.01 weight percent and at most about 2 weight percent of one or more of Ru, Rh, Pd, Os, Ir and Pt.
- the cemented carbide has an associated hardness and, in some embodiments, the hardness decrease at 300°C is at most 20%, or, in some other embodiments, is at most 17%.
- Hardness measurements were carried out according to the DIN ISO 3878 on metallurgical cross-sections at a load of 30 kgf at room temperature as well as at 300°C, 500°C and 800°C in an Ar atmosphere. After achieving the elevated temperatures the cross-section was annealed for 10 min, after which a Vickers indentation was made under the load of 30 kgf and the load was applied for 15 sec.
- the cemented carbide material may, for example, have a hardness decrease at 500°C of at most 30% or, in some other embodiments, at most 27%.
- the hardness-toughness coefficient may be calculated by multiplying the Vickers hardness in GPa and indentation fracture toughness in MPa m 2 , and, in some embodiments, this is above 150.
- the cemented carbide material has a Vickers hardness
- the binder phase of the cemented carbide material has one or more residual compressive stresses and these may, for example, be between around -5 MPa to around 100 MPa.
- An embodiment of a cemented carbide material may be made by a method including milling a cemented carbide mixture containing carbides with Re, Co, Ni and/or Fe and optionally grain growth inhibitors including V, Cr, Ta, Ti, Mo, Zr,, Nb and Hf or their carbides and then pressing a cemented carbide article from the mixture.
- the article is then sintered at temperatures of above 1450°C in vacuum for 1 to 10 min and afterwards under pressure of Ar (HIP) for 5 to 120 min.
- the article is then cooled from the sintering temperatures to approximately 1300 degrees Centigrade (°C) in an atmosphere comprising inert gases, nitrogen, hydrogen or a mixture thereof, or in a vacuum, at a cooling rate of approximately 0.2 to 2 degrees per minute.
- Tungsten carbide powder wherein the WC grains had an average grain size of about 0.6 ⁇ with carbon content of 6.13 wt.%, was milled with 5.5%Re powder and 3.7%Co powder.
- the Co grains had an average grain size of about 1 ⁇ .
- the powder mixture was produced by milling the powders together for 24 hours using a ball mill in a milling medium comprising hexane with 2 wt.% paraffin wax, and using a powder-to-ball ratio of 1 :6. After milling 0.35 wt.% carbon black was added and additional milling was performed for 1 hr resulting in the fact that the equivalent total carbon (ETC) content with respect to WC of the mixture was equal to 6.51 wt.%.
- ETC equivalent total carbon
- a control batch of conventional WC-Co cemented carbides without Re was made from the same WC powder batch and 6 wt.% Co, which corresponds to the same volume percentage of binder as in the WC-Co-Re material, without adding carbon black.
- the batch was milled in the same way as the WC-Co-Re carbide and sintered at 1440°C for 1 hr including 30 sintering vacuum and 30 min sintering under pressure (HIP).
- the carbon content was measured on sintered samples in the same way as for the WC-Co-Re cemented carbides and found to be equal to 5.77 wt.% providing evidence that the equivalent total carbon (ETC) content with respect to WC is equal to 6.13 wt%.
- Metallurgical cross-sections of the WC-Co-Re and WC-Co cemented carbides were made and examined by optical microscopy and SEM.
- the hardness (HV20), indentation fracture toughness (Kic), transverse rupture strength (TRS), compressive strength and Young's modulus as well as coercive force and magnetic moment (saturation) of the sintered bodies were examined.
- the WC mean grain size was measured on the basis of the EBSD image of the cross-sections according to the procedure described in: K.P. Mingard, B. Roebuck a, E.G. Bennett , M.G. Gee, H. Nordenstrom, G. Sweetman, P. Chan . Comparison of EBSD and conventional methods of grain size measurement of hard metals. Int. Journal of Refractory Metals & Hard Materials 27 (2009) 213-223.
- Figures 1 and 2 show SEM and EBSD images respectively of the WC-Co-Re cemented carbide formed according to Example 1
- Figure 3 shows the microstructure of the conventional WC- Co cemented carbides without Re and having the Equivalent Total Carbon content with respect to WC of 6.13 wt.%.
- the WC-Co-Re carbide shown in Figure 1 and Figure 2 has a WC mean grain size of 0.44 ⁇ . It will be seen that there is neither eta-phase nor free carbon nor porosity in the microstructure of both carbide materials shown in Figures 1 and 2.
- Table 1 shows the grain size distribution in the microstructure of the WC-Co-Re cemented carbide shown in Figures 1 and 2.
- the magnetic moment of the WC-Co-Re carbide material of Figure 1 and Figure 2 was equal to 4.7 Gcm 3 /g, which is 64% of the theoretical value for cemented carbide with 3.7 % of nominally pure Co providing evidence for its specific magnetic saturation in per cent (SMS).
- the hardness-toughness coefficient calculated by multiplying the Vickers hardness in GPa and fracture toughness in MPa m 2 was therefore equal to 195.
- the compressive strength of the WC-Co-Re cemented carbide was determined to be 6020 MPa and its Young's modules to be equal to 712 GPa. Its hot hardness was found to be equal to 16.9 GPa at 300°C and 14.9 GPa at 500°C providing evidence that the hardness decrease at the elevated temperatures was about 9.1 % and 19.8% correspondingly. The compressive strength almost did not change when increasing the temperatures from room temperature to 300°C and 500°C.
- the residual stress in the Co-Re binder phase of the WC-Co-Re cemented carbide was measured using a Bruker D8 Discover d iff racto meter using the Cu- ⁇ radiation. This wavelength of X-ray typically obtained diffraction information from a depth of around 5 ⁇ .
- the diffracted beam was collected using a Braun Position Sensivite Detector with a bin size of 0.01059°.
- the residual stress measurement was performed by use of the Co (21 1 ) peak at an angle of 146.6° using a step size of 0.01059° and a count time of 10 sec. per step.
- the residual stress measurements were performed using the standard iso. inclination ⁇ 2 ⁇ technique in accordance with the ref. "Fitzpatrick M, Fry T, Holdway P, et al. NPL Good Practice Guide No. 52: Determination of Residual Stresses by X-ray Diffraction - Issue 2. September 2005".
- Young's modulus is a type of elastic modulus and is a measure of the uni-axial strain in response to a uni-axial stress, within the range of stress for which the material behaves elastically.
- a method of measuring the Young's modulus E is by means of measuring the transverse and longitudinal components of the speed of sound through the material using ultrasonic waves.
- the longitudinal and transverse speeds of sound may be measured using ultrasonic waves, as is well known in the art.
- the cemented carbide material of one or more embodiments may find particular application in use in high-pressure components for synthesis of diamond or c-BN, or in fabrication of poly- crystalline diamond or c-BN operating at pressures of above 5 GPa and temperatures of above 1 100°C.
- PCD composite compact elements may comprise a PCD structure bonded along an interface to an embodiment of a cemented carbide substrate comprising particles of a metal carbide and the binder material described above.
- An embodiment of a PCD composite compact element may be made by a method including providing the cemented carbide substrate, contacting an aggregated, substantially unbonded mass of diamond particles against a surface of the substrate to form an pre-sinter assembly, encapsulating the pre-sinter assembly in a capsule for an ultra-high pressure furnace and subjecting the pre-sinter assembly to a pressure of at least about 5.5 GPa and a temperature of at least about 1 ,250 degrees centigrade, and sintering the diamond particles to form a PCD composite compact element comprising a PCD structure integrally formed on and joined to the cemented carbide substrate.
- the pre-sinter assembly may be subjected to a pressure of at least about 6 GPa, at least about 6.5 GPa, at least about 7 GPa or even at least about 7.5 GPa.
- the hardness of cemented tungsten carbide substrate may be enhanced by subjecting the substrate to an ultra-high pressure and high temperature, particularly at a pressure and temperature at which diamond is thermodynamically stable.
- the magnitude of the enhancement of the hardness may depend on the pressure and temperature conditions.
- the hardness enhancement may increase the higher the pressure. Whilst not wishing to be bound by a particular theory, this is considered to be related to the Co drift from the substrate into the PCD during press sintering, as the extent of the hardness increase is directly dependent on the decrease of Co content in the substrate.
- the cemented carbide material forming the substrate may comprise between around 2 to around 9 wt.% Re, and around 3 to around 9 wt.%Co, with the remainder being WC.
- the working temperature on the surface of the high-pressure components may be at least around 200°C and at most around 800°C.
- the cemented carbide contains cobalt (Co) and rhenium (Re) and the proportion of Re and Co lies in a certain range it may be possible to improve significantly the Young's modulus of the cemented carbide material.
- the cemented carbide hot hardness at temperatures dramatically of up to 800°C.
- the recycling procedure may comprise melting the cemented carbide material in a protective atmosphere with liquid Zn with consequent evaporation of Zn from the mixture, and milling the resulting product.
- the cemented carbide material may be subjected to an acid leaching treatment to remove the binder phase of the cemented carbide article and chemically recover the Co and Re.
- a further method of recycling the cemented carbide material may comprise oxidation of the cemented carbides articles with consequent dissolution of carbides, Re and Co and their recovery.
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Abstract
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US201361763343P | 2013-02-11 | 2013-02-11 | |
GBGB1302345.2A GB201302345D0 (en) | 2013-02-11 | 2013-02-11 | Cemented carbide material and method of making same |
PCT/EP2014/052549 WO2014122306A2 (en) | 2013-02-11 | 2014-02-10 | Cemented carbide material and method of making same |
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EP2954082A2 true EP2954082A2 (en) | 2015-12-16 |
EP2954082B1 EP2954082B1 (en) | 2020-07-22 |
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EP14703394.8A Active EP2954082B1 (en) | 2013-02-11 | 2014-02-10 | Cemented tungsten carbide material, method of making same and use thereof |
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US (3) | US20150376744A1 (en) |
EP (1) | EP2954082B1 (en) |
JP (1) | JP6275750B2 (en) |
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Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2528272B (en) * | 2014-07-15 | 2017-06-21 | Tokamak Energy Ltd | Shielding materials for fusion reactors |
EP3514124A1 (en) * | 2014-09-26 | 2019-07-24 | Diamond Innovations, Inc. | Method for making a superabrasive compact |
US10161017B2 (en) * | 2015-06-08 | 2018-12-25 | Korea Institute Of Geoscience And Mineral Resources | Method for crushing hard tungsten carbide scraps |
CN105154747B (en) * | 2015-09-14 | 2017-04-12 | 江西耀升钨业股份有限公司 | Composite tungsten carbide hard alloy bar and preparation methods thereof |
JP6608941B2 (en) * | 2015-09-26 | 2019-11-20 | 京セラ株式会社 | Rod and cutting tool |
JP6608945B2 (en) * | 2015-09-29 | 2019-11-20 | 京セラ株式会社 | Rod and cutting tool |
US10287824B2 (en) | 2016-03-04 | 2019-05-14 | Baker Hughes Incorporated | Methods of forming polycrystalline diamond |
CN105648296B (en) * | 2016-03-23 | 2018-06-19 | 水利部杭州机械设计研究所 | A kind of high temperature resistance tungsten carbide-base metal-ceramic composite powder end, coating and its preparation process containing Re |
CN105903955B (en) * | 2016-04-27 | 2018-05-22 | 石家庄蓝海工具有限公司 | A kind of diamond segment production technology based on vacuum cooling equipment |
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 |
JP6209300B1 (en) * | 2017-04-27 | 2017-10-04 | 日本タングステン株式会社 | Anvil roll, rotary cutter, and workpiece cutting method |
US11396688B2 (en) | 2017-05-12 | 2022-07-26 | Baker Hughes Holdings Llc | Cutting elements, and related structures and earth-boring tools |
US11292750B2 (en) | 2017-05-12 | 2022-04-05 | Baker Hughes Holdings Llc | Cutting elements and structures |
CN107881389B (en) * | 2017-11-06 | 2019-06-25 | 株洲科力特新材料有限公司 | Ti (C, N) based ceramic metal and the preparation method for being used to prepare it |
CN108160997B (en) * | 2017-12-21 | 2019-12-13 | 株洲硬质合金集团有限公司 | Low-cobalt hard alloy and method for reducing welding cracks of low-cobalt hard alloy |
US11536091B2 (en) | 2018-05-30 | 2022-12-27 | Baker Hughes Holding LLC | Cutting elements, and related earth-boring tools and methods |
WO2019244429A1 (en) | 2018-06-19 | 2019-12-26 | 住友電工ハードメタル株式会社 | Diamond joined body, and method for manufacturing diamond joined body |
KR102167990B1 (en) * | 2018-11-30 | 2020-10-20 | 한국야금 주식회사 | Cutting insert for heat resistant alloy |
DE102019110950A1 (en) | 2019-04-29 | 2020-10-29 | Kennametal Inc. | Hard metal compositions and their applications |
JP6972508B2 (en) * | 2019-12-19 | 2021-11-24 | 株式会社タンガロイ | Carbide and coated cemented carbide, and tools with them |
GB201919479D0 (en) * | 2019-12-31 | 2020-02-12 | Element Six Uk Ltd | Polycrystalline diamond constructions & methods of making same |
GB201919480D0 (en) * | 2019-12-31 | 2020-02-12 | Element Six Uk Ltd | Polycrystalline diamond constructions & methods of making same |
DE102021111371A1 (en) | 2021-05-03 | 2022-11-03 | Betek Gmbh & Co. Kg | Cemented Carbide Material |
CN115466896B (en) * | 2022-07-18 | 2023-04-07 | 广东理工学院 | Preparation method of rare earth modified superfine WC-Co hard alloy |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AT348264B (en) * | 1976-05-04 | 1979-02-12 | Eurotungstene | HARD METALS AND METHOD FOR PRODUCING THEM |
SE505425C2 (en) * | 1992-12-18 | 1997-08-25 | Sandvik Ab | Carbide metal with binder phase enriched surface zone |
US5603075A (en) * | 1995-03-03 | 1997-02-11 | Kennametal Inc. | Corrosion resistant cermet wear parts |
RU2105825C1 (en) * | 1995-06-06 | 1998-02-27 | Санкт-Петербургский государственный технологический институт | Composition of hard-alloy material |
SE521488C2 (en) * | 2000-12-22 | 2003-11-04 | Seco Tools Ab | Coated cutting with iron-nickel-based bonding phase |
US6911063B2 (en) * | 2003-01-13 | 2005-06-28 | Genius Metal, Inc. | Compositions and fabrication methods for hardmetals |
JP5393004B2 (en) * | 2007-06-27 | 2014-01-22 | 京セラ株式会社 | Cemented carbide small diameter rod and cutting tool and miniature drill |
RU2351676C1 (en) * | 2007-10-02 | 2009-04-10 | Юлия Алексеевна Щепочкина | Sintered hard alloy on basis of tungsten carbide |
GB0903343D0 (en) * | 2009-02-27 | 2009-04-22 | Element Six Holding Gmbh | Hard-metal body with graded microstructure |
JP2011235410A (en) * | 2010-05-12 | 2011-11-24 | Mitsubishi Materials Corp | Cutting tool made from wc-based cemented carbide and cutting tool made from surface coating wc-based cemented carbide which exhibit excellent chipping resistance in cutting work of heat resistant alloy |
CN102699330A (en) * | 2012-04-30 | 2012-10-03 | 自贡硬质合金有限责任公司 | Method for producing hard-alloy stud assembled on roll surfaces |
-
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---|
See references of WO2014122306A3 * |
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EP2954082B1 (en) | 2020-07-22 |
WO2014122306A2 (en) | 2014-08-14 |
US20210222273A1 (en) | 2021-07-22 |
WO2014122306A3 (en) | 2015-04-09 |
US20150376744A1 (en) | 2015-12-31 |
CN105074029B (en) | 2019-08-06 |
CN105074029A (en) | 2015-11-18 |
GB2512983A (en) | 2014-10-15 |
GB201302345D0 (en) | 2013-03-27 |
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JP2016513177A (en) | 2016-05-12 |
US20190368011A1 (en) | 2019-12-05 |
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