EP3297782B1 - A method of producing a tool for cutting, drilling or crushing of solid material, and such a tool - Google Patents
A method of producing a tool for cutting, drilling or crushing of solid material, and such a tool Download PDFInfo
- Publication number
- EP3297782B1 EP3297782B1 EP16725458.0A EP16725458A EP3297782B1 EP 3297782 B1 EP3297782 B1 EP 3297782B1 EP 16725458 A EP16725458 A EP 16725458A EP 3297782 B1 EP3297782 B1 EP 3297782B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cobalt content
- cemented carbide
- compact
- carbide body
- cobalt
- 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.)
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Links
- 238000000034 method Methods 0.000 title claims description 41
- 238000005520 cutting process Methods 0.000 title claims description 16
- 238000005553 drilling Methods 0.000 title claims description 14
- 239000011343 solid material Substances 0.000 title claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 173
- 239000010941 cobalt Substances 0.000 claims description 173
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 173
- 150000001875 compounds Chemical class 0.000 claims description 73
- 230000001737 promoting effect Effects 0.000 claims description 62
- 229910000831 Steel Inorganic materials 0.000 claims description 46
- 239000010959 steel Substances 0.000 claims description 46
- 238000005219 brazing Methods 0.000 claims description 35
- 239000011651 chromium Substances 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 238000005245 sintering Methods 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 20
- 229910052804 chromium Inorganic materials 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 19
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 10
- 230000009422 growth inhibiting effect Effects 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 150000004767 nitrides Chemical class 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 230000001965 increasing effect Effects 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 230000002401 inhibitory effect Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910003470 tongbaite Inorganic materials 0.000 description 22
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 239000002002 slurry Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000001939 inductive effect Effects 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 7
- 239000007952 growth promoter Substances 0.000 description 7
- 229910000679 solder Inorganic materials 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- IYLGZMTXKJYONK-ACLXAEORSA-N (12s,15r)-15-hydroxy-11,16-dioxo-15,20-dihydrosenecionan-12-yl acetate Chemical compound O1C(=O)[C@](CC)(O)C[C@@H](C)[C@](C)(OC(C)=O)C(=O)OCC2=CCN3[C@H]2[C@H]1CC3 IYLGZMTXKJYONK-ACLXAEORSA-N 0.000 description 6
- -1 Cr3C2 Chemical compound 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 150000001247 metal acetylides Chemical class 0.000 description 6
- IYLGZMTXKJYONK-UHFFFAOYSA-N ruwenine Natural products O1C(=O)C(CC)(O)CC(C)C(C)(OC(C)=O)C(=O)OCC2=CCN3C2C1CC3 IYLGZMTXKJYONK-UHFFFAOYSA-N 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- 238000005255 carburizing Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000011435 rock Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 229910000914 Mn alloy Inorganic materials 0.000 description 3
- UTICYDQJEHVLJZ-UHFFFAOYSA-N copper manganese nickel Chemical compound [Mn].[Ni].[Cu] UTICYDQJEHVLJZ-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 238000007373 indentation Methods 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- 239000004071 soot Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000007542 hardness measurement Methods 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000013074 reference sample Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000003966 growth inhibitor Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
- B22F7/08—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder
-
- 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
- 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
- C22C1/053—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds
- C22C1/055—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds using carbon
-
- 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
- C22C1/053—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds
- C22C1/056—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds using gas
-
- 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
- C22C1/10—Alloys containing non-metals
- C22C1/1094—Alloys containing non-metals comprising an after-treatment
-
- 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
- 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
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21C—MINING OR QUARRYING
- E21C35/00—Details of, or accessories for, machines for slitting or completely freeing the mineral from the seam, not provided for in groups E21C25/00 - E21C33/00, E21C37/00 or E21C39/00
- E21C35/18—Mining picks; Holders therefor
- E21C35/19—Means for fixing picks or holders
-
- 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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Definitions
- the present invention relates to a method of producing a tool for cutting, drilling or crushing of solid material, said tool comprising a cemented carbide body attached to a steel holder, wherein said method comprises the steps of providing said cemented carbide body by; providing a powder mixture, compacting said powder mixture into a compact, sintering the compact into said cemented carbide body, and attaching the compact to said steel holder.
- the present invention also relates to a tool produced in accordance with the principles of the method of the present invention.
- Tools for cutting, drilling or crushing of solid material often comprise a cemented carbide body attached to a steel holder.
- the joint between the cemented carbide body and the steel holder may be a braze joint between a base surface of the cemented carbide body and the steel holder.
- the braze joint may be accomplished by means of a brazing process in which a solder, typically comprised by Nickel-Copper-Manganese alloy, is positioned between the base surface of the cemented carbide body and a surface of the steel holder, and in which the solder is melted and then forced to diffuse into the cemented carbide body and into the steel by means of inductive heating thereof.
- convective heating in an oven may be applied.
- the brazing process may be performed in an inert gas atmosphere, or a fluxing means may be applied onto the cemented carbide body.
- the cobalt in the cemented carbide body plays a vital role in the sense that is responsible for the generation of heat through the induction of an eddy current therein.
- a too low content of cobalt will result in a low wettability of the cemented carbide by the solder, and therefore a poor bonding between the cemented carbide and the steel.
- Cemented carbide bodies with low cobalt contents are therefore generally considered as unsuitable for joining by means of brazing, especially when using inductive brazing which is the most suitable brazing method to use when producing tools for cutting or drilling minerals or rock.
- attachment by means of clamping or similar mechanical joining is considered to be the only reasonable option.
- AU2013273604 A1 discloses a method of sintering a tungsten carbide body for producing a tool, wherein gradients of grain refiner (chromium or vanadium) and binder (cobalt) content are formed inwards from the surface of the compact during sintering.
- cemented carbide with a mean cobalt content of up to 10 wt% actually has an outer surface that is depleted with cobalt as a result of the sintering process, making such a material unsuitable for attachment to steel by means of brazing unless said zone is cobalt enriched.
- WO201298102A1 as well as further prior art, such as disclosed in US4951762A , therefore suggests methods of generating a cobalt gradient in a cemented carbide body by enriching said zone with cobalt in order make such a cemented carbide body, which has a relatively low mean content of cobalt therein, more suitable for attachment to a steel holder by means of brazing.
- the object of the invention is achieved by means of a method of producing a tool for cutting, drilling or crushing of solid material, said tool comprising a cemented carbide body attached to a steel holder, wherein said method comprises the steps of
- cemented carbide body having a low mean cobalt content and/or a low cobalt content in the tip that is active in cutting, crushing etc. at the same time the cemented carbide body has a base region having more a sufficiently high cobalt content to enable strong braze joints to steel.
- the cobalt content at said base surface of the cemented carbide body being cobalt content level (B) becomes ⁇ 5.0 wt%, or ⁇ 5.5 wt%, or ⁇ 6.0 wt%.
- the ratio cobalt content level (B) to cobalt content level (A) is ⁇ 1.12, or ⁇ 1.14, or ⁇ 1.16, or ⁇ 1.2.
- the ratio cobalt content level (B) to cobalt content level (A) is ⁇ 1.5, or ⁇ 1.4.
- said tip region of the cemented carbide body has a mean cobalt content, being cobalt content level (C), of ⁇ 4.5 wt%, or ⁇ 4.0 wt%, or ⁇ 3.5 wt%, or ⁇ 3.0 wt%.
- C cobalt content level
- the extent of the tip region into the body is suitably defined as starting at the surface and going about 2 mm down into the cemented carbide body.
- the ratio cobalt content level (B) to cobalt content level (C) is ⁇ 1.2, or ⁇ 1.3, or ⁇ 1.4.
- the cobalt content of the cemented carbide body is ⁇ about 5.0 wt%.
- the cobalt content of the cemented carbide body is ⁇ about 4.5 wt%.
- said compact comprises top and lateral surfaces and said base surface, and said compound and said grain growth promoting element is applied to at least 50% of the total area of the top and lateral surfaces.
- the degree of coverage of the applied compound and grain growth promoting element, and the amount thereof applied, is decisive for the generation of the required cobalt gradient in the cemented carbide body.
- said compact comprises top and lateral surfaces and said base surface, and said compound and said grain growth promoting element is applied to at least 70% of the total area of the top and lateral surfaces.
- said compact comprises top and lateral surfaces and said base surface, and said compound and said grain growth promoting element is applied to at least 80% of the total area of the top and lateral surfaces.
- said compact comprises top and lateral surfaces and said base surface, and wherein the distance between the top surface and the base surface, which is opposed to the top surface, is less than 25 mm, preferably less than 15 mm, and more preferably less than 10 mm, and wherein said compound and said grain growth promoting element are applied onto at least a part of said top surface. Thanks to a sufficiently low distance between top and base surfaces, sufficiently high cobalt content can be obtained in the base surface due to the generated cobalt gradient.
- said compact comprises top and lateral surfaces and, in a zone of the lateral surface or surfaces neighbouring the base surface, the lateral surface or surfaces are excluded from the application of said compound and said grain growth promoting element. Thereby, the generation of a cobalt-depleted zone in the transition region between lateral surfaces and base surface is avoided.
- said compact has a generally knob-like shape, has a generally circular bottom surface with a diameter d, and has a height h, wherein 0.5 ⁇ h/d ⁇ 2, and said bottom surface defines said base surface.
- said compact has a generally plate-like shape, has width w, a height h and a thickness t, and wherein 0.2 ⁇ h/w ⁇ 2, t ⁇ w, 2mm ⁇ t ⁇ 20mm, and, said base surface is a large side of said compact, and said tip region includes at least a part of an opposite large side thereof.
- the element that has a grain growth inhibiting effect on WC is any of chromium, vanadium, tantalum or niobium, preferably chromium or vanadium, most preferably chromium.
- the grain refiner compound is suitably selected from the group of carbides, mixed carbides, carbonitrides or nitrides of vanadium, chromium, tantalum and niobium.
- the grain refiner compound is a carbide or nitride of chromium or vanadium, such as Cr 3 C 2 , Cr 23 C 6 , Cr 7 C 3 , Cr 2 N, CrN or VC, most preferably carbides of chromium, such as Cr 3 C 2 , Cr 23 C 6 , or Cr 7 C 3 .
- said compound is applied onto the compact in an amount of more than 0.5 mg/cm 2 , preferably more than 2.5 mg/cm 2 , preferably more than 3.0 mg/cm 2 .
- said compound is applied onto the compact in an amount of not more than 10.0 mg/cm 2 , preferably not more than 7.0 mg/cm 2 , preferably not more than 6.0 mg/cm 2 .
- the above-mentioned limits are generally applicable for the different compounds mentioned above and particularly applicable for Cr 3 C 2 . Too high levels of said compound may result in the unwanted generation of brittle phases.
- said grain growth promoting element is carbon in the form of graphite.
- the carbon provided onto the surface of the compact may be in the form of deposited carbon from a carburizing atmosphere, amorphous carbon, which is present in e.g. soot and carbon black, or graphite.
- the carbon is in the form of soot or graphite.
- the weight ratio of grain refiner compound, to grain growth promoter is suitably from about 0.05 to about 50, preferably from about 0.1 to about 25, more preferably from about 0.2 to about 15, even more preferably from about 0.3 to about 12, most preferably from about 0.5 to about 8.
- the weight ratio Cr 3 C 2 /C may preferably be from about 1 to about 14, preferably from about 1.5 to about 6.
- said grain growth element is applied onto the compact in an amount of more than 0.2 mg/cm 2 , preferably more than 0.5 mg/cm 2 , preferably more than 1.0 mg/cm 2 .
- said grain growth-promoting element is applied onto the compact in an amount of not more than 3.0 mg/cm 2 , preferably not more than 2.5 mg/cm 2 .
- the above-mentioned limits are particularly applicable when said grain growth promoting element is carbon. Too high levels of carbon may result in an unwanted generation of a carbon shell on the sintered compact and negative effects on the sintering process.
- the grain refiner compound and/or grain growth promoter may be provided by application in the form of a separate or combined liquid dispersion or slurry to the compact.
- the liquid phase is suitably water, an alcohol or a polymer such as polyethylene glycol.
- the grain refiner compound and grain growth promoter may alternatively be provided by application in the form of solid substances to the compact, preferably powder.
- the application of the grain refiner compound and grain growth promoter onto the compact is suitably made by applying the grain refiner compound and grain growth promoter onto the compact by, dipping, spraying, painting, or application onto the compact in any other way.
- the grain growth promoter is carbon, it may alternatively be provided onto the compact from a carburizing atmosphere.
- the carburizing atmosphere suitably comprises one or more of carbon monoxide or a C1-C4 alkane, i.e. methane, ethane, propane or butane.
- the carburizing is suitably conducted at a temperature of from about 1200 to about 1550°C.
- the compact presents an open porosity and said compound and said grain growth promoting element is provided as powder in slurry which is applied onto the compact, and the powder particle size of said compound and said grain growth promoting element is small enough to enable said powder thereof to be introduced into pores of the compact by capillary forces generated by said pores.
- Open porosity may be referred to as continuous porosity, typical for a not yet fully dense material.
- the grain refiner is diffused away from the surface or surfaces provided with the grain refiner compound, thereby suitably forming a zone with an in average decreasing content of grain refiner when going deeper into the body.
- a zone is also suitably formed during sintering with an in average increasing content of binder when going deeper into the body.
- the sintering temperature is suitably from about 1000°C to about 1700°C, preferably from about 1200°C to about 1600°C, most preferably from about 1300°C to about 1550°C.
- the sintering time is suitably from about 15 minutes to about 5 hours, preferably from about 30 minutes to about 2 hours.
- said brazing is inductive brazing.
- the braze joint may be accomplished by means of a brazing process in which a solder, typically comprised by Nickel-Copper-Manganese alloy, is positioned between the base surface of the cemented carbide body and a surface of the steel holder, and in which the solder is forced to diffuse into the cemented carbide body and into the steel by means of inductive heating thereof.
- the object of the invention is also achieved by means of a tool for cutting, drilling or crushing of solid material, wherein
- the cobalt content at said base surface of the cemented carbide body being cobalt content level (B) is at least 5.0 wt%, or at least 5.5 wt%, or at least 6 wt%.
- the ratio cobalt content level (B) to cobalt content level (A) is ⁇ 1.12, or ⁇ 1.14, or ⁇ 1.16, or ⁇ 1.2.
- the ratio cobalt content level (B) to cobalt content level (A) is ⁇ 1.5, or ⁇ 1.4.
- said tip region of the cemented carbide body has a mean cobalt content, being cobalt content level (C), of ⁇ 4.5 wt%, or ⁇ 4.0 wt%, or ⁇ 3.5 wt%, or ⁇ 3.0 wt%.
- C cobalt content level
- the extent of the tip region into the body is suitably defined as starting at the surface and going about 2 mm down into the cemented carbide body.
- the ratio cobalt content level (B) to cobalt content level (C) is ⁇ 1.2, or ⁇ 1.3, or ⁇ 1.4.
- the cobalt content of the cemented carbide body is ⁇ about 5.0 wt%.
- the cobalt content of the cemented carbide body is ⁇ about 4.5 wt%.
- the Co content gradient and the Co content at the base surface of the cemented carbide body are suitably determined by using the hardness, cobalt concentration and tungsten grain size equation (Eq. 1) by Roebuck et al, "A national measurement good practice guide” No. 20, Mechanical Tests for Hardmetals, National Physics Laboratory, 2009 .
- the WC grain size dWC is first calculated using equation 1 on HV5 hardness data from a reference sample with the same mean Co content. Then HV5 measurements on a sample having a Co content gradient are done by making numerous indentations on a cross sectional cut. As an example, if the cemented carbide body has a thickness of 12 mm one could program the hardness tester to make indentations at 0.3, 0.8, 1.3, 1.8, 2.3, 2.8, 3.3, 3.8, 4.3, 4.8, 5.3 and 5.8 mm distance to the edge on a cross sectional cut. The distance between the indentations can for example be set to 0.5 mm. From the results a HV5 iso lines map is provided. The HV5 hardness iso lines map can then be transformed into a Co content iso lines map by using equation 1.
- the mean Co content for the whole, or part, of the cemented carbide body is suitably determined by chemical analysis.
- said element that has a grain growth inhibiting effect on WC is any of chromium, vanadium, tantalum or niobium, preferably chromium or vanadium, most preferably chromium.
- the grain refiner compound is suitably selected from the group of carbides, mixed carbides, carbonitrides or nitrides of vanadium, chromium, tantalum and niobium.
- the grain refiner compound is a carbide or nitride of chromium or vanadium, such as Cr 3 C 2 , Cr 23 C 6 , Cr 7 C 3 , Cr 2 N, CrN or VC, most preferably carbides of chromium, such as Cr 3 C 2 , Cr 23 C 6 , or Cr 7 C 3 .
- said element that has a grain growth promoting effect on WC is carbon.
- the cemented carbide body can be coated with one or more layers according to known procedures in the art. For example, layers of TiN, TiCN, TiC, and/or oxides of aluminum may be provided onto the cemented carbide body. However, the base surface, aimed for attachment by means of brazing may not be provided with such coating.
- the braze joint has been accomplished by means of inductive brazing.
- the braze joint may be accomplished by means of a brazing process in which a solder, typically comprised by Nickel-Copper-Manganese alloy, is positioned between the base surface of the cemented carbide body and a surface of the steel holder, and in which the solder is forced to diffuse into the cemented carbide body and into the steel by means of inductive heating thereof.
- the cemented carbide body is a cemented carbide tool body.
- the cemented carbide body is a body for a mining tool, such as a rock drilling tool or a mineral cutting tool, or for an oil and gas drilling tool.
- the cemented carbide body is a coldforming tool, such as a tool for forming thread, beverage cans, bolts and nails.
- said cemented carbide body comprises top and lateral surfaces and said base surface, and wherein the distance between the top surface and the base surface, which is opposed to the top surface, is less than 21.2 mm, preferably less than 12.5 mm, and more preferably less than 8.3 mm, wherein the cemented carbide body presents a cobalt content gradient therein in a direction from said top surface towards said base surface as a result of the presence of said grain growth promoting element and said grain growth inhibiting element in the region of said top surface. All measures correspond to the previously mentioned measures of a compact adjusted with regard to the fact that the dimensions of the compact are about 1.2 times larger than the corresponding measures of the sintered compact, i.e. the cemented carbide body.
- the geometry of the body is typically ballistic, spherical or conical shaped, but also chisel shaped and other geometries are suitable in the present invention.
- said compact has a generally knob-like shape (including ballistic, semi-spherical or conical shape), has a generally circular bottom surface with a diameter h, and has a height h, wherein 0.5 ⁇ h/d ⁇ 2, and said bottom surface defines said base surface.
- said compact has a generally plate-like shape, has width w, a height h and a thickness t, and wherein 0.2 ⁇ h/w ⁇ 2, t ⁇ w, 1.7mm ⁇ t ⁇ 17mm, and, said base surface is a large side of said compact, and said tip region includes at least a part of an opposite large side thereof. All measures correspond to the previously mentioned measures of a compact adjusted with regard to the fact that the dimensions of the compact are about 1.2 times larger than the corresponding measures of the sintered compact, i.e. the cemented carbide body.
- the present invention further relates to the use of the cemented carbide tool body in rock drilling or mineral cutting operations.
- Fig. 1 shows an embodiment of a tool 1 according to the invention, comprising a cemented carbide body 2 and a holder 3.
- the cemented carbide body 1 is connected to the holder 3 by means of brazing.
- the tool 1 shown in fig. 1 is an example of a so called MGT-tool designed for mining and graveling applications (MGT: Mineral and Grounds Tools).
- MGT Mineral and Grounds Tools
- the invention is not limited to such tools but could be applied to all kind of tools comprising a cemented carbide body attached to a steel holder by means of brazing.
- the body 2 shown in fig. 1 is produced by means of a process in which a powder mixture is compacted into a compact which is then sintered to the body 2.
- the process includes selection of a suitable powder mixture composition including tungsten carbide and cobalt, compaction thereof to a suitable compact geometry, and treatment of the compact in order to affect the grain size of the tungsten carbide in connection to the subsequent sintering, and to induce a cobalt gradient therein, wherein in the cobalt content increases towards a surface of the sintered body that could preferably be used as a surface which is attached to a steel holder by means of brazing.
- a compact produced in accordance with the teaching is shown in fig. 2 and indicated with reference number 4.
- a process step in which the compact 4 is provided with a coating comprising an element that has a grain growth inhibiting effect on tungsten carbide and an element that has a grain growth inhibiting effect on tungsten carbide is shown in fig. 3 .
- the invention thus includes a method of producing a tool 1 for cutting, drilling or crushing of solid material, said tool comprising a cemented carbide body 2 attached to a steel holder 3, wherein said method comprises the steps of providing said cemented carbide body 2 by; providing a powder mixture, compacting said powder mixture into a compact 4 comprising a hard phase mainly comprised by tungsten carbide, WC, and a binder consisting of cobalt, wherein the cobalt content of the compact 4 is equal to or lower than about 5.5 wt%, providing a compound comprising a carbide or a nitride formed by carbon or nitrogen and an element that has a grain growth inhibiting effect on tungsten carbide, and providing an element that has a grain growth promoting effect on WC, and applying said compound and said grain growth promoting element onto at least a tip region 5 of said compact 4, wherein said tip region 5 will form a tip region 6 of the cemented carbide body 2 aimed for engagement with material to be cut, drilled into, turned or crushed
- the compact 4 provided with said compound and said grain growth promoting element is then sintered into said cemented carbide body 2 such that the cobalt content at said base surface 8 becomes equal to or higher than 4.5 wt% as a result of said induced generation of a cobalt content gradient, the ratio cobalt content level at the base surface 8 to cobalt content of the compact becomes ⁇ 1.09, and said base surface 8 of the cemented carbide body 2 is attached to the steel holder 3 by means of brazing.
- the cobalt content at the base surface 8 of the body 2 is surprisingly high and therefore enables brazing as a means of attaching the body to the steel holder 3.
- bodies with a very low mean content of cobalt can be attached to a steel holder by means of brazing.
- the mean cobalt content may be below 5 wt% or even below 4.5 wt%.
- the compact 4 as presented in figs. 2-4 , as well as the body 2 formed therefrom, is cylindrical with a conical tip. It may be generally defined as knob-shaped.
- the generally circular base surface 7 of the compact 4, and thus the base surface 8 of the body 2 is formed by a bottom surface thereof located opposite to the tip region 5, 6 of the compact 4 and body 2 respectively.
- the base surface 7 of the compact 4 and the base surface 8 of the body 2 are generally flat, but could have some other geometry if necessitated by the design of the steel holder 3 or because of other design-related or function-related reasons.
- slurry 9 comprising said compound, said grain growth promoting element and a solvent, suitably water, an alcohol or a polymer such as polyethylene glycol, is provided in a can 10, and the compact 4 is dipped into the slurry 9, as shown in fig. 3 .
- the compact 4 has an open porosity, and the particles of said compound and said grain growth promoting element in the slurry 9 are of such size that particles of said compound and said grain growth promoting element will be introduced into pores of the compact 4 by capillary forces generated by said pores.
- a solvent suitably water, an alcohol or a polymer such as polyethylene glycol
- said compound consists of particles of Cr 3 C 2 and said grain growth promoting element consists of carbon in the form of soot.
- said grain growth promoting element consists of carbon in the form of soot.
- the amount of said compound and said grain growth promoting element adopted by the compact 4 should be above a predetermined level in relation to the mass of the compact 4.
- a primary reason for introducing said compound and said grain growth promoting element in the compact may be to control the grain size of the tungsten carbide during the subsequent sintering of the compact 4 in order to obtain a body presenting a tip surface having higher hardness due to lower binder content (and slightly larger tungsten carbide grains) and a more ductile region below said surface having higher binder content.
- the shape of the compact 4 in order to promote sufficiently high cobalt content at the base surface 8 of the body 2, the shape of the compact 4, in particular the height is designed with regard thereto.
- the height h of the compact 4 should be less than 25 mm, preferably less than 20 mm, preferably less than 15 mm, and more preferably less than 10 mm.
- a too high cylindrical compact will result in insufficiently high cobalt content at the base surface thereof. Referring to fig. 4 , for a cylindrical compact having a height h and a generally circular base surface with a diameter d, 0.5 ⁇ h/d ⁇ 2.
- the mass of compact into which cobalt is displaced from the region in which said compound and grain growth promoting element is added should be delimited such that a significant cobalt gradient is achieved and remarkably increased cobalt content is obtained at said base surface.
- the porosity of the compact may be in the region of 50%, whereby the measures of the non-sintered compact 4 are about 1.2 times the measures of the sintered compact, i.e. the cemented carbide body 2.
- said compound and grain growth promoting element may also be applied onto lateral surfaces 11 of the compact 4.
- said compound and grain growth promoting element may have a negative effect on the cobalt content of the base surface 7 in the region of said edge 12 or transition region. Therefore, it is preferred that, in a zone 11' of the lateral surface or surfaces 11 neighbouring the base surface 7, the lateral surface or surfaces 11 are excluded from the application of said compound and said grain growth promoting element.
- Figs. 2-4 show the presence of such a zone.
- said compound and said grain growth promoting element should be applied to at least 50%, preferably at least 70%, and most preferably to at least 80% of the total area of the top and lateral surfaces.
- the tip region 5 defines a rounded or conical top surface 5.
- Fig. 6 shows an alternative embodiment of a compact 13, wherein said compact 13 has a generally plate-like shape, has a width w, a height h and a thickness t, and wherein 0.2 ⁇ h/w ⁇ 2, t ⁇ w, 2mm ⁇ t ⁇ 20mm, and, said base surface 14 is a large side of said compact, and said tip region 16 includes at least a part of an opposite large side 15 thereof.
- Fig. 7 shows an alternative approach of where to apply said compound and grain growth element onto the compact 13.
- the tip region 16 of the compact 13 which will form a tip region of the cemented carbide body aimed for engagement with material to be cut, drilled into, turned or crushed by means of said tool, is provided with said compound and grain growth promoting element.
- Application is achieved by means of dipping of the compact 13 into a can filled with slurry corresponding to the can 10 and slurry 9 shown in fig. 3 .
- ⁇ is the angle between the large side of the compact opposite to said base surface
- Fig. 10 shows an example in which ⁇ is approximately 45°, and only an edge region defining said tip region 16 is provided with said compound and grain growth promoting element.
- Fig. 11 shows an alternative embodiment in which the whole large side 15 opposite said based surface 14 has been provided with said compound and grain growth promoting element by using a dipping angle ⁇ of approximately 0°. Parts of the lateral sides 17, from the large side 15 and a distance x towards the base surface 14 of the compact 13 has been provided with said compound and grain growth promoting element.
- the compact 13 has lateral surfaces 18 neighbouring the base surface 14. A zone 18' of the lateral surface or surfaces neighbouring the base surface 14, is excluded from the application of said compound and said grain growth promoting element.
- Fig. 9 shows a body 19 formed by means of sintering of a compact 13 provided with said compound and grain growth promoting element in accordance with the principles disclosed in figs. 7 and 8 .
- a base surface 20, corresponding to the base surface 14 of the compact 13, is attached to a steel holder 21 by means of brazing.
- an end region of the body 19 opposite to the end at which the tip region is located may be attached to steel holder 21 by means of brazing.
- the body 19 and the steel holder 21 together define a tool 22.
- the tip region of the body is indicated with 23.
- the design of the compact will have an impact on the possibility of obtaining sufficiently high cobalt content at the base surface 20 of the body 19.
- the mass of compact into which cobalt is displaced should be delimited. Accordingly, for a compact with the design presented in fig. 6 , 2 mm ⁇ t ⁇ 20 mm.
- the lower the mean cobalt content in the compact the more important it becomes that the thickness thereof is relatively low in order to reduce the mass of compact into which cobalt displaced from regions in which said compound and grain growth promoting element are applied is low, such that a high level of cobalt (equal to or higher than 6 wt%) is obtained at the base surface 20.
- t is less than 20 mm, preferably less than 15 mm, and more preferably less than 10 mm, wherein said compound and said grain growth promoting element are applied onto at least a part of said top surface (here large side 15), preferably on the whole top surface.
- the porosity of the compact may be in the region of 50%, whereby the measures of the non-sintered compact are about 1.2 times the measures of the sintered compact, i.e. the cemented carbide body.
- the following examples should be regarded as supporting the general inventive concept of providing a sufficiently high cobalt content at the base surface of a sintered compact, including for different shapes of the cemented carbide body, such that the latter may be attached to a steel holder by means of brazing, preferably inductive brazing.
- the powder used in the test samples was granulated by spray drying, had a mixture of tungsten carbide, cobalt binder and polymer binder having a carbon balance in such way that no eta phase is found after sintering without green body surface treatment with grain growth promoters and grain growth inhibitors and in the same time having a carbon balance that is compensated for the carbon absorbed from the treatment.
- the sintering was done under normal production sintering conditions for hardmetals.
- the sintered samples were cut along their cylindrical center line and then ground and polished before the HV5 measurement.
- the amount of C and Cr 3 C 2 is roughly 12 mg and 60 mg respectively and hence the specific treatment would be 0.012 mg/mm 2 and 0.061 mg/mm 2 C and Cr 3 C 2 respectively.
- Figure 14 shows that the cobalt concentration difference between the zone closest to the treated surface and zone most distant from the treated surface is about 2.2 wt%.
- Green bodies, compacts, were powder pressed to 50% porosity into 15x15x6 mm rectangular samples.
- the green bodies were dipped according to the drawing showed by figure 7 .
- Sintering was done with standard production sintering furnaces.
- the samples were cut after sintering followed by grinding, polishing and HV5 measurement.
- the added amount of C and Cr 3 C 2 is 2.8 mg and 14.0 mg respectively and hence the specific treatment is 0.010 mg/mm 2 and 0.049 mg/mm 2 respectively.
- the planar treated or dipped sample of the 6% Co grade shows that the HV5 is highest at the treated side and lowest at the opposite side, see figure 15 .
- the calculation of the Co distribution shows that the difference in cobalt concentration between treated surface and opposite surface is about 1.8%.
- the amount of C and Cr 3 C 2 is 3.0 mg and 15.1 mg respectively and hence the specific treatment is 0.011 mg/mm 2 and 0.053 mg/mm 2 respectively.
- the planar treated or dipped sample of the 8% Co grade shows that the HV5 is highest at the treated side and lowest at the opposite side, see figure 16 .
- the calculation of the Co distribution shows that the difference in cobalt concentration between treated surface and opposite surface is about 2.2%.
- the amount of C and Cr 3 C 2 is 0.6 mg and 3.2 mg respectively and hence the specific treatment is 0.010 mg/mm 2 and 0.051 mg/mm 2 respectively.
- the edge treated or dipped sample of the 8% Co grade shows that the HV5 is highest at the treated edge and lowest at the opposite side, see figure 17 .
- the calculation of the Co distribution shows that the difference in cobalt concentration between treated surface and opposite surface is about 2.3%.
- Table 4 shows a summary of the found differences in cobalt concentration (iso-lines maps) between zones closest and most far away from the treated surface.
- Table 4 5.0%Co (ex.1) 10.0%Co (ex. 2) 6.0%Co (ex. 3) 8.0%Co (ex. 4) 8.0%Co (ex. 5) Averaged %Co difference 1.7 2.2 1.8 2.2 2.3
- Example 1 (table 2) and Example 2 (table 3). It is therefore appropriate to use the hardness, cobalt concentration and tungsten grain size equation by Roebuck et al. for determining cobalt content.
- Example 6 (brazing of 5% sample onto steel)
- Example 1 Samples of Example 1 were brazed onto steel plates 20 mm in diameter and 5 mm in thickness made of EN 42CrMo4. Before brazing the steel plates where shot blasted with steel grains. Afterwards the plates where cleaned in an ultrasound cleaner in an ethanol solvent. The cemented carbide samples were grit blasted with SiC grit and also afterwards cleaned in an ultrasound cleaner in an ethanol solvent. The used braze material was also cleaned in an ultrasound cleaner in an ethanol solvent.
- Braze material used High Temp 548 (55% Cu, 6% Ni, 35% Zn, 4% Mn) with solidus temp. 880°C and liquidus temp. 920°C.
- Flux used Superior 609 Assembling procedure: Cover braze shim with flux. Put shim on steel and cemented carbide-disc on top. Cover with flux.
- Inductive brazing under ambient conditions was used.
- the brazing unit consisted of two 20kW generators, but just one was used due to the reason that just one coil (single coil) was necessary to heat the assembly.
- the frequency was adjusted to between 70 and 450kHz according to resonance frequency which guarantees fast heating.
- the assembly was heated up to 950°C (temperature measured by two pyrometers). After around 15 s the braze melted. After about 10 s the assembly was let to cool down in air to room temperature.
- the braze joint was satisfactory strong.
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SE541073C2 (en) * | 2016-11-18 | 2019-03-26 | Epiroc Drilling Tools Ab | Drill bit insert for percussive rock drilling |
EP3406374B1 (en) * | 2017-05-24 | 2020-08-12 | MTC Powder Solutions AB | A method of manufacturing a component comprising a body of a cemented carbide and a body of a metal alloy or of a metal matrix composite |
CN108607999B (zh) * | 2018-06-14 | 2021-04-23 | 陕西理工大学 | 多层易焊大梯度硬质合金材料的制备方法 |
EP3653743A1 (en) * | 2018-11-14 | 2020-05-20 | Sandvik Mining and Construction Tools AB | Binder redistribution within a cemented carbide mining insert |
WO2020218241A1 (ja) * | 2019-04-22 | 2020-10-29 | 京セラ株式会社 | インサート及びこれを備えた切削工具 |
EP3763840B1 (en) * | 2019-07-10 | 2022-04-20 | Sandvik Mining and Construction Tools AB | Gradient cemented carbide body and method of manufacturing thereof |
US11092008B2 (en) | 2019-12-03 | 2021-08-17 | Ironhawk Industrial Distribution LLC | Grader bit |
EP3909707B1 (en) * | 2020-05-14 | 2024-11-06 | Sandvik Mining and Construction Tools AB | Method of treating a cemented carbide mining insert |
CN114045422B (zh) * | 2021-11-15 | 2022-09-09 | 株洲硬质合金集团有限公司 | 一种自锐硬质合金及其制备方法 |
CN114653953B (zh) * | 2022-04-01 | 2024-05-24 | 徐州巴特工程机械股份有限公司 | 一种高强破碎锤钎杆的制造方法 |
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CN1154267A (zh) * | 1996-01-10 | 1997-07-16 | 鞍山钢铁公司 | 高压合成金刚石用的硬质合金顶锤 |
CN2514006Y (zh) * | 2001-11-29 | 2002-10-02 | 江汉石油钻头股份有限公司 | 一种掺有金刚石的梯度硬质合金块 |
CN100365166C (zh) * | 2003-03-18 | 2008-01-30 | 浙江工业大学 | 一种刀具及其加工方法 |
AU2013273604B2 (en) * | 2008-11-11 | 2015-12-03 | Sandvik Intellectual Property Ab | Cemented carbide body and method |
EP2184122A1 (en) * | 2008-11-11 | 2010-05-12 | Sandvik Intellectual Property AB | Cemented carbide body and method |
GB201100966D0 (en) * | 2011-01-20 | 2011-03-02 | Element Six Holding Gmbh | Cemented carbide article |
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