EP3864183A1 - Hard metal having toughness-increasing microstructure - Google Patents
Hard metal having toughness-increasing microstructureInfo
- Publication number
- EP3864183A1 EP3864183A1 EP19769529.9A EP19769529A EP3864183A1 EP 3864183 A1 EP3864183 A1 EP 3864183A1 EP 19769529 A EP19769529 A EP 19769529A EP 3864183 A1 EP3864183 A1 EP 3864183A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hard metal
- metal
- carbide
- phase
- hard
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
-
- 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
- B22F3/02—Compacting only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
- B22F3/15—Hot isostatic pressing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
-
- 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
- C22C1/10—Alloys containing non-metals
- C22C1/1084—Alloys containing non-metals by mechanical alloying (blending, milling)
-
- 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
-
- 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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Definitions
- the present invention relates to a nanoscale or ultrafine hard metal comprising tungsten carbide, a further metal carbide phase which is present in a cubic crystal structure and a binder metal phase, a process for its production and its use for the production of tools and wear parts. Furthermore, the present invention relates to a component that was produced from the hard metal described.
- Hard metals are metal matrix composite materials, in which hard materials, which are present as small particles, are held together by a matrix made of metal. Hard metals are mainly used in applications in which materials with high wear resistance and hardness with high strength are required. For example, hard metals are used as cutting material for tools (such as turning tools, drills and milling tools) and as wear-resistant dies. B. used in forming or punching tools.
- tools such as turning tools, drills and milling tools
- B. used in forming or punching tools.
- conventional hard metals have the disadvantage that they have a very low fracture toughness, which significantly limits their applicability. An increase in fracture toughness is conventionally possible by increasing the binder metal content, but this leads to a decrease in hardness.
- a tool made of hard metal should have a high hardness with high fracture toughness.
- US 5,593,474 describes a sintered article made of a composite material which has a plurality of regions of a first metal carbide and a plurality of regions of a second metal carbide, the first metal carbide having a larger particle size than the second metal carbide.
- a polycrystalline hard material powder which consists of polycrystalline hard material grains which consist of crystals of the carbides, nitrides and / or carbonitrides of the transition metals of the fourth, fifth and sixth subgroup.
- WO 2017/186468 relates to a hard metal comprising a phase made of hard material grains and a phase made of a heterogeneously distributed binder metal, the hard material grains having an average grain size in the range from 1 nm to 1000 nm and the heterogeneously distributed binder metal in the hard metal is in the form of binder islands, which have an average size of 0.1 mm to 10 mm and an average distance between the binder islands of 1 to 7 mm.
- EP 1526189 discloses a cemented carbide comprising WC, a binder phase based on Co, Ni or Fe and a g-phase, the G-phase has an average particle size of less than 1 m M.
- the g phase is produced by pre-synthesized mixed carbides in the form (Me, W) C.
- CN 103540823 describes a hard metal composition which contains 40 to 50% by weight of WC, 5 to 10% by weight of vanadium carbide, 3 to 8% by weight of chromium carbide, 5 to 9% by weight of titanium carbide, 6 to 11% by weight Tantalum carbide, 2 to 5 wt .-% niobium carbide and 12 to 18 wt .-% cobalt.
- the particle size of the toilet is in the range of 0.1 to 0.8 ⁇ m.
- EP 1 557 230 relates to a hard metal body which has 10 to 12% by weight cobalt, less than 3% by weight tantalum carbide, 1 to 5.5% by weight niobium carbide and 3 to 5% by weight titanium carbide, with WC make up the rest.
- the toilet has a particle size of 0.4 to 1.5 pm, in particular 0.8 to 1.5 pm.
- US 4,698,266 discloses a cutting tool having at most 70% by weight WC and 5 to 10% by weight cobalt binder phase, the rest of the composition being formed from metal carbides selected from the group consisting of TiC, TaC, NbC, HfC and mixtures thereof are selected.
- the average grain size of the toilet is 0.9 to 1.3 pm.
- a first subject of the present invention is therefore a hard metal comprising a) a tungsten carbide phase with an average grain size of 0.05 to 0.5 mhi, b) a further metal carbide phase and c) a binder metal phase, the further metal carbide phase at room temperature in a cubic crystal structure is present, and the proportion of the further metal carbide phase in the hard metal is at least 4% by volume, based on the total volume of the hard metal, and the mean grain size was determined according to the line-cutting method according to ISO 4499-2.
- volume percent to weight percent or weight percent to volume percent are converted using the following formulas:
- rrh denotes the mass fraction
- v the volume fraction
- p ⁇ the density of the respective component
- the hard metal according to the invention is a nanoscale or ultra-fine hard metal, which is classified according to ISO 4499-2.
- hard metal describes a sintered composite material.
- the further metal carbide phase which is present in a cubic crystal structure at room temperature, in the context of the present invention 25 ° C., is hereinafter referred to as being cubic metal carbide.
- the hard metal according to the invention has high hardness and high fracture toughness.
- the problem that occurs with conventional hard metals, that the fracture toughness decreases with increasing hardness of the hard metal, that is to say the material becomes brittle and brittle, did not arise in the case of the hard metal according to the invention observed.
- the positive properties of the hard metal according to the invention are due in particular to the combination of the small grain size of the tungsten carbide and the presence of the cubic metal carbide phase. Therefore, the tungsten carbide used in the hard metal according to the invention has an average grain size of 0.05 to 0.5 pm, preferably 0.05 to 0.23 pm, particularly preferably 0.05 to 0.09 pm, determined according to the ISO line-cut method 4499-2.
- the metal carbide phase which is present in a cubic crystal structure at room temperature, is selected from the group consisting of titanium carbide, tantalum carbide, niobium carbide, hafnium carbide, zirconium carbide, mixtures thereof and mixed carbides of these compounds.
- the metal carbide phase used in the hard metal according to the invention preferably has an average grain size of 0.3 to 4.0 pm, preferably 0.5 to 1.5 pm, determined according to the line cutting method according to ISO 4499-2.
- the metal carbide phases present in the hard metal according to the invention are homogeneously distributed.
- An embodiment is therefore preferred in which the metal carbide phase contained in the hard metal is present in a regularly recurring distribution with an average spacing of 0.5 to 10 pm, preferably 1 to 3 pm.
- the mean distance can be determined by linear analysis (line cutting method) on micrographs using an electron microscope and refers to the distance from the center of the grain to the center of the grain.
- the particular homogeneous distribution of the metal carbide phase in the hard metal according to the invention is attributed, among other things, to the use of a tungsten carbide powder with the grain sizes mentioned above.
- tungsten carbide powder with an average particle size ÜBET of 0.05 to 0.30 pm, preferably 0.05 to 0.25 pm, particularly preferably 0.05 to 0.2 pm is used as the starting material.
- the specific surface can be determined using the BET method in accordance with DIN ISO 9277.
- the density corresponds to the physical density of the pure solid and can be found in the literature, the density for tungsten carbide generally being given as 15.7 g / cm 3 .
- a cubic metal carbide powder which has an average particle size d ⁇ ET of 0.3 to 5 pm, particularly preferably 0.4 to 1 pm, is preferably used as the starting material for the cubic metal carbide , determined according to the BET surface area of the starting material and by conversion according to the formula dß ET 6 / (BET surface area * density).
- the physical density of the respective cubic carbide is to be used as the density. The values can be found in the literature.
- the binding metal is a compound selected from the group consisting of cobalt, iron, nickel and mixtures thereof.
- the binding metal cobalt is particularly preferred.
- the binding metal is a mixture consisting of iron, cobalt and nickel, the proportion of the respective metals in the mixture being more than 1% by mass.
- the hard metal further has grain growth inhibitors, preferably those selected from the group consisting of vanadium carbide, chromium carbide, mixtures thereof and mixed carbides of these compounds.
- the proportion of grain growth inhibitor in the hard metal is preferably 0.05 to 6% by volume, based on the total volume of the hard metal.
- the proportion of tungsten carbide in the hard metal according to the invention does not exceed a proportion of 95% by volume. Therefore, an embodiment is preferred in which the The proportion of tungsten carbide in the hard metal according to the invention is 40 to 90% by volume, based on the total volume of the hard metal. In this way, sufficient hardness and fracture toughness of the hard metal can be ensured.
- the proportion of binding metal in the hard metal is not more than 40% by volume, preferably 10 to 32% by volume, in each case based on the total volume of the hard metal.
- the hardness of the hard metal can be increased while the fracture toughness remains the same if the volume fraction of the further metal carbide phase in the hard metal according to the invention is at least 4% by volume.
- An embodiment is therefore preferred in which the proportion of the further metal carbide phase is 4 to 30% by volume, preferably 10 to 20% by volume, alternatively 25 to 37% by volume, in each case based on the total volume of the hard metal.
- the hard metal according to the invention has the following composition: i) 40 to 90% by volume of tungsten carbide phase; and ii) 10 to 32 vol .-% binder metal phase, and the rest: further metal carbide phase, the proportion of the further metal carbide phase making up at least 4 vol .-%, based on the total volume of the hard metal, and wherein the vol .-% each refer to the Obtain the total volume of the hard metal and add up to 100% by volume, optionally taking into account other components such as grain growth inhibitors.
- the hard metal according to the invention has an advantageous thermal conductivity.
- the hard metal according to the invention has a Thermal conductivity of less than 50 W / m * K, preferably less than 40 W / m * K, determined using laser flash technology at 40 ° C.
- the hard metal according to the invention is further characterized by improved fracture toughness. Therefore, an embodiment is preferred in which the hard metal according to the invention has a fracture toughness of more than 8.0 MPa * m 1/2 , determined on Vickers hardness impressions according to the Palmquist method, as described in Shetty et al. Journal of Materials Science 20 (1985), pp. 1873 to 1882.
- the present invention further provides a process for producing the hard metal according to the invention, comprising: i) providing a powder mixture comprising a) tungsten carbide powder with an average particle size d ⁇ ET of 0.05 to 0.3 ⁇ m, preferably 0.05 to 0.25 pm, particularly preferably 0.05 to 0.2 pm; b) a further metal carbide powder which is at room temperature (25 ° C.) in a cubic crystal structure and has an average particle size dß ET of 0.3 to 5 pm; and c) binder metal powder; and ii) shaping and sintering the mixture.
- a powder mixture comprising a) tungsten carbide powder with an average particle size d ⁇ ET of 0.05 to 0.3 ⁇ m, preferably 0.05 to 0.25 pm, particularly preferably 0.05 to 0.2 pm; b) a further metal carbide powder which is at room temperature (25 ° C.) in a cubic crystal structure and has an average particle size dß ET of 0.3 to 5 pm; and c) binder
- the proportion of the further, cubic metal carbide powder in the powder mixture is selected such that the hard metal obtained has a proportion of at least 4% by volume of the cubic metal carbide phase, based on the total volume of the hard metal.
- binder metal powder those listed above are preferably used.
- the mixture is shaped and sintered to obtain a hard metal body.
- the hard metal body can be a component, for example.
- the sintering in the process according to the invention is carried out at a temperature of 1150 to 1550 ° C. performed.
- the hard metal according to the invention is accessible by means of a process that is simple to implement industrially.
- the hard metal according to the invention can be produced from the pure metal carbides or their mixtures.
- the hard metal according to the invention is particularly suitable for use in areas of application in which high hardness and good fracture toughness are required. Another object of the present invention is therefore the use of the hard metal according to the invention for the production of tools.
- the tools are preferably tools with specific and indefinite cutting edges and tools for machining materials of all kinds.
- Another object of the present invention is a component which is obtained by shaping the hard metal according to the invention.
- the component is preferably selected from the group consisting of drills, solid carbide milling cutters, indexable inserts, saw teeth, forming tools, sealing rings, press punches, press dies and wear parts.
- a 200 g mixture of 62.7% by volume (77% by weight) WC, 15.9% by volume (11% by weight) Co, 12.9% by volume (5% by weight) ) TiC, 4.4% by volume (5% by weight) TaC, 1.9% by volume (1% by weight) Cr 3 C2 and 2.2% by volume (1% by weight) ) VC was ball milled in n-heptane for 48 hours.
- the hard metal dispersion obtained was dried and at a pressure of 300 MPa pressed uniaxially into rectangular test specimens with a green density> 50% of the density expected for the dense body (theoretical density).
- test specimens were compressed in a vacuum at a temperature of 1450 ° C and a holding time of 30 min to over 95% of the theoretical density and then finally compressed in an argon atmosphere at the same temperature (SinterHIP technology).
- the specimens turned out to be completely sealed under the light microscope.
- the porosity according to ISO 4505 corresponded to> A02, B00, C00.
- the Vickers hardness was determined to be 1770 HV10 and the fracture toughness (Kic) was determined by measuring the crack lengths and using the formula from Shetty (Shetty 1985 - Indentation fracture of WC-Co cermets, see reference above) to 9.5 MPa * m 1 / 2 calculated.
- the thermal conductivity (WLF) was determined to be 29 W / m * K (measurement at 40 ° C. using the laser flash technique).
- Table 1 shows the specific parameters compared to a hard metal with a composition without cubic metal carbide additives but otherwise comparable binder metal content.
- the test specimens were compressed in a vacuum at a temperature of 1450 ° C and a holding time of 30 min to over 95% of the theoretical density and then finally compressed in an argon atmosphere at the same temperature (SinterHIP technology).
- the specimens turned out to be completely sealed under the light microscope.
- the porosity according to ISO 4505 corresponded to> A02, B00, C00.
- the Vickers hardness was determined to be 1690 HV10 and the fracture toughness (Kic) was determined by measuring the crack lengths and using the formula from Shetty (Shetty 1985 - Indentation fracture of WC-Co cermets, see reference above) calculated to 9.7 MPa * m 1/2 .
- the thermal conductivity (WLF) was determined to be 39 W / m * K (measurement at 40 ° C. using the laser flash technique).
- Table 1 shows the determined characteristic values in comparison to the characteristic values from example 1.
- Table 1 Composition and achieved hardness, fracture toughness and thermal conductivity of nanoscale or ultra-fine hard metals with a binder metal content of 16 ⁇ 0.2 vol.% Without and with cubic metal carbide additives (MeC) of 17 and 11 vol.%.
- the hard metal dispersion obtained was dried and pressed uniaxially at a pressure of 300 MPa to form rectangular test specimens with a green density> 50% of the density to be expected for the dense body (theoretical density).
- the test specimens were in a vacuum at a temperature of 1460 ° C and a Holding time compressed from 30 min to over 95% of the theoretical density and then finally compressed in an argon atmosphere at the same temperature (SinterHIP technology).
- the specimens turned out to be completely sealed under the light microscope.
- the porosity according to ISO 4505 corresponded to> A02, B00, C00.
- the Vickers hardness was determined to be 2020 HV10 and the fracture toughness (Kic) was determined by measuring the crack lengths and using the formula from Shetty (Shetty 1985 - Indentation fracture of WC-Co cermets, see reference above) to 8.5 MPa * m 1 / 2 calculated.
- the thermal conductivity (WLF) was determined to be 35 W / m * K (measurement at 40 ° C. using the laser flash technique).
- Table 2 shows the specific parameters compared to a hard metal with a composition without cubic metal carbide additives but otherwise comparable binder metal content.
- Table 2 Composition and achieved hardness, fracture toughness and thermal conductivity of nanoscale or ultra-fine hard metals with a binder metal content of 10 ⁇ 0.2% by volume without and with cubic metal carbide additives (MeC)
- the hard metals according to the examples according to the examples have improved fracture toughness and lower thermal conductivity than conventional hard metals, without the Vickers hardness of the hard metals according to the invention being impaired within the accepted tolerance of ⁇ 20 HV10.
- Figure 1 shows a scanning electron image of a hard metal according to the invention, which shows the regularly recurring distribution of the further metal carbide phase with an average distance of about 1 to 3 pm.
- the recording was on an electron microscope with ESB detector at an acceleration voltage of 2 kV and a magnification of 10,000 times. It shows
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP18200028 | 2018-10-12 | ||
PCT/EP2019/075352 WO2020074241A1 (en) | 2018-10-12 | 2019-09-20 | Hard metal having toughness-increasing microstructure |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3864183A1 true EP3864183A1 (en) | 2021-08-18 |
Family
ID=64023937
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19769529.9A Pending EP3864183A1 (en) | 2018-10-12 | 2019-09-20 | Hard metal having toughness-increasing microstructure |
Country Status (9)
Country | Link |
---|---|
US (1) | US20220267882A1 (en) |
EP (1) | EP3864183A1 (en) |
JP (1) | JP2022504253A (en) |
KR (1) | KR20210075078A (en) |
CN (2) | CN112840050B (en) |
CA (1) | CA3114969A1 (en) |
IL (1) | IL281952A (en) |
MX (1) | MX2021003781A (en) |
WO (1) | WO2020074241A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020086971A1 (en) | 2018-10-26 | 2020-04-30 | Oerlikon Metco (Us) Inc. | Corrosion and wear resistant nickel based alloys |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4698266A (en) * | 1985-11-18 | 1987-10-06 | Gte Laboratories Incorporated | Coated cemented carbide tool for steel roughing applications and methods for machining |
US5593474A (en) | 1988-08-04 | 1997-01-14 | Smith International, Inc. | Composite cemented carbide |
SE527348C2 (en) * | 2003-10-23 | 2006-02-14 | Sandvik Intellectual Property | Ways to make a cemented carbide |
SE527679C2 (en) * | 2004-01-26 | 2006-05-09 | Sandvik Intellectual Property | Carbide body, especially spiral drill, and its use for rotary metalworking tools |
DE102004051288B4 (en) | 2004-10-15 | 2009-04-16 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Polycrystalline hard material powder, composite material with a polycrystalline hard material powder and method for producing a polycrystalline hard material powder |
CN103540823A (en) * | 2013-10-17 | 2014-01-29 | 常熟市良益金属材料有限公司 | Hard alloy |
DE102016207028A1 (en) | 2016-04-26 | 2017-10-26 | H.C. Starck Gmbh | Carbide with toughening structure |
CN108570589B (en) * | 2018-04-09 | 2020-05-05 | 广东翔鹭钨业股份有限公司 | Hard alloy cutter material and preparation method thereof |
-
2019
- 2019-09-20 CA CA3114969A patent/CA3114969A1/en active Pending
- 2019-09-20 CN CN201980065576.7A patent/CN112840050B/en active Active
- 2019-09-20 CN CN202310280386.5A patent/CN116287927A/en active Pending
- 2019-09-20 EP EP19769529.9A patent/EP3864183A1/en active Pending
- 2019-09-20 WO PCT/EP2019/075352 patent/WO2020074241A1/en active Application Filing
- 2019-09-20 US US17/282,062 patent/US20220267882A1/en active Pending
- 2019-09-20 KR KR1020217009568A patent/KR20210075078A/en not_active Application Discontinuation
- 2019-09-20 MX MX2021003781A patent/MX2021003781A/en unknown
- 2019-09-20 JP JP2021518593A patent/JP2022504253A/en active Pending
-
2021
- 2021-03-31 IL IL281952A patent/IL281952A/en unknown
Also Published As
Publication number | Publication date |
---|---|
CN112840050B (en) | 2023-06-09 |
CA3114969A1 (en) | 2020-04-16 |
JP2022504253A (en) | 2022-01-13 |
CN116287927A (en) | 2023-06-23 |
KR20210075078A (en) | 2021-06-22 |
CN112840050A (en) | 2021-05-25 |
MX2021003781A (en) | 2021-05-27 |
WO2020074241A1 (en) | 2020-04-16 |
IL281952A (en) | 2021-05-31 |
US20220267882A1 (en) | 2022-08-25 |
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