EP1364732A2 - Hartmetallbauteil mit gradiertem Aufbau - Google Patents
Hartmetallbauteil mit gradiertem Aufbau Download PDFInfo
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- EP1364732A2 EP1364732A2 EP03008539A EP03008539A EP1364732A2 EP 1364732 A2 EP1364732 A2 EP 1364732A2 EP 03008539 A EP03008539 A EP 03008539A EP 03008539 A EP03008539 A EP 03008539A EP 1364732 A2 EP1364732 A2 EP 1364732A2
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- component
- hard metal
- carbide
- metal alloy
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- 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
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- 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
- B22F7/02—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 layers
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- 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
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- 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
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- 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 invention relates to a powder metallurgically produced component of a Hard metal alloy with a binder content of 0.1 to 20 wt.%,
- The contains at least one grain growth inhibiting additive and a method for its production.
- hard metal is meant a composite material consisting essentially of a carbide component and a binder.
- Carbide components include the carbides or mixed carbides of the metals W, Ti, Zr, Hf, V, Nb, Ta, Mo and Cr.
- Typical binder metals are Co, Ni and Fe.
- the properties of hard metals are determined by the ratio of carbide content to binder content, chemical composition, carbide grain size and carbide grain size distribution. This opens up many possibilities to adapt the properties of carbide to the respective field of application.
- increasing binder content improves fracture toughness and flexural strength while reducing hardness, stiffness and compressive strength.
- a reduction in the carbide grain size leads to an increase in hardness, compressive and flexural strength, with reduced impact and fracture toughness.
- carbide powders in the particle size range 0.2 ⁇ m to 15 ⁇ m are used today for the production of carbide components.
- grain growth inhibitors are added.
- the most effective grain growth inhibiting additives are vanadium carbide, chromium carbide, titanium carbide, tantalum carbide and niobium carbide.
- two or more additives are used, such as mixtures of VC and Cr 3 C 2 or TaC, NbC and TiC.
- the grain growth-inhibiting additive can be finely distributed in the main component before or during the carburization. However, the effectiveness is also present when the grain growth inhibitor is added to the hard metal powder or individual constituents of the hard metal powder before, during or after the grinding.
- Hard metal components can be locally loaded very differently. Therefore are early solutions have been known or implemented on a Composite of two or more carbide alloys based. So describes the US 5,543,235 a hard metal composite material, which by powder metallurgical composite pressing is produced, wherein the individual material areas by their composition or microstructure differ. A rotating compound tool that consists of two Hard metal alloys is constructed, is also in PCT / US00 / 33644 described. The preparation is also preferably via composite presses.
- a disadvantage of the material composites described here is that in the areas of the composite where materials with different Properties meet, stress concentrations arise. Furthermore, it has to be considered that every material component has its own Having sintering behavior. This can cause a distortion of the component during the Trigger sintering.
- composition graded construction it is understood that the composition is gradual over a range of continuously changes.
- graded Finishes in the area of the layer, in the area of the transition Layer / base material and in the neighboring base material for a long time known.
- This grading is achieved, for example, by the addition of Carbonitrides.
- the nitrogen is broken down in the edge zone of the carbide body.
- the metallic carbide or nitride forming elements diffuse towards the center of the Carbide body. This achieves a binder enrichment in the field of Edge zone and a graded transition to the matrix composition.
- indexable inserts with a binder-rich edge zone, adjacent the hard material layer, long used for steel cutting.
- grading is limited to a small, near-surface area.
- EP 0247985 and EP 0498 781 are also carbide body with a gradient of the binder phase and a method of preparation described. It is first using a carburized Starting powder mixture by means of conventional process steps a sintered body with evenly distributed ⁇ -phase produced. About a subsequent Treatment in a carburizing atmosphere achieves a dissolution of the ⁇ -phase in the area of the edge zone. Towards the center of the carbide body As the proportion of ⁇ -phase gradually increases, the binder metal content gradually decreases. The disadvantage, however, is that the ⁇ phase has an embrittling effect. In addition, the additional carburizing step time and energy consuming.
- EP 0 111 600 is a highly stressed tool for the Rockwork described. This consists of an inner and an outer area, with a continuous transition of mechanical properties between these areas.
- Process engineering is proposed a complex powder feed, with the it is possible during the filling process, the concentration of the powder to change continuously. Such a powder feed is expensive in terms of apparatus and technically difficult to master.
- a component made of a hard metal alloy and a method for its production wherein the hard metal alloy at least a carbide, mixed carbide or carbonitride of the metals of group W, Ti, Ta, Mo, Zr, Hf, V, Nb, Cr and V, at least one grain growth inhibiting additive the group V, Cr, Ti, Ta and Nb or a compound of these metals and contains at least one metallic binder of the group Co, Ni and Fe, wherein at least one of the grain growth inhibiting additives at least locally Has graded concentration curve.
- the hard metal alloy at least a carbide, mixed carbide or carbonitride of the metals of group W, Ti, Ta, Mo, Zr, Hf, V, Nb, Cr and V, at least one grain growth inhibiting additive the group V, Cr, Ti, Ta and Nb or a compound of these metals and contains at least one metallic binder of the group Co, Ni and Fe, wherein at least one of the grain growth inhibiting additives at least locally Has graded concentration curve.
- the graded concentration course of the grain growth inhibiting additive leads to a graded course of the carbide grain size. Subsequently, the mechanical properties also show a graded course. This is advantageous, for example, where a high level of wear resistance and bending strength at the surface and at the same time a high level of toughness in the core is required, for example in the case of forming tools or tools for diamond production. If now the concentration profile of the grain growth-inhibiting additive is adjusted so that the concentration values are higher in the region of the edge zone and they decrease in the direction of the center of the component, the edge zone is fine-grained, with a graded transition to the coarse-grained center.
- components with excellent wear resistance and bending strength in the region of the edge zone, combined with a high toughness of the center can be produced. These have improved tool life.
- a high fracture toughness in the region of the edge zone may be advantageous. This is achieved by a reduced content of grain growth inhibiting additive in the region of the edge zone.
- the compressive and flexural strength properties are improved in the core of the component.
- This version is also favorable for coated parts.
- the effect of the invention is also given if the hard metal alloy contains other non-carbide hard material phases, as long as the mechanical properties are not appreciably affected unfavorably.
- Advantageous grain growth inhibiting additives are vanadium and chromium compounds, the maximum concentration being 2% by weight. Higher levels lead to embrittlement effects.
- a particularly advantageous process is the superficial application of a dispersion or solution on a green body.
- the dispersion contains the grain growth inhibiting additive in very finely divided form.
- the green compact can be in the as-pressed state. If the green compact contains waxing or plasticizing agent additives, it can also be present in the dewaxed or partially dewaxed state, in accordance with an advantageous embodiment of the present invention.
- the dispersion or solution can be applied, for example, by dipping, spraying or brushing on. Subsequently, the dispersion or solution penetrates into the interior of the green body along open pore channels.
- the reaction time and the content of the dispersion or solution of grain growth inhibiting additive essentially determine the amount introduced or the penetration depth. It is therefore possible, depending on the requirement profile, to set a grading which extends only on the micrometer scale. However, it is also possible to perform the grading so that it extends to the center of the component. Furthermore, the process can also be carried out so that initially the green compact is completely soaked with the dispersion. This is then removed again by appropriate solvents or by thermal processes from the near-surface areas. Furthermore, the dispersion can be applied over the entire surface or even only locally. Specifically, the local application allows the production of components or tools that only have a high hardness where wear resistance is required. The remaining areas have a coarser texture with high fracture toughness.
- FIGS. 1 to 5 show the vanadium content over the sample cross-section.
- Fig. 1 shows the vanadium content over the sample cross-section.
- Figure 2 in addition to the vanadium content and the carbide grain size is indicated.
- 3 and 5 each show the hardness profile over the sample cross-section.
- Fig. 4 shows schematically the cross section of a drawing tool.
- FIG. 1 and FIG. 2 relate to example 1, FIG. 3 to example 2, FIG. 4 and FIG. 5 to example 3.
- green compacts were produced in the form of indexable inserts.
- the greenlings were subjected to a usual eviscerating process.
- a dispersion of distilled water and V 2 O 5 was prepared, the solid content being 2% by weight and the average V 2 O 5 particle size being less than 50 nm.
- the green compacts were immersed for 5 seconds in the above-described dispersion and then dried in air at 50 ° C.
- Fig. 1 shows that the vanadium content in the region of the edge zone is 0.24% by weight and this value decreases gradually over the cross section of the sample towards the inside.
- the vanadium content at a distance of 3.8 mm from the sample edge is 0.08 wt.%.
- the corresponding vanadium concentrations were below the detection limit of the microprobe.
- the graded vanadium distribution results in a graded grain stabilization effect, as documented by the WC grain size values in FIG. As the average grain size increases from the edge zone toward the center, the corresponding hardness values decrease, as shown in FIG.
- a cemented carbide approach with 89.5 wt.% WC micron a mean grain size of 0.8, 0.5 wt.% Cr 3 C 2, balance Co was prepared according to the usual method in the hard metal industry.
- samples were sintered with reference green sheets that were not aftertreated at a temperature of 1400 ° C under vacuum.
- the analysis of the samples was carried out by means of electron microprobe, the microstructural and mechanical characterization by a light microscopic examination or hardness testing.
- the samples according to the invention again show a graded vanadium concentration course, with a marginal zone value of 0.21 wt.% V and a center value of 0.03 wt.% V.
- the corresponding hardness values are 1698 HV30 or 1648 HV30.
- the hardness profile is reproduced in FIG.
- the reference sample shows a uniform hardness profile over the cross section with an average value of 1605 HV30.
- the samples according to the invention and the reference samples were also subjected to a bending test.
- the mean value of ten measurements is 3950 MPa for the samples according to the invention and 3500 MPa for the comparative samples.
- a hard metal batch with 93.4 wt.% WC with an average particle size of 2.0 .mu.m, 0.2 wt.% TiC, 0.4 wt.% TaC / NbC, remainder Co was prepared according to the methods customary in the hard metal industry. Cylindrical green compacts were produced by isostatic pressing with a compacting pressure of 100 MPa, which were formed by mechanical machining into a hard metal drawing tool. The greenlings were subjected to a usual eviscerating process. In turn, a dispersion of distilled water and V 2 O 5 was prepared, wherein the solids content was 2 wt.%, With a particle size of dispersed V 2 O 5 particles of less than 50 nm.
Abstract
Description
So bewirkt eine Erhöhung des Bindergehaltes eine Verbesserung der Bruchzähigkeit und Biegefestigkeit, bei gleichzeitiger Verringerung der Härte, Steifigkeit und Druckfestigkeit. Eine Verringerung der Karbidkorngröße führt zu einer Erhöhung der Härte, der Druck- und Biegefestigkeit, bei reduzierter Schlag- und Bruchzähigkeit.
Als vorteilhafte kornwachstumshemmende Zusätze sind Vanadium- und Chromverbindungen zu nennen, wobei die maximale Konzentration 2 Gew.% beträgt. Höhere Gehalte führen zu Versprödungseffekten. Als besonders vorteilhaftes Verfahren ist das oberflächliche Aufbringen einer Dispersion oder Lösung auf einem Grünling zu nennen. Die Dispersion enthält dabei den kornwachstumshemmenden Zusatz in feinst verteilter Form. Der Grünling kann im wie-gepressten Zustand vorliegen. Enthält der Grünling Wachs-, bzw. Plastifizierungsmittelzusätze, kann dieser, entsprechend einer vorteilhaften Ausgestaltung der vorliegenden Erfindung, auch im entwachsten oder teilentwachsten Zustand vorliegen. Das Aufbringen der Dispersion bzw. Lösung kann beispielsweise durch Tauchen, Aufsprühen oder Aufpinseln erfolgen. In weiterer Folge dringt die Dispersion bzw. Lösung entlang offener Porenkanäle in das Innere des Grünlings ein. Die Einwirkzeit und der Gehalt der Dispersion bzw. Lösung an kornwachstumshemmendem Zusatz bestimmen im wesentlichen die eingebrachte Menge bzw. die Eindringtiefe. Es kann daher, je nach Anforderungsprofil, eine Gradierung eingestellt werden, die sich nur im Mikrometermassstab erstreckt. Es ist jedoch auch möglich, die Gradierung so auszuführen, dass diese bis zum Zentrum des Bauteils reicht. Des weiteren kann der Prozess auch so durchgeführt werden, dass zunächst der Grünling vollständig mit der Dispersion getränkt wird. Diese wird dann durch entsprechende Lösungsmittel oder durch thermische Verfahren wieder aus den oberflächennahen Bereichen entfernt. Weiters kann die Dispersion auf der gesamten Oberfläche oder auch nur örtlich aufgebracht werden. Speziell das örtliche Aufbringen ermöglicht die Herstellung von Bauteilen bzw. Werkzeugen, die nur dort eine hohe Härte aufweisen, wo Verschleißbeständigkeit erforderlich ist. Die restlichen Bereiche weisen ein gröberes Gefüge mit hoher Risszähigkeit auf. Weiters erweist es sich als vorteilhaft, wenn die karbidische Komponente des Grünlings eine mittlere Korngröße von kleiner 2 µm aufweist.
Im folgenden sind Herstellbeispiele angeführt, die exemplarisch die erfindungsgemäße Ausführung erläutern sollen. Zur Veranschaulichung der Ergebnisse der Beispiele 1 bis 3 dienen Fig. 1 bis Fig. 5.
Fig. 1 zeigt den Vanadium-Gehalt über den Probenquerschnitt. In Fig.2 ist neben dem Vanadium-Gehalt auch die Karbidkorngröße angegeben. Fig.3 und Fig. 5 zeigen jeweils den Härteverlauf über den Probenquerschnitt. Fig. 4 zeigt schematisch den Querschnitt eines Ziehwerkzeuges. Fig. 1 und Fig. 2 beziehen sich dabei auf Beispiel 1, Fig. 3 auf Beispiel 2, Fig. 4 und Fig. 5 auf Beispiel 3.
Claims (13)
- Bauteil aus einer Hartmetalllegierung, enthaltend zumindest ein Karbid, Mischkarbid oder Karbonitrid der Metalle der Gruppe W, Ti, Ta, Mo, Zr, Hf, V, Nb, Cr und V, zumindest einen kornwachstumshemmenden Zusatz der Gruppe V, Cr, Ti, Ta und Nb oder eine Verbindung dieser Metalle, und zumindest einen metallischen Binder der Gruppe Co, Ni und Fe, wobei der Bindergehalt 0,1 - 20 Gewichtsprozent beträgt, dadurch gekennzeichnet, dass zumindest einer der kornwachstumshemmenden Zusätze zumindest lokal einen gradierten Konzentrationsverlauf aufweist.
- Bauteil aus einer Hartmetalllegierung nach Anspruch 1, dadurch gekennzeichnet, dass dieses zumindest örtlich einen gradierten Verlauf der Korngröße aufweist.
- Bauteil aus einer Hartmetalllegierung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass dieses zumindest örtlich einen gradierten Härteverlauf aufweist.
- Bauteil aus einer Hartmetalllegierung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der kornwachstumshemmende Zusatz von der Randzone des Bauteils in Richtung Zentrum des Bauteils gradiert abnimmt.
- Bauteil aus einer Hartmetalllegierung nach Anspruch 4, dadurch gekennzeichnet, dass die Karbidkorngröße von der Randzone des Bauteils in Richtung des Zentrums des Bauteils gradiert zunimmt.
- Bauteil aus einer Hartmetalllegierung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der kornwachstumshemmende Zusatz von der Randzone des Bauteils in Richtung Zentrum des Bauteils gradiert zunimmt.
- Bauteil aus einer Hartmetalllegierung nach Anspruch 6, dadurch gekennzeichnet, dass die Karbidkorngröße von der Randzone des Bauteils in Richtung Zentrum des Bauteils gradiert abnimmt.
- Bauteil aus einer Hartmetalllegierung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass der kornwachstumshemmendem Zusatz aus Cr und/oder V oder einer Verbindung dieser Metalle besteht und der maximale Gehalt bezogen auf die Hartmetalllegierung 2 Gew.% beträgt und dieser graduell auf einen Wert x absinkt, mit 0 < x < 1.0 Gew.%.
- Verfahren zur Herstellung eines Bauteils nach Anspruch 1, dadurch gekennzeichnet, dass dessen Herstellung zumindest folgende Verfahrensschritte umfasst:Herstellen eines Grünlings aus einer Hartmetalllegierung, enthaltend zumindest ein Karbid, Mischkarbid oder Karbonitrid der Metalle der Gruppe W, Ti, Ta, Mo, Zr, Hf, V, Nb, Cr und V, zumindest einen metallischen Binder aus der Gruppe Co, Ni und Fe und optional einen Wachszusatz oder ein Plastifizierungsmittel, nach den üblichen pulvermetallurgischen Kompaktierungs- bzw. Formgebungsverfahren;Herstellen einer Dispersion oder Lösung, die zumindest einen kornwachstumshemmenden Zusatz aus der Gruppe V, Cr, Ti, Ta und Nb oder einer Verbindung dieser Metalle in fein verteilter oder gelöster Form enthält;Aufbringen und dieser Dispersion oder Lösung auf die Oberfläche des Grünlings durch beispielsweise Tauchen, Aufsprühen oder Aufpinseln;Gezieltes Einwirkenlassen zur Einstellung des KonzentrationsgradientenWarmkonsolidierung.
- Verfahren zur Herstellung eines Bauteils nach Anspruch 1, dadurch gekennzeichnet, dass dessen Herstellung zumindest folgende Verfahrensschritte umfasst:Herstellen eines Grünlings aus einer Hartmetalllegierung, enthaltend zumindest ein Karbid, Mischkarbid oder Karbonitrid der Metalle der Gruppe W, Ti, Ta, Mo, Zr, Hf, V, Nb, Cr und V, zumindest einen metallischen Binder aus der Gruppe Co, Ni und Fe und optional einen Wachszusatz oder ein Plastifizierungsmittel, nach den üblichen pulvermetallurgischen Kompaktierungs- bzw. Formgebungsverfahren;Herstellen einer Lösung, die zumindest einen kornwachstumshemmenden Zusatz aus der Gruppe V, Cr, Ti, Ta und Nb oder eine Verbindung dieser Metalle enthält;Aufbringen dieser Lösung auf die Oberfläche des Grünlings durch beispielsweise Tauchen, Aufsprühen oder Aufpinseln;Gezieltes Einwirkenlassen zur Einstellung eines Konzentrationsgradienten oder vollständiger Durchdringung;Gradueller Abbau des Kornwachstumshemmers aus oberflächennahen Bereichen durch eine thermische Behandlung und/oder ein Lösungsmittel;Warmkonsolidierung.
- Verfahren zur Herstellung eines Bauteils nach Anspruch 9 oder 10, dadurch gekennzeichnet, dass die Dispersion oder Lösung nur auf einen Teilbereich der Bauteiloberfläche aufgebracht wird.
- Verfahren zur Herstellung eines Bauteils nach Anspruch 9 oder 10, dadurch gekennzeichnet, dass die karbidische Pulverkomponente des Grünlings eine mittlere Korngröße von < 2 µm aufweist.
- Verfahren zur Herstellung eines Bauteils nach Anspruch 9 oder 10, dadurch gekennzeichnet, dass der Grünling durch einen Wärmebehandlungsschritt zumindest teilentwachst wird.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT0024502U AT5837U1 (de) | 2002-04-17 | 2002-04-17 | Hartmetallbauteil mit gradiertem aufbau |
AT2452002U | 2002-04-17 |
Publications (3)
Publication Number | Publication Date |
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EP1364732A2 true EP1364732A2 (de) | 2003-11-26 |
EP1364732A3 EP1364732A3 (de) | 2005-12-21 |
EP1364732B1 EP1364732B1 (de) | 2008-03-05 |
Family
ID=3485393
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP03008539A Expired - Lifetime EP1364732B1 (de) | 2002-04-17 | 2003-04-14 | Hartmetallbauteil mit gradiertem Aufbau |
Country Status (7)
Country | Link |
---|---|
US (2) | US20040009088A1 (de) |
EP (1) | EP1364732B1 (de) |
JP (1) | JP2003328067A (de) |
CN (1) | CN100482836C (de) |
AT (2) | AT5837U1 (de) |
DE (1) | DE50309292D1 (de) |
IL (1) | IL155430A (de) |
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DE102008040093A1 (de) | 2008-07-02 | 2008-12-18 | Basf Se | Verfahren zur Herstellung eines ringähnlichen oxidischen Formkörpers |
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EP3653743A1 (de) * | 2018-11-14 | 2020-05-20 | Sandvik Mining and Construction Tools AB | Bindemittelumverteilung in einem hartmetallbergbaueinsatz |
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CN111069610A (zh) * | 2019-12-20 | 2020-04-28 | 株洲硬质合金集团有限公司 | 一种梯度结构硬质合金球齿及其制备方法 |
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CN114737097B (zh) * | 2022-04-27 | 2022-12-09 | 山东大学 | 一种三层梯度结构硬质合金及其制备方法 |
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CN1636654B (zh) * | 2003-12-15 | 2011-09-21 | 山特维克知识产权股份有限公司 | 硬质合金工具及其制造方法 |
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DE102008040094A1 (de) | 2008-07-02 | 2009-01-29 | Basf Se | Verfahren zur Herstellung eines oxidischen geometrischen Formkörpers |
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Also Published As
Publication number | Publication date |
---|---|
IL155430A (en) | 2009-05-04 |
CN100482836C (zh) | 2009-04-29 |
AT5837U1 (de) | 2002-12-27 |
US20080075621A1 (en) | 2008-03-27 |
EP1364732B1 (de) | 2008-03-05 |
EP1364732A3 (de) | 2005-12-21 |
JP2003328067A (ja) | 2003-11-19 |
US7537726B2 (en) | 2009-05-26 |
ATE387978T1 (de) | 2008-03-15 |
CN1480543A (zh) | 2004-03-10 |
DE50309292D1 (de) | 2008-04-17 |
IL155430A0 (en) | 2003-11-23 |
US20040009088A1 (en) | 2004-01-15 |
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