US20040009088A1 - Hard metal component with a graduated structure and methods of producing the component - Google Patents

Hard metal component with a graduated structure and methods of producing the component Download PDF

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Publication number
US20040009088A1
US20040009088A1 US10/417,487 US41748703A US2004009088A1 US 20040009088 A1 US20040009088 A1 US 20040009088A1 US 41748703 A US41748703 A US 41748703A US 2004009088 A1 US2004009088 A1 US 2004009088A1
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component
group
green compact
grain growth
hard metal
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US10/417,487
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Johannes Glatzle
Rolf Kosters
Wolfgang Glatzle
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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
    • 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
    • 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
    • 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the invention lies in the metallurgy field. More specifically, the invention relates to a component produced by powder metallurgy from a hard metal alloy with a binder content of from 0.1 to 20% by weight which contains at least one grain growth-inhibiting additive. The invention, furthermore, pertains to a process for producing the component.
  • hard metal is understood as meaning a composite material which substantially comprises a carbidic component and a binder.
  • the most important carbidic 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. Additions of further hard materials, such as for example carbonitrides, are also used.
  • the properties of hard metals are determined by the ratio of carbide content to binder content, by the chemical composition, the carbide grain size and the carbide grain size distribution. This opens up numerous options for matching the properties of hard metal to the corresponding application area.
  • carbidic powders in the grain size range from 0.2 ⁇ m to 15 ⁇ m are used for the production of hard metal components according to the intended use.
  • 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 for example mixtures of VC and Cr 3 C 2 or TaC, NbC and TiC.
  • the grain growth-inhibiting additive can be distributed extremely finely in the main component as early as before or during the carburizing step. However, it is also effective if the grain growth inhibitor is admixed with the hard metal powder or individual constituents of the hard metal powder before, during or after milling.
  • Hard metal components may be subject to very differing local loads. Therefore, from a very early stage solutions which are based on a material composite comprising two or more hard metal alloys have been discovered and implemented.
  • U.S. Pat. No. 5,543,235 describes a hard metal material composite which is produced by powder metallurgy composite pressing, the individual material regions differing in terms of their composition or microstructure.
  • a rotating composite tool which is composed of two hard metal alloys is also described in U.S. Pat. No. 6,511,265 B1 and international PCT publication WO 01/43899. Production is likewise preferably effected by composite pressing.
  • a further process technique for the manufacture of a hard metal composite-body is described in U.S. Pat. No. 5,594,931.
  • a surface layer or slip which consists of a powder mixture, a solvent, a binder and a plasticizer is applied to a green compact or core.
  • the composite green compact produced in this way is densified by sintering.
  • a structure of graduated composition is understood to mean that the composition changes gradually and continuously over a certain region.
  • graduated formations in the region of the layer, in the region of the layer/base material transition and in the adjacent base material have long been known. This graduation is achieved, for example, by the addition of carbonitrides.
  • the nitrogen in the edge zone of the hard metal body is broken down.
  • the metallic carbide-forming or nitride-forming elements diffuse toward the center of the hard metal body. This results in an increase in the levels of binder in the region of the edge zone and a graduated transition to the matrix composition.
  • disposable cutting tool tips with a binder-rich edge zone adjacent to the hard-material layer have long been in use for the machining of steel.
  • the graduation is restricted to a small region close to the surface.
  • binder metals such as for example cobalt
  • concentration compensation in the transition zone between two hard metal alloys which have a differing cobalt content by means of diffusion processes. In this way, it is possible to establish a continuous transition.
  • a process for that purpose is described, for example, in U.S. Pat. No. 5,762,843 and European patent EP 0 871 556.
  • a composite body which comprises at least two regions which differ in terms of their binder content is produced by composite pressing. During the sintering, the temperature is to be set in such a way that the binder metal diffuses out of the composite region with the higher binder content into the composite region with a lower binder content.
  • a drawback of this process is that the sintering temperature has to be set very accurately in order not to produce complete concentration balancing and thereby lose the different materials properties.
  • a further drawback is that composite pressing is associated with higher production costs than is the case when a monolithic green compact is being produced.
  • European patent applications EP 0 247 985 and EP 0 498 781 likewise describe hard metal bodies with a binder phase gradient and a process for producing them. In this case, first of all a sintered body with a uniformly distributed ⁇ phase is produced by means of standard process steps using a reduced-carbon starting powder mixture. A subsequent treatment in a carburizing atmosphere leads to partial dissolution of the ⁇ phase in the region of the edge zone.
  • the level of ⁇ phase increases gradually and the binder content decreases gradually in the direction of the center of the hard metal body.
  • a drawback is that the ⁇ phase has an embrittling action.
  • the additional carburizing step is time-consuming and energy-consuming.
  • European patent application EP 0 111 600 describes a highly loaded tool for rock drilling.
  • the device comprises an inner region and an outer region, with a continuous transition of the mechanical properties between these regions.
  • the proposed process technology is a complex powder feed making it possible to continuously adjust the powder concentration during the filling operation.
  • a powder feed of this nature requires complex apparatus and is difficult to control in terms of process technology.
  • an article of manufacture made from a hard metal alloy comprising:
  • At least one grain growth-inhibiting additive selected from the group consisting of V, Cr, Ti, Ta, and Nb or a compound thereof, at least one of said grain growth-inhibiting additives, at least locally, having a graduated concentration profile;
  • the hard metal alloy has a graduated grain size profile, at least locally. Also preferably, the hard metal alloy has a graduated hardness profile.
  • the concentration of the grain growth-inhibiting additive decreases gradually from the edge zone of the component toward the center of the component.
  • the carbide grain size increases gradually from the edge zone of the component toward the center of the component.
  • the concentration of the grain growth-inhibiting additive increases gradually from the edge zone of the component toward the center of the component.
  • the carbide grain size decreases gradually from the edge zone of the component toward the center of the component.
  • the grain growth-inhibiting additive consists of Cr and/or V, or a compound thereof.
  • a maximum content of the grain growth-inhibiting additive, based on the hard metal alloy, is 2% by weight, and its content decreases gradually to a value x, where 0 ⁇ x ⁇ 1.0% by weight.
  • a green compact from a hard metal alloy, containing at least one carbide, mixed carbide or carbonitride of the metals selected from the group consisting of W, Ti, Ta, Mo, Zr, Hf, V, Nb, Cr, and V, at least one metallic binder selected from the group consisting of Co, Ni, and Fe, an optional addition of wax or a plasticizer, with a standard powder metallurgy compacting process or a standard shaping process;
  • the manufacture comprises the following steps:
  • a green compact from a hard metal alloy, containing at least one carbide, mixed carbide or carbonitride of the metals selected from the group consisting of W, Ti, Ta, Mo, Zr, Hf, V, Nb, Cr, and V, at least one metallic binder selected from the group consisting of Co, Ni, and Fe, an optional addition of wax or a plasticizer;
  • the above objects are achieved by a component made from a hard metal alloy and by a process for producing it, in which the hard metal alloy contains at least one carbide, mixed carbide or carbonitride of the metals from the group consisting of W, Ti, Ta, Mo, Zr, Hf, V, Nb, Cr and V, at least one grain growth-inhibiting additive from the group consisting of V, Cr, Ti, Ta and Nb or a compound of these metals, and at least one metallic binder from the group consisting of Co, Ni and Fe, at least one of the grain growth-inhibiting additives, at least locally, having a graduated concentration profile.
  • the hard metal alloy contains at least one carbide, mixed carbide or carbonitride of the metals from the group consisting of W, Ti, Ta, Mo, Zr, Hf, V, Nb, Cr and V, at least one grain growth-inhibiting additive from the group consisting of V, Cr, Ti, Ta and Nb or a compound of these metals, and at least one metallic binder
  • the graduated concentration profile of the grain growth-inhibiting additive leads to a graduated profile of the carbide grain size. Consequently, the mechanical properties also have a graduated profile. This is advantageous, for example, where a high wear resistance and bending fracture strength is required at the surface and, at the same time, a high toughness is required in the core, such as for example in forming tools or tools for diamond production. If the concentration profile of the gain growth-inhibiting additive is now set in such a way that the concentrations are higher in the regions of the edge zone and decrease in the direction of the center of the component, the edge zone is in fine-grain form, with a graduated transition to the more coarse-grained center.
  • a high fracture toughness in the region of the edge zone may also be advantageous in the event of a high cyclical or impact shock loading. This is achieved by a reduced grain growth-inhibiting additive content in the region of the edge zone.
  • the compressive and bending strength properties in the core of the component are improved by a graduated profile of the grain size and a more fine-grained center. This embodiment is also favorable for coated components.
  • the action of the invention is also achieved if the hard metal alloy contains further, non-carbidic hard material phases, provided that the mechanical properties are not significantly adversely affected as a result.
  • Advantageous grain growth-inhibiting additives worthy of mention are vanadium and chromium compounds, the maximum concentration being 2% by weight. Higher contents lead to embrittlement effects.
  • a particularly advantageous process is the application of a dispersion or solution to the surface of a green compact.
  • the dispersion contains the grain growth-inhibiting additive in extremely finely distributed form.
  • the green compact may be in the as-pressed state. If the green compact contains additions of wax and/or plasticizer, it may also, according to an advantageous configuration of the present invention, be in the dewaxed or partly dewaxed state.
  • the application of the dispersion or solution can be carried out, for example, by dipping, spraying or brushing.
  • the dispersion or solution then penetrates into the interior of the green compact along open pores.
  • the duration of action and the grain growth-inhibiting additive content in the dispersion or solution substantially determine the introduction quantity and the penetration depth. Therefore, depending on the profile of requirements, it is possible to set a graduation which extends only on the micrometer scale. However, it is also possible to make the graduation such that it extends all the way to the center of the component.
  • the process can also be carried out in such a way that first of all the green compact is completely impregnated with the dispersion. This is then removed again from the regions close to the surface by means of suitable solvents or by thermal processes.
  • the dispersion may be applied to the entire surface or alternately only to local parts of the surface.
  • the local application makes it possible to produce components or tools which only have a high hardness where resistance to wear is required.
  • the remaining regions have a coarser microstructure with a high fracture toughness.
  • the carbidic component of the green compact has a mean grain size of less than 2 ⁇ m.
  • FIG. 1 is a graph showing the vanadium content over the specimen cross section in a production example according to the invention
  • FIG. 2 is a graph showing the carbide grain size in addition to the vanadium content, plotted over the cross section;
  • FIG. 3 is a graph showing a hardness profile over the specimen cross section
  • FIG. 4 is a perspective view of a cross section through a drawing tool.
  • FIG. 5 is a graph showing a hardness profile over the specimen cross section.
  • FIG. 1 and FIG. 2 relate to example 1;
  • FIG. 3 relates to example 2;
  • FIG. 4 and FIG. 5 relate to example 3.
  • the specimens were analyzed by means of electron beam microprobe, and the microstructural and mechanical characteristics were determined by a light-microscope examination and hardness testing, in each case on microsections.
  • FIG. 1 shows that the vanadium content in the region of the edge zone is 0.24% by weight, and this value decreases gradually toward the inside over the cross section of the specimen.
  • the vanadium content at a distance of 3.8 mm from the specimen edge is 0.08% by weight.
  • the corresponding vanadium concentrations were below the detection limit of the microprobe.
  • the graduated vanadium distribution leads to a graduated grain stabilization effect, as documented by the WC grain size values shown in FIG. 2. While the mean grain size increases from the edge zone toward the center, the corresponding hardness values decrease, as shown in FIG. 3.
  • a hard metal batch containing 89.5% by weight of WC with a mean grain size of 0.8 ⁇ m, 0.5% by weight of Cr 3 C 2 , remainder Co was produced using the processes which are standard in the hard metal industry. Green compacts in the shape of disposable cutting tool tips were produced by die pressing with a pressure of 50 kN. The green compacts were subjected to a standard dewaxing process. Furthermore, a dispersion of distilled water and V 2 O 5 was prepared, with a solids content of 2% by weight and a mean V 2 O 5 particle size of less than 50 nm. Then, the green compacts were dipped into the above-described dispersion for 5 seconds and then dried in air at 50° C.
  • specimens were sintered in vacuum at a temperature of 1400° C. together with reference green compacts which had not been subjected to any further treatment.
  • the specimens were analyzed by means of electron beam microprobe, and the microstructural and mechanical characteristics were determined by a light-microscope examination and hardness testing.
  • the specimens according to the invention once again have a graduated vanadium concentration profile with an edge zone value of 0.21% by weight of V and a center value of 0.03% by weight of V.
  • the corresponding hardness values are 1 698 HV30 and 1 648 HV30.
  • the hardness profile is shown in FIG. 3.
  • the reference specimen has a hardness profile which is uniform over the cross section, with a mean value of 1605 HV30.
  • the specimens according to the invention and the reference specimens were also subjected to a bending test.
  • the mean obtained from ten measurements is 3950 MPa for the specimens according to the invention and 3500 MPa for the comparison specimens.
  • a hard metal batch containing 93.4% by weight of WC with a mean grain size of 2.0 ⁇ m, 0.2% of TiC, 0.4% by weight of TaC/NbC, remainder Co was produced using the processes which are standard in the hard metal industry. Cylindrical green compacts were produced by isostatic pressing at a pressure of 100 MPa and were shaped into a hard metal drawing tool by machining. The green compacts were subjected to a standard dewaxing process. Once again, a dispersion of distilled water and V 2 O 5 was produced, with a solids content of 2% by weight and a particle size of the dispersed V 2 O 5 particles of less than 50 nm.
  • FIG. 4 also shows the region where the characterization was performed by means of electron beam microprobe and hardness testing.
  • the vanadium content in the edge zone is 0.18% by weight but is only 0.11% by weight at a distance of 2 mm from the edge of the specimen.
  • FIG. 5 shows the gradual hardness profile.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
US10/417,487 2002-04-17 2003-04-17 Hard metal component with a graduated structure and methods of producing the component Abandoned US20040009088A1 (en)

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AT0024502U AT5837U1 (de) 2002-04-17 2002-04-17 Hartmetallbauteil mit gradiertem aufbau
ATATGM245/2002 2002-04-17

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EP (1) EP1364732B1 (he)
JP (1) JP2003328067A (he)
CN (1) CN100482836C (he)
AT (2) AT5837U1 (he)
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US20050147850A1 (en) * 2003-12-15 2005-07-07 Sandvik Ab Cemented carbide tools for mining and construction applications and method of making same
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US20160122250A1 (en) * 2013-05-31 2016-05-05 Sandvik Intellectual Property Ab New process of manufacturing cemented carbide and a product obtained thereof
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EP3763840A1 (en) * 2019-07-10 2021-01-13 Sandvik Mining and Construction Tools AB Gradient cemented carbide body and method of manufacturing thereof
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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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CN101429618B (zh) * 2008-11-21 2012-10-31 嘉应学院 型内熔化扩散形成梯度耐磨材料及其制造方法
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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
DE102020120576A1 (de) * 2020-08-04 2022-02-10 Hauni Maschinenbau Gmbh Hartmetallmesser für Strangschnitt und Messerhalter
CN114698373A (zh) * 2020-10-30 2022-07-01 住友电工硬质合金株式会社 硬质合金及具备该硬质合金的切削工具
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AT5837U1 (de) 2002-12-27
EP1364732A3 (de) 2005-12-21
IL155430A0 (en) 2003-11-23
US7537726B2 (en) 2009-05-26
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DE50309292D1 (de) 2008-04-17

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