WO2012128708A1 - Procédé de préparation d'un matériau à gradient de fonctionnalité métal/carbure métallique - Google Patents

Procédé de préparation d'un matériau à gradient de fonctionnalité métal/carbure métallique Download PDF

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Publication number
WO2012128708A1
WO2012128708A1 PCT/SE2012/050303 SE2012050303W WO2012128708A1 WO 2012128708 A1 WO2012128708 A1 WO 2012128708A1 SE 2012050303 W SE2012050303 W SE 2012050303W WO 2012128708 A1 WO2012128708 A1 WO 2012128708A1
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Prior art keywords
sintering
layer
temperature
fgm
electrically insulating
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PCT/SE2012/050303
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English (en)
Inventor
Mohamed Radwan
Katarina Flodström
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Diamorph Ab
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Publication of WO2012128708A1 publication Critical patent/WO2012128708A1/fr

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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
    • 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
    • B22F3/10—Sintering only
    • B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
    • 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
    • B22F7/008—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 characterised by the composition
    • 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
    • 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
    • B22F7/04—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 with one or more layers not made from powder, e.g. made from solid metal
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C04B35/645—Pressure sintering
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0292—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with more than 5% preformed carbides, nitrides or borides
    • 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
    • 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 generally to a method of preparation of a metal / cemented carbide, such as a steel / cemented tungsten carbide, functionally graded material shape by sintering, preferably by spark plasma sintering (SPS) .
  • a metal / cemented carbide such as a steel / cemented tungsten carbide
  • SPS spark plasma sintering
  • the common cemented carbide graded tools are usually fabricated by making tungsten carbide (WC, often referred to as hard metal) bi-layers with different content of binder phase, such as cobalt (Co), and/or various tungsten carbide grain sizes and sinter-bonding them with steel.
  • WC tungsten carbide
  • binder phase such as cobalt (Co)
  • Co cobalt
  • This process is metastable and the graded microstructure is very sensitive to the sintering conditions such as sintering temperature, holding time and other factors. It is usually difficult to make a final material with a cobalt gradient because of the flow of liquid phase cobalt and its homogenization during sintering at high temperature.
  • a functionally graded material is a material design concept which provides a joining solution to relieve the residual thermal stresses and to incorporate incompatible properties of two dissimilar materials, such as the heat, the wear, and the oxidation resistance of a refractory ceramic, such as for example cemented carbide, with the high toughness, the high strength, and the machinability of a metal, such as steel, by placing graded composite interlayers of the two materials between the pure end layers.
  • microstructure with the composition change The matrix is replaced gradually from metal to ceramic, and the microstructure profile varies concurrently from (i) a pure metal, (ii) a metal-rich region (the ceramic particles are dispersed in metal matrices), (iii) intertwined composites (networks of metal and ceramic phases with comparable volume fractions), (iv) a ceramic-rich region (the metal matrix diminishes and turns into discrete phases or particles in ceramic matrices), to finally (v) a pure ceramic.
  • FGMs can be prepared through different techniques such as conventional powder metallurgy processing, vapour deposition and sintering techniques.
  • the spark plasma sintering method also referred to as for example field assisted sintering technique (FAST) is a powerful sintering technique which allows very rapid heating under high mechanical pressures. This process, hereafter referred to as SPS, has proved to be very well suited for the production of functionally graded materials.
  • Other sintering techniques could possibly also be used for preparing FGMs, such as for example direct hot-pressing, hot-pressing or hot isostatic pressing.
  • tungsten carbide has the higher sintering temperature, approximately 200°C higher than steel. It is necessary to sinter the FGM component at a proper temperature at which the whole component can be fully sintered.
  • the appropriate sintering temperature of tungsten carbide by SPS is generally 1 00- 200°C higher than this limit. The sintering temperature is influenced by the tungsten carbide grain size and the content of binder material.
  • An object of the present invention is to prepare a metal / cemented carbide functionally graded material by sintering, preferably by spark plasma sintering (SPS), in order to combine a tough metal base with a hard carbide surface in an economical way.
  • the functionally graded material can be a steel/cemented tungsten carbide (steel / WC-Co FGM) .
  • the end product is a fully dense
  • compositionally gradient shape with pure metal and pure cemented carbide alloy as two end surfaces pure metal layer / x number of composite layers / pure cemented carbide layer
  • Another end product can be a dense compositionally gradient shape with pure metal as one end surface and a metal-cemented carbide composite on the other end surface.
  • the term "cemented" means that the carbide alloy powder includes an amount of metallic binder, such as for example cobalt, nickel, iron, or their alloys. During the sintering process, the tungsten carbide particles are captured in the metallic binder and cemented together by forming a metallurgical bond.
  • metallic binder such as for example cobalt, nickel, iron, or their alloys.
  • the base layer can be a steel alloy, a stainless steel alloy or other metallic material.
  • the invention relates to a method of preparation of a FGM shape with a first surface comprising up to 1 00% of a first material and a second surface comprising up to 1 00% of a second material.
  • the method is characterized in that it comprises the steps of: selecting the first material with a first sintering temperature and a first melting temperature and the second material with a second sintering temperature and a second melting temperature , wherein the first melting temperature is higher than the second melting temperature, loading a first layer of the first material in a sintering mold referred to as die, adding at least one intermediate layer on the first layer, the intermediate layer comprising a mix of the first and second material creating an intermediate graded composite region, loading a second layer of the second material on the at least one intermediate layer, adding an electrically insulating layer on the second layer of the second material, adding a pressure on the layers creating a FGM shape, and sintering the whole shape under a predetermined time, pressure and temperature.
  • the method can further comprise adding an electrically insulating layer before loading the first layer of the first material.
  • the method can comprise adding an electrically insulating layer on all surfaces around the material to be sintered.
  • the layers are preferably added as powders, but solid blocks of the pure materials and composites can also be used.
  • the electrically insulating layer added on the second material enforces the current from the sintering process to flow only through the die and not through the second layer of the FGM- shape.
  • the temperature increase in the second layer becomes limited.
  • the temperature in the first layer is high enough to sinter the first material but it does not exceed the melting temperature of the second material.
  • the resulting end product from the process is a near fully dense FGM without any melted material.
  • said first material is a cemented carbide and said second material is a metal or metal alloy, preferably said first material is cemented tungsten carbide and said second material is steel.
  • the first material includes a metallic binder.
  • the metallic binder may be cobalt and the amount of cobalt can be between 5 and 25wt%.
  • the binder can also be nickel, iron, or their alloys.
  • said electrically insulating layer is chosen from any of the materials boron nitride, alumina, zirconia, silicon nitride, aluminum nitride, silica, magnesia.
  • the steel/cemented tungsten carbide FGM is sintered, the most preferred insulating material is boron nitride.
  • the insulating layer can either be a powder or a solid disc.
  • the insulating layer can also be added as liquid through spraying or painting.
  • the sintering takes place under a sintering temperature of between 1 000 °C and 1 200 °C, preferably between 1 050°C and 1 1 50°C, more preferably between 1 070 °C and 1 1 20°C and most preferably 1 1 00 °C, a pressure of between 20 and 1 20 MPa, preferably between 50 and 90 MPa, more preferably between 65 and 80 MPa and most preferably 75 MPa, and a sintering time of between 5 and 30 min, preferably between 1 0 and 20 min, more preferably 1 5 min.
  • the sintering takes place under a sintering temperature of between 900 °C and 1 200 °C, preferably between 950°C and 1 1 50°C, a pressure of between 20 and 1 20 MPa, preferably between 30 and 75 MPa, and a sintering holding time of between 2 and 30 min, preferably between 5 and 20 min .
  • the shape is sintered using one of the following sintering techniques; spark plasma sintering (SPS) or direct hot pressing (DHP).
  • Possible sintering techniques are also hot pressing (HP) or hot isostatic pressing (HIP). But preferably, spark plasma sintering (SPS) is used.
  • HP hot pressing
  • HIP hot isostatic pressing
  • SPS spark plasma sintering
  • the sintering pressure is applied through two punches arranged on opposite sides of the loaded material in the die.
  • the dies are lined with a graphite foil and this is also inserted between the first and second surface of the FGM shape and the two punches.
  • the dies are graphite dies surrounded by graphite felt.
  • the dies are surrounded by a carbon fiber composite material (CFC) .
  • the graphite foil ensures good electric and thermal contacts between the die and the punches and also facilitates removal of the sintered compact without damaging the die or punch surfaces.
  • the dies are lined with a layer of the insulating material.
  • the method further comprises the step: removing the electrically insulating layer after the sintering process has been performed.
  • Removal of the remains of the insulating layer after sintering can be performed through sand blasting or similar.
  • the end product is a pure FGM ready to be manufactured into a cemented carbide tool.
  • the end product can also be a finished cemented carbide tool with no need for further processing.
  • All individual features of the above methods may be combined or exchanged unless such combination or exchange is clearly contradictory.
  • the sintering conditions such as holding time and pressure, depend on the size of the FGM shape and the die dimension .
  • Fig. 1 shows a longitudinal cross-section of a FGM die setup
  • Table 1 lists the relative densities and the sintering conditions during sintering of individual steel and cemented carbide powders by SPS
  • Table 2 lists the relative densities and the sintering conditions during sintering of steel / WC-Co FGM compacts by SPS at 1 1 00°C/75MPa/l 5min/50°C/min.
  • the read temperatures mentioned in the description can differ between different sintering furnaces depending on how the temperature is measured.
  • the temperature is measured with a pyrometer focused on a hole on the outer surface of the die.
  • FIG. 1 shows a longitudinal cross-section of the die setup for producing a FGM-shape 4 according to the invention.
  • Powders of at least a first and a second material M l , M2 are sintered under a pressure created by punches 3a, 3b in a die 1 , preferably a graphite die.
  • the sintering process creates samples of the FGM shape 4, for example cylindrical-shaped discs. Other shapes including any polygonal-shaped discs can also be sintered.
  • the sintering process is performed by spark plasma sintering under a high temperature and pressure on the closed die to create a dense/near fully dense FGM-shape.
  • the powder layers to be sintered can be cold-pressed prior to the sintering.
  • the sintering takes preferably place at a sintering temperature of between 1 000 °C and 1 200 °C, preferably between 1 050°C and 1 1 50°C, more preferably between 1 070 °C and 1 1 20°C and most preferably 1 1 00 °C, a pressure of between 20 and 1 20 MPa, preferably between 50 and 90 MPa, more preferably between 65 and 80 MPa and most preferably 75 MPa, and a sintering time of between 5 and 30 min, preferably between 1 0 and 20 min, more preferably 1 5 min.
  • Different sintering techniques can be used, such as for example spark plasma sintering (SPS) or direct hot pressing (DHP) .
  • SPS spark plasma sintering
  • DHP direct hot pressing
  • Other sintering techniques are also hot pressing (HP) or hot isostatic pressing (HIP) .
  • the FGM shape has a first layer 11 with a first surface 4a comprising up to 1 00% of the first material M l and a second layer 12 with a second surface 4b comprising up to 1 00% of the second material M2.
  • a third layer 13 comprising a mix of the first and second material M l , M2 is added.
  • the at least one third layer is creating an intermediate graded composite region l c.
  • the numbers of graded layers are between two and ten, with a 50- 1 0vol% gradient change.
  • other numbers of layers are of course also possible, as is a non-linear gradient change in composition .
  • the first material M l has a first sintering temperature Ts l and a first melting temperature Tm l and the second material M2 has a second sintering temperature Ts2 and a second melting temperature Tm2.
  • the sintering temperature during the SPS- process needs to reach the first sintering temperature Ts l of the first material but not exceed the second melting temperature Tm2 of the second material. Otherwise, this can lead to melting of the second material M2.
  • an electrically insulating layer 5 of an electrically insulating powder is placed on the second surface 4b of the FGM-shape 4, between the second layer 12 of the second material M2 and the graphite punch 3b.
  • the function of the electrically insulating powder is to enforce the current to flow only through the die and not through the second layer 12 of the FGM-shape.
  • the first material M l is preferably a cemented carbide and the second material M2 a metal. More preferably, the first material M l is cemented tungsten carbide and the second material M2 is steel.
  • the first material M l includes a metallic binder such as for example cobalt Co or an iron-nickel alloy Fe-Ni.
  • the electrically insulating layer can be chosen from any of the electrically insulating materials of boron nitride, alumina, zirconia, silicon nitride, aluminum nitride, silica, magnesia, but preferably boron nitride BN is used. This material can either be a powder or a solid disc.
  • the inner walls of the dies 1 can be lined with thin graphite foil 2 inserted between the shape 4 and the two punches 3a, 3b.
  • a graphite foil can also be inserted between the first and second surface l a, 1 b of the FGM shape 1 and the two punches (3a, 3b) .
  • the graphite foil 2 ensures good electric and thermal contacts between the die 1 and the punches 3a, 3b, and also facilitates removal of the sintered compact without damaging the die 1 or punch surfaces 3a, 3b.
  • the graphite dies 1 can be surrounded by graphite felt 6 to reduce the heat loss by radiation from the outer die surface.
  • the temperature can for example be measured at a hole 7 in the graphite die 6.
  • the steel and tungsten carbide composite powder mixtures were dry mixed at room temperature for one hour in plastic containers with tungsten carbide milling rods on a jar rolling mill.
  • the steel / WC-Co FGMs were designed to comprise four composite interlopers between the pure steel and tungsten carbide layers at the two ends.
  • the composites consisted of steel - cemented carbide mixtures with a 20vol% gradient change (i.e. 80/20, 60/40, 40/60, 20/80 vol%).
  • the total six layers were loaded in order, layer by layer, in a graphite die and a BN insulating layer was interposed between the punch and the steel layer.
  • a steel / cemented tungsten carbide FGM disc ( ⁇ 20x6 mm) was successfully sintered according to the above conditions. It was fully dense and no cracks could be observed. Experiments have also successfully been performed with discs of the sizes 020x8.25 mm and I 2x7.25 mm.
  • the samples 4 were sintered with and without an electrically insulating layer 5 of boron nitride powder BN placed between the steel powder to be sintered and the graphite punches 3a, 3b.
  • the powders inside the closed dies were first cold-pressed. Then, the samples were sintered in vacuum in a spark plasma sintering unit (SPS-5.40 MK-VI system from SPS Syntex Inc, Japan). Once the p re-determined SPS-pressure was applied, the dies were heated to 600 °C in 3 minutes and then heated further at a rate of 50-1 00 °C/min to the desired holding temperature. The holding time was between 5 and 1 5 minutes. The temperature was measured with an optical pyrometer focused on a hole 7 at the half height of the outer surface of the die.
  • SPS-5.40 MK-VI system from SPS Syntex Inc, Japan
  • the resulting sintered discs were blasted to remove the residues of graphite foil and BN layer, and then polished with # 1 20 silicon carbide grinding paper.
  • the relative densities were measured by Archimedes method (European Standard EN 993-1 ) using deionized water as the immersion medium.
  • the possible existence of surface cracks in the sintered pellets was examined visually and through optical microscopy (Olympus SZxl 2 model, Olympus Optical Co. Ltd, Japan).
  • Tables 1 and 2 The relative densities and the sintering conditions are listed in Tables 1 and 2, wherein Table 1 lists sintering of individual steel and cemented carbide powders by SPS and Table 2 lists sintering of steel / WC-Co FGM compacts by SPS at 1 1 00°C/75MPa/1 5min/50°C/min .

Abstract

L'invention concerne un procédé de préparation d'une forme MGF avec une première surface comprenant jusqu'à 100% d'un premier matériau et une seconde surface comprenant jusqu'à 100% d'un second matériau au moyen d'un frittage, de préférence un frittage flash (FF). Le procédé comprend les étapes consistant à : sélectionner le premier matériau ayant une première température de frittage et une première température de fusion et le second matériau ayant une seconde température de frittage et une seconde température de fusion, la première température de fusion étant supérieure à la seconde température de fusion ; charger une première couche du premier matériau dans un moule, en ajoutant au moins une couche intermédiaire sur la première couche, la couche intermédiaire comprenant un mélange des premier et second matériaux, ce qui crée une zone composite progressive intermédiaire ; et charger une seconde couche du second matériau sur ladite couche intermédiaire. L'invention est caractérisée en ce qu'on ajoute une couche électro-isolante sur la seconde couche du second matériau qui oblige le courant provenant du processus de frittage à s'écouler uniquement à travers la filière et non à travers la seconde couche de la forme MGF.
PCT/SE2012/050303 2011-03-22 2012-03-20 Procédé de préparation d'un matériau à gradient de fonctionnalité métal/carbure métallique WO2012128708A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE1150254-9 2011-03-22
SE1150254A SE535684C2 (sv) 2011-03-22 2011-03-22 Metod att framställa en gradientkomponent av metall/cementerad karbid

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CN103182506A (zh) * 2013-03-29 2013-07-03 华南理工大学 一种TiCp/M2高速钢复合材料及其SPS制备方法
CN105081323A (zh) * 2015-09-16 2015-11-25 哈尔滨工业大学 一种放电等离子烧结及包套热轧制备TiAl/Ti合金层状复合板材的方法
WO2015185969A1 (fr) * 2014-04-24 2015-12-10 Consejo Superior De Investigaciones Científicas Procédé de fabrication de matériaux avancés par concentration de courant électrique
FR3030324A1 (fr) * 2014-12-17 2016-06-24 Commissariat Energie Atomique Procede de fabrication d'une couche conductrice sur une face d'une piece metallique par frittage par compression uniaxiale d'une poudre
CN106216674A (zh) * 2016-06-08 2016-12-14 四川大学 W‑v合金功能梯度材料及其放电等离子体烧结方法
FR3060427A1 (fr) * 2016-12-21 2018-06-22 Centre National De La Recherche Scientifique Procede de traitement d'un materiau composite superdur destine a etre utilise pour la realisation d'outils de coupe
CN109421262A (zh) * 2017-09-05 2019-03-05 波音公司 制造具有空间分级特性的组件的方法
WO2019069701A1 (fr) * 2017-10-02 2019-04-11 日立金属株式会社 Matériau composite de carbure cémenté, son procédé de production et outil en carbure cémenté
CN109755143A (zh) * 2017-11-01 2019-05-14 天津环鑫科技发展有限公司 一种硅片合金工艺
CN110465670A (zh) * 2019-09-12 2019-11-19 哈尔滨工业大学 一种通过放电等离子烧结制备层状复合材料的方法
WO2021187964A1 (fr) * 2020-03-19 2021-09-23 서울대학교산학협력단 Procédé de formation de corps fritté métallique
FR3108919A1 (fr) * 2020-04-01 2021-10-08 Commissariat A L'energie Atomique Et Aux Energies Alternatives Pièce en un matériau multicouche à gradient de composition et son procédé de fabrication
EP4212266A1 (fr) 2022-01-14 2023-07-19 Drill Holding ApS Pointe de foret et foreuse avec pointe de foret, moule et procédé de fabrication de la pointe de foret

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JPWO2019069701A1 (ja) * 2017-10-02 2020-11-19 日立金属株式会社 超硬合金複合材およびその製造方法ならびに超硬工具
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