EP2584057B1 - Procédé de fabrication de carbure cimenté ou poudre de cermet par un melangeur acoustique résonnant - Google Patents

Procédé de fabrication de carbure cimenté ou poudre de cermet par un melangeur acoustique résonnant Download PDF

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Publication number
EP2584057B1
EP2584057B1 EP11185483.2A EP11185483A EP2584057B1 EP 2584057 B1 EP2584057 B1 EP 2584057B1 EP 11185483 A EP11185483 A EP 11185483A EP 2584057 B1 EP2584057 B1 EP 2584057B1
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EP
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Prior art keywords
powder
powders
slurry
binder
mixing
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EP11185483.2A
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German (de)
English (en)
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EP2584057A1 (fr
Inventor
Carl-Johan Maderud
Tommy Flygare
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Sandvik Intellectual Property AB
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Sandvik Intellectual Property AB
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Priority to EP11185483.2A priority Critical patent/EP2584057B1/fr
Application filed by Sandvik Intellectual Property AB filed Critical Sandvik Intellectual Property AB
Priority to ES11185483.2T priority patent/ES2599641T3/es
Priority to KR1020147013160A priority patent/KR102229047B1/ko
Priority to CN201280051186.2A priority patent/CN103890204B/zh
Priority to KR1020197029813A priority patent/KR20190120394A/ko
Priority to ES12772790.7T priority patent/ES2613643T3/es
Priority to PCT/EP2012/070557 priority patent/WO2013057136A2/fr
Priority to JP2014536215A priority patent/JP6139538B2/ja
Priority to US14/352,314 priority patent/US9777349B2/en
Priority to EP12772790.7A priority patent/EP2768995B1/fr
Publication of EP2584057A1 publication Critical patent/EP2584057A1/fr
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Publication of EP2584057B1 publication Critical patent/EP2584057B1/fr
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/50—Mixing liquids with solids
    • B01F23/55—Mixing liquids with solids the mixture being submitted to electrical, sonic or similar energy
    • B01F23/551—Mixing liquids with solids the mixture being submitted to electrical, sonic or similar energy using vibrations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F31/00—Mixers with shaking, oscillating, or vibrating mechanisms
    • B01F31/80—Mixing by means of high-frequency vibrations above one kHz, e.g. ultrasonic vibrations
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/026—Spray drying of solutions or suspensions
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • 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
    • B22F2202/00—Treatment under specific physical conditions
    • B22F2202/01—Use of vibrations

Definitions

  • the present relates to a method of making a cemented carbide or cermet powder where the powder constituents are subjected to a non-milling mixing operation by using an acoustic mixer.
  • Cemented carbide and cermet powders used for making sintered bodies for e.g. cutting tools, wear parts etc. are usually made by first forming a slurry by milling the powder constituents together with binder metal powders, organic binder (e.g. polyethylene glycol) and a milling liquid in either a ball mill or an attritor mill for several hours. The slurry is then usually subjected to a spray drying operation to form granulated cemented carbide or cermet powders which can be used to press green parts that are subsequently sintered.
  • binder metal powders e.g. polyethylene glycol
  • organic binder e.g. polyethylene glycol
  • the main purpose of the milling operation is to obtain a good binder phase distribution and good wettability between the hard constituent grains and the binder phase powder.
  • a good binder phase distribution and good wettability is essential for achieving cemented carbide and cermet materials of high quality. If the phase distribution or wettability is poor, pores and cracks will be formed in the final sintered body which is detrimental for the material.
  • obtaining a good binder phase distribution and wettability is very difficult for these types of materials and requires a high input of energy, i.e. quite long milling times, usually 10-40 hours depending on the type of mill used and/or the grade produced.
  • Ball mills and attritor mills both provide good, homogenous mixing of the powder constituents, binder metal powders and the organic binder. These processes provides a large energy input that can overcome the static friction and binding forces that is required to obtain a good binder phase distribution and good wettability.
  • Such mills will subject the powders to a milling operation. Hence, the powders, both hard constituent powders and binder metal powders, will partly be grinded so that a fine fraction will be formed. This fine fraction can cause uncontrolled grain growth during the subsequent sintering. Hence, narrow sized raw material can be destroyed by milling.
  • EP 1 900 421 A1 discloses a process where the slurry is homogenized in a mixer comprising a rotor, a dispersing device and means to circulate the slurry.
  • the dispersion device contains moving parts.
  • WO 02/06545 discloses superhard filler hardmetal having a porosity rating of substantially A06, B00, C00 or better.
  • the superhard filler hardmetal is formed by mechanically mixing (including ultrasonic mixing), shaping the mixture into a green body and consolidating the green body at a preselected temperature, superatmospheric pressure and time at temperature and time at superatmospheric pressure sufficient to form the superhard filler hardmetal.
  • EP 1231288 discloses a method of manufacturing composite material. The method comprises a step of ultrasonic mixing.
  • One object of the present invention is to obtain a homogenous powder blend without milling.
  • Another object of the present invention is to obtain a powder blend where the grain size distribution of the raw materials can be maintained while still obtaining a homogenous powder blend.
  • Another object of the present invention is to obtain a powder blend using a mixing process that does not contain any moving parts and is subjected to a minimum amount of wear.
  • the present invention relates to the method defined in claim 1.
  • This is a method of making a cemented carbide or cermet agglomerated powder without milling where the powder constituents are subjected to a non-milling operation, comprising the steps of first forming a slurry of one or more powders forming hard constituents, wherein said one or more powders forming the hard constituents is selected from borides, carbides, nitrides or carbonitrides of metals from groups 4, 5 and 6 of the periodic table metal binder powders and a mixing liquid. Then the slurry is mixed and dried to form an agglomerated powder. The mixing is done in a non-contact mixer wherein acoustic waves achieving resonance conditions are utilized. Those types of mixers are usually called resonant acoustic mixers.
  • Acoustic mixers are known in the art, see e.g. WO 2008/088321 and US 7,188,993 . Such mixers use low-frequency, high intensity sound energy for mixing. They have shown good results when mixing fragile organic compounds but also other types of materials have been mixed. Acoustic mixers are non-contact mixers, i.e. they do not contain any mechanical means for mixing such as stirrers, baffles or impellars. Instead, the mixing is performed by creating micro-mixing zones throughout the entire mixing vessel by mechanical resonance applied to the materials to be mixed by the propagation of an acoustic pressure wave in the mixing vessel.
  • the grain size of the powders forming hard constituents depends on the application for the alloy and is preferably from 0.2 to 30 ⁇ m. If not otherwise specified, all amounts in wt% given herein are the wt% of the total dry weight of the dry powder constituents.
  • the binder metal powders can either be in a powder of one single binder metal, or a powder blend of two or more metals, or a powder of an alloy of two or more metals.
  • the binder metals are selected from Cr, Mo, Fe, Co or Ni, preferably from Co, Cr or Ni.
  • the grain size of the added binder metal powders is suitably between 0.5 to 3 ⁇ m, preferably between 0.5 to 1.5 ⁇ m.
  • cemented carbide is a WC-Co based powder, which also can contain, in addition to WC and Co, additions such as grain growth inhibitors, cubic carbides etc. commonly used in the art of making cemented carbides.
  • a cemented carbide powder is made of hard constituents suitably comprising WC with a grain size of between 0.5 to 2 ⁇ m, preferably between 0.5 to 0.9 ⁇ m.
  • the binder metal content is suitably between 3 to 17 wt%, preferably 5 to 15 wt% of the total dry weight of the dry powder constituents.
  • Cemented carbides made from these powders are commonly used in cutting tools such as inserts, drills end-mills etc.
  • a cemented carbide powder is made of hard constituents suitably comprising WC having a grain size between 1 to 8 ⁇ m, preferably between 1.5 to 4 ⁇ m.
  • the binder metal content is suitably between 3 to 30 wt%, preferably 5 to 20 wt% of the total dry weight of the dry powder constituents.
  • Cemented carbides made from these powders are commonly used in tool forming tools and wear parts, e.g. buttons for drillbits mining or asphalt milling hot rolls , parts for mining applications, wire drawing etc.
  • a cemented carbide powder is made of hard constituents suitably comprising WC having a grain size between 4 to 25 ⁇ m, preferably between 4.5 to 20 ⁇ m.
  • the binder metal content is suitably between 3 to 30 wt%, preferably 6 to 30 wt% of the total dry weight of the dry powder constituents.
  • Cemented carbides made from these powders are commonly used in buttons for drillbits, mining or asphalt milling, hot rolls.
  • cermet powder is herein meant a powder where the hard constituents comprising large amounts of TiCN and/or TiC.
  • Cermets comprise carbonitride or carbide hard constituents embedded in a metallic binder phase.
  • group VIa elements such as Mo, W and sometimes Cr, are added to facilitate wetting between binder and hard constituents and to strengthen the binder by means of solution hardening.
  • Group IVa and/or Va elements i.e., Zr, Hf, V, Nb and Ta, can also be added in commercial alloys available today. All these additional elements are usually added as carbides, nitrides and/or carbonitrides.
  • the grain size of the powders forming hard constituents is usually ⁇ 2 ⁇ m.
  • An organic binder is also optionally added to the slurry in order to facilitate the granulation during the following spray drying operation but also to function as a pressing agent for any following pressing and sintering operations.
  • the organic binder can be any binder commonly used in the art.
  • the organic binder can e.g. be paraffin, polyethylene glycol (PEG), long chain fatty acids etc.
  • the amount of organic binder is suitably between 15 and 25 vol% based on the total dry powder volume, the amount of organic binder is not included in the total dry powder volume.
  • a mixing liquid is required. Any liquid commonly used as a milling liquid in conventional cemented carbide manufacturing can be used.
  • the milling liquid is preferably water, alcohol or an organic solvent, more preferably water or a water and alcohol mixture and most preferably a water and ethanol mixture.
  • the properties of the slurry are dependent on amount of grinding liquid added. Since the drying of the slurry requires energy, the amount of liquid should be minimized in order to keep costs down. However, enough liquid need to be added in order to achieve a pumpable slurry and avoid clogging of the system.
  • Drying of the slurry is preferably done according to known techniques, in particular spray-drying.
  • the slurry containing the powdered materials mixed with the organic liquid and possibly the organic binder is atomized through an appropriate nozzle in the drying tower where the small drops are instantaneously dried by a stream of hot gas, for instance in a stream of nitrogen, to form agglomerated granules.
  • the formation of granules is necessary in particular for the automatic feeding of compacting tools used in the subsequent stage.
  • other drying methods can also be used, like pan drying.
  • Green bodies are subsequently formed from the dried powders/granules.
  • Any kind of forming operation known in the art can be used, e.g. injection molding, extrusion, uniaxel pressing, multiaxel pressing etc. If injection moulding or extrusion is used, additional organic binders are also added to the powder mixture.
  • the green bodies formed from the powders/granules made according to the present invention is subsequently sintered according to any conventional sintering methods e.g. vacuum sintering, Sinter HIP, plasma sintering etc..
  • the sintering technique used for each specific slurry composition is preferably the technique that would have been used for that slurry composition when the slurry was made according to conventional methods, i.e. ball milling or attritor milling.
  • Different slurries of cemented carbide were prepared by blending powders of hard constituents like WC and Cr 3 C 2 , Co and PEG with a liquid with an ethanol/water ratio of 90/10 by weight.
  • the WC grain size and the Co grain size given is the Fisher grain size (FSSS).
  • the composition of the dry constituents of the slurries and the properties of the raw material are shown in Table 1.
  • the amount of Co, WC and Cr 3 C 2 given in wt% are based on the total dry powder constituents in the slurry.
  • the amount of PEG is based on the total dry powder constituents of the slurry, where the amount of PEG is not included into the dry powder constituents of the slurry.
  • the slurry with Composition 1 from Example 1 were then subjected to a mixing operation either using a Resodyn Acoustic Mixer (LabRAM) according to the invention or a conventional paint shaker (Natalie de Lux), the slurries were then pan dried at 90°C.
  • the mixing conditions are displayed in Table 2.
  • Table 2 Powders Composition Mixer Mixing time (s) Energy (G) Invention 1 Composition 1 RAM 300 95 Comparison 1 Composition 1 Natalie 300 N/A
  • the powders were then first subjected to a conventional uniaxel pressing operation forming a green body which is subsequently subjected to a Sinter HIP operation at a sintering temperature of 1410°C.
  • the properties of the sintered material made from the powders are displayed in Table 3.
  • a slurry with Composition 1 made according to conventional techniques is included as Reference 1.
  • the Reference 1 sample has been made according by first making a slurry through ball milling for 56 hours and then subjecting them to a spray drying operation. The powder was then pressed and sintered in the same way as the other samples.
  • the average grain size for fine grained WC is not that affected by the ball milling. Where two values have been given, those represent measurements done on two different pieces from the same sintering batch.
  • the cemented carbide made according to the invention obtains about the same properties as the Comparison 1 and the Reference 1 samples.
  • the slurry with Composition 2a from Example 1 were subjected to a mixing operation either using a Resodyn Acoustic Mixer (LabRAM) or a conventional paint shaker (Natalie de Lux), the slurries were then pan dried at 90°C.
  • the mixing conditions are displayed in Table 4.
  • Table 4 Powders Composition Mixer Mixing time (s) Energy (G) Invention 2 Composition 2a RAM 300 95 Comparison 2 Composition 2a Natalie 300 N/A
  • Example 2 The powders were then pressed and sintered in the same way as the samples in Example 2.
  • the properties of the sintered material made from the powders are displayed in Table 5.
  • a slurry with Composition 2b is included as Reference 2.
  • the Reference 2 sample has been made from Composition 2b according to conventional techniques, i.e. ball milling for 20 hours and then subjecting them to a spray drying operation. The powder was then pressed and sintered in the same way as the other samples.
  • the WC grain size prior to the ball milling step is 5 ⁇ m.
  • the WC grain size is then drastically reduced by the milling operation.
  • the WC grain size is approx. 2.7 ⁇ m. All values given herein on the WC grain size as measured on the sintered material is estimated from the Hc value.
  • the cemented carbide made according to the invention obtains about the same properties as the Comparison 2 and Reference 2 samples.
  • the narrow WC grain size distribution of the WC raw material is maintained in the sintered structure.
  • Fig. 1 shows a SEM-image (Scanning Electron Microscope) of Invention 1.
  • Figure 2 is showing a LOM-image (Light Optic Microscope) of the Reference 2 sample which clearly is affected by the milling which can be seen by the presence of a number of larger grains originating from the grain growth of the fine fraction of WC grains.
  • composition 3a The slurry with composition 3a from Example 1 were subjected to a mixing operation either using a Resodyn Acoustic Mixer (LabRAM) the slurry were then pan dried at 90°C.
  • the mixing conditions are displayed in Table 6.
  • Table 6 Powders Composition Mixer Mixing time (s) Energy (G) Invention 3 Composition 3a RAM 300 95
  • Table 7 Powders Density (g/cm 3 ) Com Hc (kA/m) porosity HV30 Invention 3 14.97 5.72 5.65 A02,B00,C00 1240 Reference 3 14.95 5.7 6.8 ⁇ A02 1280
  • the cemented carbide made according to the invention obtains about the same properties as the Comparison 3 and Reference 3 samples. Also, it can be seen that about the same properties can be obtained for the Invention 3 where the WC is uncoated compared to Reference 3, where the WC has been coated with Co with use of the complex and expensive sol-gel process.
  • the Examples show that the method according to the present invention can lead to products having the same properties as products been produced with conventional methods. Hence, considerable shorter milling times can be achieved leading to a decrease in energy consumption. Also, the complex sol-gel process commonly used for can be avoided.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Claims (9)

  1. Procédé de fabrication d'une poudre agglomérée de carbure cémenté ou de cermet sans broyage, dans lequel les constituants de la poudre sont soumis à une opération de mélange sans broyage,
    comprenant les étapes consistant à :
    former une bouillie d'une ou plusieurs poudres formant des constituants durs, des poudres de liants métalliques et un liquide de mélange, dans lequel lesdites une ou plusieurs poudres formant les constituants durs sont sélectionnés à partir des borures, des carbures, des nitrures ou des carbonitrures de métaux des groupes 4, 5 et 6 du tableau périodique,
    mélanger et sécher ladite bouillie, pour former une poudre agglomérée, dans lequel le mélange est réalisé dans un mélangeur acoustique à résonance, qui est un mélangeur sans contact, dans lequel des ondes acoustiques atteignant des conditions de résonance sont utilisées.
  2. Procédé selon la revendication 1 dans lequel la bouillie contient un liant organique.
  3. Procédé selon l'une quelconque des revendications précédentes dans lequel le séchage est réalisé par séchage par pulvérisation.
  4. Procédé selon l'une quelconque des revendications précédentes dans lequel les poudres de liants métalliques sont une ou plusieurs poudres sélectionnées parmi Cr, Mo, Fe, Co ou Ni.
  5. Procédé selon l'une quelconque des revendications précédentes dans lequel une poudre de carbure cémenté est réalisée.
  6. Procédé selon la revendication 5 dans lequel les constituants durs comprennent du carbure de tungstène WC avec une taille de grain entre 0,5 et 2 µm, et une teneur en métal de liant entre 3 et 17 % en poids.
  7. Procédé selon la revendication 5 dans lequel les constituants durs comprennent du carbure de tungstène WC avec une taille de grain entre 1 et 8 µm, et une teneur en métal de liant entre 3 et 30 % en poids.
  8. Procédé selon la revendication 5 dans lequel les constituants durs comprennent du carbure de tungstène WC avec une taille de grain entre 4 et 25 µm, et une teneur en métal de liant entre 3 et 30 % en poids.
  9. Procédé selon l'une quelconque des revendications 1 à 4 dans lequel une poudre de cermet est réalisée.
EP11185483.2A 2011-10-17 2011-10-17 Procédé de fabrication de carbure cimenté ou poudre de cermet par un melangeur acoustique résonnant Active EP2584057B1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
ES11185483.2T ES2599641T3 (es) 2011-10-17 2011-10-17 Método para producir un polvo de carburo cementado o de metal cerámico usando un mezclador acústico resonante
EP11185483.2A EP2584057B1 (fr) 2011-10-17 2011-10-17 Procédé de fabrication de carbure cimenté ou poudre de cermet par un melangeur acoustique résonnant
CN201280051186.2A CN103890204B (zh) 2011-10-17 2012-10-17 通过使用共振声混合器制造硬质合金或金属陶瓷粉末的方法
KR1020197029813A KR20190120394A (ko) 2011-10-17 2012-10-17 공진 음향 믹서를 사용함으로써 초경합금 또는 서멧 분말을 제조하는 방법
ES12772790.7T ES2613643T3 (es) 2011-10-17 2012-10-17 Método para producir un polvo de carburo cementado o de metal cerámico usando un mezclador acústico resonante
PCT/EP2012/070557 WO2013057136A2 (fr) 2011-10-17 2012-10-17 Procédé de fabrication de carbure métallique ou de corps en cermet
KR1020147013160A KR102229047B1 (ko) 2011-10-17 2012-10-17 공진 음향 믹서를 사용함으로써 초경합금 또는 서멧 분말을 제조하는 방법
JP2014536215A JP6139538B2 (ja) 2011-10-17 2012-10-17 超硬合金又はサーメット体を作成する方法
US14/352,314 US9777349B2 (en) 2011-10-17 2012-10-17 Method of making a cemented carbide or cermet body
EP12772790.7A EP2768995B1 (fr) 2011-10-17 2012-10-17 Procédé de fabrication de carbure métallique ou de corps en cermet par un melangeur acoustique resonant

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP11185483.2A EP2584057B1 (fr) 2011-10-17 2011-10-17 Procédé de fabrication de carbure cimenté ou poudre de cermet par un melangeur acoustique résonnant

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EP2584057A1 EP2584057A1 (fr) 2013-04-24
EP2584057B1 true EP2584057B1 (fr) 2016-08-03

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CN103890204B (zh) * 2011-10-17 2016-11-16 山特维克知识产权股份有限公司 通过使用共振声混合器制造硬质合金或金属陶瓷粉末的方法

Citations (1)

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Publication number Priority date Publication date Assignee Title
US7188993B1 (en) * 2003-01-27 2007-03-13 Harold W Howe Apparatus and method for resonant-vibratory mixing

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