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WO2016061721A1 - Procédé de préparation de matériau en tungstène à grains fins, renforcé par une dispersion d'oxyde de terres rares - Google Patents

Procédé de préparation de matériau en tungstène à grains fins, renforcé par une dispersion d'oxyde de terres rares Download PDF

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Publication number
WO2016061721A1
WO2016061721A1 PCT/CN2014/088882 CN2014088882W WO2016061721A1 WO 2016061721 A1 WO2016061721 A1 WO 2016061721A1 CN 2014088882 W CN2014088882 W CN 2014088882W WO 2016061721 A1 WO2016061721 A1 WO 2016061721A1
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Prior art keywords
rare earth
earth oxide
tungsten
rare
preparing
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PCT/CN2014/088882
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English (en)
Chinese (zh)
Inventor
范景莲
韩勇
李鹏飞
刘涛
成会朝
田家敏
Original Assignee
中南大学
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Priority to CN201480034843.1A priority Critical patent/CN105518169B/zh
Priority to PCT/CN2014/088882 priority patent/WO2016061721A1/fr
Priority to US14/901,780 priority patent/US20170225234A1/en
Publication of WO2016061721A1 publication Critical patent/WO2016061721A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
    • 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
    • B22F3/16—Both compacting and sintering in successive or repeated 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
    • 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
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
    • 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
    • C22C1/045—Alloys based on refractory metals
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1026—Alloys containing non-metals starting from a solution or a suspension of (a) compound(s) of at least one of the alloy constituents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0031—Matrix based on refractory metals, W, Mo, Nb, Hf, Ta, Zr, Ti, V or alloys thereof
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • 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
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/20—Refractory metals
    • 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
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/25—Oxide
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2200/00—Crystalline structure
    • C22C2200/04—Nanocrystalline

Definitions

  • the invention relates to the field of nano materials and powder metallurgy, in particular to a preparation method of rare earth oxide dispersion strengthened fine grain tungsten material prepared by nano composite technology.
  • Tungsten has high melting point, high hardness, good high temperature strength, thermal conductivity, electrical conductivity, low coefficient of thermal expansion, low sputtering with plasma, no chemical reaction with H, low H + retention, etc.
  • High-temperature structural materials and functional materials are widely used as materials for plasma materials and divertor components in the field of nuclear fusion.
  • pure tungsten materials are typical high temperature materials that are widely used at present.
  • high-purity powder and material grain boundary purification methods are used at home and abroad to prepare sintered pure tungsten materials, and then tungsten materials are strengthened by large deformation processing methods.
  • the grain size is about 100 ⁇ m
  • the ductile-brittle transition temperature (DBTT) is 300-350 °C.
  • the crystallization temperature is 1300 ⁇ 1350 °C
  • the tensile strength at room temperature is above 500MPa
  • the tensile strength at 1000 °C is 400MPa.
  • pure tungsten materials have defects such as very coarse structure, fibrous orientation, high DBTT, low recrystallization temperature, and high brittleness.
  • second phase particles to refine tungsten grains and to diffusely strengthen pure tungsten has become an important direction of current development. Based on this, domestic Zhou Zhangjian et al.
  • the above preparation method has some problems: the preparation of the powder by high-energy ball milling or mechanical alloying tends to produce uneven distribution of components and introduction of heterogeneous impurities, and the sintering method of SPS and hot pressing is not suitable for large-scale preparation of engineering. While Guo Zhimeng et al.'s method improves the uniformity of dispersion distribution of oxides in tungsten matrix, Ni element must be added as a sintering activator, while Ni element is strictly prohibited in many fields, such as nuclear fusion and nuclear fission. This will impose huge limitations on the scope of its application.
  • the inventor of the present patent has applied for and obtained a national invention patent 'Preparation method of ultrafine activated tungsten powder (patent number: ZL201010049432.3)', in which sol-spray drying-heat is applied.
  • the ultrafine or nano-activated tungsten powder is prepared by a reduction technique, and any one or more of Ni, Co, and Fe trace activation elements are added to the powder.
  • the powder composition of the invention is uniformly distributed and does not introduce an impurity element as compared with high energy ball milling or mechanical alloying.
  • the sol-spray drying method is used to directly prepare tungsten materials containing trace rare earth oxides.
  • the dispersion strengthening effect of rare earth oxide particles on tungsten is very limited, resulting in poor performance of materials. It is difficult to meet the requirements for the use of nuclear fusion tungsten materials.
  • the present invention employs heterogeneous precipitation - spray drying - Calcination - Thermal reduction - Preparation by conventional sintering technology
  • High performance rare earth oxide dispersion strengthened fine grain tungsten material The rare earth oxide dispersion-enhanced fine-grained tungsten material prepared by the method of the invention has a density close to full density ( ⁇ 98.5%), the rare earth oxide particles are uniformly distributed in the tungsten grains and the tungsten grain boundaries, the structure is uniform and fine, and the average grain size is 10 ⁇ m. Below, it has good room temperature, high temperature mechanical properties and high heat load impact resistance.
  • the present invention provides a rare earth oxide super-uniform dispersion-distributed fine-grained tungsten material, characterized in that the fine-grained tungsten material contains one or more of Y 2 O 3 , La 2 O 3 and CeO 2 And the mass percentage of the rare earth oxide ranges from 0.1 to 2%, and the remaining component is W.
  • the mass percentage of the rare earth oxide is 0.1 to 2%, and the remaining component is W.
  • the soluble rare earth salt and the tungstate are weighed and prepared into a rare earth salt solution of 50 to 100 g/L and a tungstate solution of 150 to 300 g/L, respectively.
  • the colloid is spray-dried at 350 ⁇ 450 °C to obtain a composite precursor powder of tungsten and rare earth oxide; the composite precursor powder is calcined at 300 ⁇ 600 °C, and the calcination time is 1 ⁇ 4h, and the solution is agglomerated and sieved.
  • the hydrogen is reduced at 600 ⁇ 850 °C for 2 ⁇ 6h to prepare ultrafine/nano tungsten powder containing trace rare earth oxides with a particle size of 50 ⁇ 500nm; the rare earth oxide is Y 2 O 3 One or more of La 2 O 3 or CeO 2 ;
  • the ultrafine/nano tungsten powder containing trace rare earth oxide in step (1) is 150 ⁇ 300MPa Forming or cold isostatic pressing;
  • the press-formed compact is subjected to conventional high-temperature sintering in a high-temperature sintering furnace at a sintering temperature of 1800 to 2000 °C.
  • the holding time is 1 ⁇ 5h, and the dense high-performance rare earth oxide super-diffused distribution enhanced fine-grained tungsten material is obtained.
  • the tungstate is ammonium metatungstate, ammonium paratungstate or ammonium tungstate.
  • the rare earth salt is a nitrate, oxalate, carbonate, chloride or sulfate of Y, La or Ce.
  • the stirring speed is 1000 ⁇ 5000 rpm.
  • the spray drying head rotates at a speed of 20,000 to 30,000 rpm.
  • the reaction dispersant is stearic acid, polyethylene glycol, urea, N, N-dimethylformamide, OP emulsifier, Tween-20 Or sodium dodecyl sulfate, the mass of the reaction dispersant is 0.1 ⁇ 1.5% of the mass of the rare earth salt solution or the tungstate solution.
  • the pH is controlled, the added acid is HCl, HNO 3 or oxalic acid; the added base is NaOH, KOH or ammonia.
  • the ultrafine tungsten composite powder containing trace rare earth oxide prepared by hydrogen reduction method has greater sintering activity; the powder prepared by the invention can reach 98.5% by conventional sintering at 1800-2000 °C.
  • the above density, sintered body grain size is 5 ⁇ 10 ⁇ m, and the structure is more uniform, with excellent room temperature, high temperature and toughness.
  • the invention adopts the conventional sintering method to prepare the rare earth oxide dispersion-strengthened fine-grained tungsten material, and the process is simple and suitable for engineering preparation.
  • a dispersion-strengthened fine-grained tungsten material having a composition of W-0.1 wt% Y 2 O 3 is prepared.
  • the soluble rare earth salt and the tungstate are weighed according to the mass ratio, that is, weighed 1.02 g of cerium nitrate, 411.27 g of ammonium metatungstate, respectively, was prepared into a 50 g/L rare earth salt solution and a 150 g/L tungsten salt solution.
  • Dispersing agent under the action of ultrasonic vibration and electric mixer stirring, the tungstate forms tungsten acid microparticles, and Y(OH) 3 colloidal particles are used as the core, and the precipitate is coated around the Y(OH) 3 colloidal particles to form a total Precipitating coated particle colloid;
  • the composite precursor powder was calcined at 350 °C for 2 h; after deagglomeration and sieving, it was kept at 78 ° C for 2 h under H 2 atmosphere; and an ultra-containing Y 2 O 3 was obtained . Fine tungsten powder.
  • a dispersion-strengthened fine-grained tungsten material having a composition of W-0.3 wt% La 2 O 3 is prepared.
  • the soluble rare earth salt and the tungstate are weighed according to the mass ratio, that is, weighed 1.53 g of bismuth oxalate, 410.45 g of ammonium paratungstate, respectively, were prepared into a 60 g/L rare earth salt solution and a 200 g/L tungsten salt solution.
  • the rare earth salt reacts with the base to form a uniform suspension of La(OH) 3 colloid; then the tungsten salt solution is added to the La(OH) 3 colloid, and the concentration of 10 wt% HCl is slowly added dropwise to adjust the pH to 6.8, and adding 1.5g PEG400 as a reaction dispersant, the tungstate is formed into tungstic acid microparticles under the action of ultrasonic vibration and electric mixer stirring, and La(OH) 3 colloidal particles are used as the core, and the precipitate is coated on La(OH). 3 ) around the colloidal particles, eventually forming a coprecipitated coated particle colloid;
  • the composite precursor powder was calcined at 350 °C for 2 h; after deagglomeration and sieving, it was kept at 78 ° C for 2 h under H 2 atmosphere; and an ultra-containing 0.3 wt% La 2 O 3 was obtained . Fine tungsten powder.
  • a dispersion-strengthened fine-grained tungsten material having a composition of W-0.5 wt% CeO 2 is prepared.
  • the soluble rare earth salt and the tungstate are weighed according to the mass ratio, that is, 2.10 g Barium carbonate, 409.6 g of ammonium tungstate, was prepared into a 70 g/L rare earth salt solution and a 220 g/L tungsten salt solution, respectively.
  • the tungstate is formed into tungstic acid microparticles under the action of ultrasonic vibration and electric mixer stirring, and Ce(OH) 3 colloidal particles are used as the core, and the precipitate is coated with Ce(OH) 3 colloid. Around the particles, a coprecipitated coated particle colloid is finally formed;
  • the composite precursor powder is calcined at 400 °C for 2 hours; after deagglomeration and sieving, it is reduced in two steps under H 2 atmosphere, the first step is kept at 60 ° C for 2 h, the second step is The steel was kept at 800 ° C for 2 h to obtain an ultrafine tungsten powder containing 0.5 wt% of CeO 2 .
  • the ultrafine W composite powder containing trace rare earth CeO 2 is cold isostatically pressed, and the compact is calcined and then sintered at 1950 ° C for 4 h to obtain W-0.5 wt% CeO 2 material.
  • the density of the material is 99.3.
  • the microstructure is fine and uniform, and the grain size is below 8 ⁇ m; the material does not crack on the surface of the sample under the impact of high heat flux density of 200 MW/m 2 .
  • a dispersion-strengthened fine-grained tungsten material having a composition of W-0.3 wt% Y 2 O 3 -0.3 wt% La 2 O 3 is prepared.
  • the soluble rare earth salt and the tungstate are weighed according to the mass ratio, that is, respectively weighed 1.52g bismuth nitrate, 2.18g lanthanum chloride, 409.2g ammonium metatungstate, lanthanum nitrate and lanthanum chloride are mixed to form 80g/L rare earth salt solution, 250g/L Tungsten salt solution.
  • the composite precursor powder was calcined at 400 °C for 3 h; after deagglomeration and sieving, it was kept at 80 ° C for 2 h under H 2 atmosphere; and 0.3 wt% La 2 O 3 -0.3 was obtained. Ultrafine tungsten powder of wt% La 2 O 3 .
  • the compact After molding the ultrafine WY 2 O 3 -La 2 O 3 composite tungsten powder, the compact is pre-fired at 1000 °C for 2 h and then sintered at 1920 °C for 3 h to obtain W-0.3 wt% Y 2 O 3 - 0.3wt% La 2 O 3 material, the density of the material is above 99.4%, the microstructure is fine and uniform, and the grain size is below 6 ⁇ m; the material does not crack on the surface of the sample under the impact of high heat flux density of 300MW/m 2 .
  • a dispersion-strengthened fine-grained tungsten material having a composition of W-0.3 wt% Y 2 O 3 - 0.3 wt% La 2 O 3 - 0.3 wt% CeO 2 is prepared.
  • the soluble rare earth salt and the tungstate are weighed according to the mass ratio, that is, respectively weighed 1.85g barium sulfate, 0.8g barium nitrate, 1.52g barium nitrate, 409g ammonium metatungstate, mixed with barium sulfate, barium nitrate and barium nitrate to prepare a 100g/L rare earth salt solution. 300 g / L of tungsten salt solution.
  • the tungstate is formed into a tungstic acid microparticle, and the Y(OH) 3 + La(OH) 3 + Ce(OH) 3 colloidal particle is used as a core, and the precipitate is coated on Y(OH) 3 + La(OH) 3 + Around the colloidal particles of Ce(OH) 3 , a coprecipitated coated particle colloid is finally formed;
  • the composite precursor powder is calcined at 500 °C for 3 hours; after deagglomeration and sieving, in the H 2 atmosphere, the first step is kept at 60 ° C for 2 h, and the second step is kept at 800 ° C. 4h, an ultrafine tungsten powder containing 0.3% by weight of La 2 O 3 -0.3% by weight of La 2 O 3 -0.3% by weight of CeO 2 was obtained.

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Abstract

L'invention concerne un procédé de préparation d'un matériau en tungstène à grains fins, renforcé par une dispersion d'oxyde de terres rares, qui comprend : selon une condition qu'un pourcentage en masse d'oxyde de terres rares est de 0,1 à 2 % et la composition restante est constituée de W, le pesage de sel de terres rares soluble et de sel d'acide tungstique et la préparation respectivement d'une solution de sel de terres rares de 50 à 100 g/l et d'une solution de sel d'acide tungstique de 150 à 300 g/l; l'ajout d'une petite quantité d'alcali dans le sel de terres rares pour régler le pH de 7 à 8, l'ajout d'un agent dispersant organique et l'agitation pour permettre au sel de terres rares de former des particules colloïdales de R(OH)3 uniformément en suspension (R représente un élément de terres rares); l'ajout de la solution de sel d'acide tungstique aux particules colloïdales de R(OH)3, l'ajout d'une petite quantité d'acide pour ajuster le pH de 6 à 7, l'ajout de l'agent dispersant organique, l'agitation pour permettre au sel d'acide tungstique de former des microparticules d'acide tungstique, la précipitation et l'enrobage des particules colloïdales de R(OH)3, les particules colloïdales de R(OH)3(OH) servant de noyau, et la formation de particules colloïdales co-précipitées enrobées; l'exécution d'un séchage par pulvérisation sur les particules colloïdales co-précipitées et enrobées pour obtenir une poudre de précurseur composite de tungstène et d'oxyde de terres rares; la calcination, l'exécution d'une réduction thermique par de l'hydrogène et la préparation de poudre de tungstène superfine nanométrique ayant une taille des particules de 50 à 500 nm; l'exécution d'un frittage à haute température normale après un formage par compression général. Le matériau en tungstène à grains fins et à efficacité élevée, dans lequel une quantité mineure d'oxyde de terres rares est dispersée, qui est renforcé par celle-ci et qui est préparé par le procédé ci-dessus, présente une densité proche d'une densité totale (≥ 98,5 %) et des petits grains uniformes de tungstène ayant une taille moyenne de 5 à 10 µm; de plus, des particules d'oxyde de terres rares ayant une taille de particule de 100 nm à 500 nm sont uniformément réparties dans un cristal de tungstène ou un contour cristallin.
PCT/CN2014/088882 2014-10-20 2014-10-20 Procédé de préparation de matériau en tungstène à grains fins, renforcé par une dispersion d'oxyde de terres rares WO2016061721A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201480034843.1A CN105518169B (zh) 2014-10-20 2014-10-20 一种稀土氧化物弥散强化细晶钨材料的制备方法
PCT/CN2014/088882 WO2016061721A1 (fr) 2014-10-20 2014-10-20 Procédé de préparation de matériau en tungstène à grains fins, renforcé par une dispersion d'oxyde de terres rares
US14/901,780 US20170225234A1 (en) 2014-10-20 2014-10-20 A preparation method of rare earth oxide dispersion strengthened fine grain tungsten materials

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PCT/CN2014/088882 WO2016061721A1 (fr) 2014-10-20 2014-10-20 Procédé de préparation de matériau en tungstène à grains fins, renforcé par une dispersion d'oxyde de terres rares

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CN116103532A (zh) * 2023-02-28 2023-05-12 南昌大学 一种微量稀土氧化物强化无氧铜材及其制备方法
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