WO2016061721A1 - Method for preparing rare-earth oxide dispersion strengthened fine-grained tungsten material - Google Patents

Method for preparing rare-earth oxide dispersion strengthened fine-grained tungsten material Download PDF

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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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rare earth
earth oxide
tungsten
rare
preparing
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PCT/CN2014/088882
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French (fr)
Chinese (zh)
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范景莲
韩勇
李鹏飞
刘涛
成会朝
田家敏
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中南大学
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Priority to CN201480034843.1A priority Critical patent/CN105518169B/en
Priority to US14/901,780 priority patent/US20170225234A1/en
Priority to PCT/CN2014/088882 priority patent/WO2016061721A1/en
Publication of WO2016061721A1 publication Critical patent/WO2016061721A1/en

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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.

Abstract

A method for preparing a rare-earth oxide dispersion strengthened fine-grained tungsten material, comprising: according to a condition that a mass percentage of rare-earth oxide is 0.1-2%, and the remaining composition is W, weighing soluble rare-earth salt and tungstic acid salt, and respectively preparing 50-100 g/L of rare-earth saline solution and 150-300 g/L of tungstic acid saline solution; adding a minor amount of alkali into the rare-earth salt to control the pH to be 7-8, adding an organic dispersing agent, and stirring to enable the rare-earth salt to form uniformly suspending R(OH)3 colloidal particles (R represents a rare-earth element); adding the tungstic acid saline solution into the R(OH)3 colloidal particles, adding a minor amount of acid to control the pH to be 6-7, adding the organic dispersing agent, stirring to enable the tungstic acid salt to form tungstic acid micro-particles, precipitating and coating the R(OH)3 colloidal particles with the R(OH)3 colloidal particles as a core, and forming coprecipitated coated colloidal particles; conducting spray drying on the coprecipitated coated colloidal particles to obtain a composite precursor powder of tungsten and rare-earth oxide; calcining, conducting thermal reduction via hydrogen, and preparing superfine nanometer tungsten powder having a particle size of 50-500 nm; and conducting normal high-temperature sintering after a general pressing forming. The high-performance fine-grained tungsten material dispersed and strengthened by a minor amount of rare-earth oxide prepared by the above method has a density approximate to full density (≥98.5%), and uniform and small tungsten grains having an average size of 5-10 μm; in addition, rare-earth oxide particles having a particle size of 100 nm - 500 nm are uniformly distributed in a tungsten crystal or a crystal boundary.

Description

一种稀土氧化物弥散强化细晶钨材料的制备方法  Method for preparing rare earth oxide dispersion strengthened fine grain tungsten material 技术领域  Technical field
本发明涉及纳米材料领域和粉末冶金领域，特别是采用纳米复合技术制备的稀土氧化物弥散强化细晶钨材料制备方法。 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.
技术背景technical background
钨具有高熔点、高硬度，良好的高温强度、导热、导电性能，低的热膨胀系数，与等离子作用时低溅射、不与 H 发生化学反应、 H+ 滞留低等特性，是一种非常重要的高温结构材料和功能材料，在核聚变领域中被广泛用作面向等离子体材料和偏滤器部件材料。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.
在已获得应用的钨材料中，纯钨材料是目前应用非常广泛的典型高温材料。目前国内外采用粉末高纯化和材料晶界净化的手段制备烧结纯钨材料，然后经过大变形加工手段强化钨材料，晶粒度在 100μm 左右，韧脆转变温度（ DBTT ） 300~350 ℃ ，再结晶温度 1300~1350 ℃ ，室温抗拉强度 500MPa 以上， 1000 ℃ 抗拉强度 400MPa 。然而，由于传统粉末烧结轧制方法的局限性，纯钨材料存在组织非常粗大、呈纤维状取向、 DBTT 高、再结晶温度低、脆性大等缺陷。添加第二相粒子细化钨晶粒、并起到弥散强化纯钨成为当前发展的一个重要方向。 基于此，国内周张健等人 2010 年在专利 ' 一种纳米氧化物弥散增强超细晶钨基复合材料的制备方法 ' （专利号： ZL201010250552.X ）中，以钨粉、 Y2O3 或 Y 、烧结助剂 Ti 为原料，采用机械合金化的方法使钨粉与 Y2O3 或 Y 、以及 Ti 固溶形成超细合金化粉末，然后采用放电等离子体法烧结制备了稀土氧化钇弥散强化钨材料，其相对密度为 96%~99% ，钨晶粒尺寸 ≤3μm ，具有良好的力学性能和抗热冲击性能。此外， 国外 Kim 等人在 2009 年文章 ' Fabrication of high temperature oxides dispersion strengthened tungsten composites by spark plasma sintering process' 、 Mu ñoz 等人在 2011 年文章 ' La2O3-reinforced W and W-V alloys produced by hot isostatic pressing' 同样采用机械合金化制备钨与稀土氧化物复合粉末，并采用电火花等离子烧结（ SPS ）和热压方法制备出氧化物弥散强化钨材料，结果表明添加微量稀土氧化物可细化钨晶粒、提高强度和抗高热负荷性能。郭志猛等人在专利 ' 一种纳米氧化钇弥散强化钨合金的制备方法 ' （申请号： 201310123415.3 ）中，对前面所述的制备方法做了改进：将硝酸钇溶于酒精，然后与仲钨酸铵（ APT ）进行混合球磨，干燥后氢还原后，然后掺入 0.1%~1%Ni 作为烧结活化剂，最后高温烧结制备出密度为 18.28~19.2g/cm3 的氧化物弥散分布的钨材料。以上的研究充分表明了在钨中添加稀土氧化物对于细化钨晶粒、提高钨的力学性能及抗热冲击性能方面的优势。但是，上述的制备方法存在一些问题：采用高能球磨或机械合金化制备粉末容易产生成分分布不均和引入异类杂质， 而 SPS 、热压的烧结方法不适合于工程的规模化制备。而郭志猛等人的方法虽然改善了氧化物在钨基体中的弥散分布均匀性，但是必须添加 Ni 元素作为烧结活化剂，而 Ni 元素在很多领域，如核聚变、核裂变领域中是严禁使用的，这将对其应用范围带来巨大限制。本专利发明人在前阶段已申请并获得了一项国家发明专利'一种超细活化钨粉的制备方法（专利号： ZL201010049432.3 ）'，在该发明中，采用溶胶 - 喷雾干燥 - 热还原技术制备超细或纳米活化钨粉，该粉末中添加有 Ni 、 Co 、 Fe 微量活化元素中的任意一种或多种。与高能球磨或机械合金化相比，该发明的粉末成分分布均匀，而且不引入杂质元素。但是由于钨与稀土氧化物颗粒表面的相容性差，采用溶胶 - 喷雾干燥法直接制备含微量稀土氧化物钨材料，稀土氧化物颗粒对钨的弥散强化作用非常有限，导致材料各项性能较差，难以满足核聚变钨材料使用要求。Among the tungsten materials that have been applied, pure tungsten materials are typical high temperature materials that are widely used at present. 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 μm, and 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, and the tensile strength at 1000 °C is 400MPa. However, due to the limitations of conventional powder sintering and rolling methods, pure tungsten materials have defects such as very coarse structure, fibrous orientation, high DBTT, low recrystallization temperature, and high brittleness. The addition of 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. in 2010, in the patent 'Method for preparing nano-oxide dispersion-reinforced ultra-fine-grained tungsten-based composite materials' (patent number: ZL201010250552.X), with tungsten powder, Y 2 O 3 or Y The sintering aid Ti is used as a raw material, and the tungsten powder is solid-dissolved with Y 2 O 3 or Y and Ti to form an ultrafine alloyed powder by mechanical alloying, and then the rare earth yttrium oxide dispersion strengthening is prepared by discharge plasma sintering. The tungsten material has a relative density of 96% to 99% and a tungsten grain size of ≤3 μm, and has good mechanical properties and thermal shock resistance. In addition, foreign Kim et al. in 2009 ' Fabrication of high temperature oxides dispersion strengthened tungsten composites by spark plasma sintering process', Mu ñoz et al. in 2011 article 'La 2 O 3 -reinforced W and WV alloys produced by hot isostatic Pressing' is also used to prepare tungsten and rare earth oxide composite powder by mechanical alloying, and the oxide dispersion strengthened tungsten material is prepared by spark plasma sintering (SPS) and hot pressing method. The results show that the addition of trace rare earth oxide can refine the tungsten crystal. Granules, increased strength and resistance to high heat load. Guo Zhimeng et al. in the patent 'Preparation method of a nano-cerium oxide dispersion-strengthened tungsten alloy' (Application No.: 201310123415.3), the preparation method described above is improved: the cerium nitrate is dissolved in alcohol, and then with ammonium paratungstate ( APT) is subjected to mixed ball milling, and after hydrogen reduction after drying, then 0.1% to 1% of Ni is added as a sintering activator, and finally a tungsten material having a density of 18.28 to 19.2 g/cm 3 is prepared by high temperature sintering. The above studies have fully demonstrated the advantages of adding rare earth oxides in tungsten to refine tungsten grains, improve the mechanical properties and thermal shock resistance of tungsten. However, 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. However, due to the poor compatibility of tungsten and rare earth oxide particles on the surface, 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.
发明内容 Summary of the invention
针对以上方法在制备高性能稀土氧化物弥散强化细晶钨材料方面存在的问题，本发明 采用非均相沉淀 - 喷雾干燥 - 煅烧 - 热还原 - 常规烧结技术制备 高性能稀土氧化物弥散强化细晶钨材料 。用本发明的方法制备的稀土氧化物弥散强化细晶钨材料，其致密度接近全致密（ ≥98.5% ），稀土氧化物颗粒在钨晶粒内和钨晶界超均匀弥散分布，组织均匀且细小，平均晶粒度在 10μm 以下，具有良好的室温、高温力学性能和抗高热负荷冲击性能。 In view of the above problems in the preparation of high performance rare earth oxide dispersion strengthened fine grain tungsten material, 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 μm. Below, it has good room temperature, high temperature mechanical properties and high heat load impact resistance.
本发明所提供的一种稀土氧化物超均匀弥散分布强化细晶钨材料，其特征在于：所述细晶钨材料含有 Y2O3 、 La2O3 、 CeO2 其中的一种或多种，且稀土氧化物的质量百分数范围为 0.1 ～ 2% ，其余成分为 W 。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.
上述的一种稀土氧化物超均匀弥散分布强化细晶钨材料，其制备过程如下： The above-mentioned ultra-uniform dispersion distribution of rare earth oxide enhances the fine-grained tungsten material, and the preparation process thereof is as follows:
（ 1 ）按稀土氧化物的质量百分数为 0.1 ～ 2% ，其余成分为 W 。 称取可溶性稀土盐和钨酸盐，分别配制成 50 ～ 100g/L 的稀土盐溶液和 150~300g/L 的钨酸盐溶液。首先在稀土盐中加入碱控制 pH 在 7~8 ，并加入有机分散剂，搅拌使稀土盐形成均匀悬浮 R(OH)3 颗粒胶体（ R 代表稀土元素）；然后将钨酸盐溶液加入到 R(OH)3 胶体中，加入酸控制 pH 在 6~7 ，并加入有机分散剂，搅拌使钨酸盐形成钨酸微粒子，并以 R(OH)3 胶体粒子为核心，沉淀包覆在 R(OH)3 胶体粒子周围，最终形成共沉淀包覆粒子胶体。再将该胶体在 350~450 ℃喷雾干燥，得到钨与稀土氧化物的复合前驱体粉末； 将 复合前驱体 粉末在 300~600 ℃下煅烧，煅烧时间为 1~4h ，经解团聚、过筛后，在 600~850 ℃ 氢气热还原，还原时间为 2~6h ，制备出含微量稀土氧化物、粒度在 50~500nm 的超细 / 纳米钨粉；所述的稀土氧化物是 Y2O3 、 La2O3 或 CeO2 中的一种或多种；(1) 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. First, adding a base to the rare earth salt to control the pH between 7 and 8, and adding an organic dispersant, stirring to form a uniform suspension of the R(OH) 3 particle colloid (R represents a rare earth element); then adding the tungstate solution to the R In the (OH) 3 colloid, add acid to control the pH at 6~7, add organic dispersant, stir to form tungstic acid microparticles, and use R(OH) 3 colloidal particles as the core, and precipitate the coating on R ( OH) 3 around the colloidal particles, eventually forming a coprecipitated coated particle colloid. 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. After that, 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 ;
（ 2 ）将步骤（ 1 ）中的含微量稀土氧化物的超细 / 纳米钨粉在 150~300MPa 下 采用模压或冷等静压普通压制成形； (2) The ultrafine/nano tungsten powder containing trace rare earth oxide in step (1) is 150~300MPa Forming or cold isostatic pressing;
（ 3 ）将压制 成形的压坯在高温烧结炉中进行常规高温烧结，烧结温度为 1800~2000 ℃ 、保温时间为 1 ～ 5h ，得到致密的高性能稀土氧化物超均匀弥散分布强化细晶钨材料。 (3) 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.
所述的钨酸盐是偏钨酸铵、仲钨酸铵或钨酸铵。 The tungstate is ammonium metatungstate, ammonium paratungstate or ammonium tungstate.
所述的稀土盐是 Y 、 La 、 Ce 的硝酸盐、草酸盐、碳酸盐、氯化物或硫酸盐。 The rare earth salt is a nitrate, oxalate, carbonate, chloride or sulfate of Y, La or Ce.
所述搅拌转速为 1000~5000 转 / 分。 The stirring speed is 1000~5000 rpm.
所述喷雾干燥喷头转速为 20000~30000 转 / 分。 The spray drying head rotates at a speed of 20,000 to 30,000 rpm.
所述的反应分散剂为硬脂酸、聚乙二醇、尿素、 N,N- 二甲基甲酰胺、 OP 乳化剂、吐温 -20 或十二烷基磺酸钠，反应分散剂质量为稀土盐溶液或钨酸盐溶液质量的 0.1~1.5% 。 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.
所述的控制 pH 值，加入的酸为 HCl 、 HNO3 或草酸；加入的碱为 NaOH 、 KOH 或氨水。The pH is controlled, the added acid is HCl, HNO 3 or oxalic acid; the added base is NaOH, KOH or ammonia.
本发明相对于现有方法制备的氧化物弥散强化钨材料，其优点如下： The oxide dispersion-strengthened tungsten material prepared by the invention relative to the prior art has the following advantages:
1. 与常规高能球磨机械合金化相比，采用'非均相沉淀 - 喷雾干燥' 将稀土氧化物加入到钨基体中，非均相沉淀改善钨与稀土氧化物颗粒表面的相容性，喷雾干燥实现粉末和合金中成分、组织的均匀性，因此稀土元素在钨基体中分布更加均匀，且不引进外来杂质； 1. 'Non-homogeneous precipitation - spray drying' compared to conventional high energy ball milling mechanical alloying The rare earth oxide is added to the tungsten matrix, the heterogeneous precipitation improves the compatibility of the surface of the tungsten and the rare earth oxide particles, and the spray drying is used to achieve the uniformity of the composition and structure of the powder and the alloy, so that the rare earth elements are more distributed in the tungsten matrix. Uniform and no introduction of foreign matter;
2. 与高能球磨机械合金化相比，采用'非均相沉淀 - 喷雾干燥 - 煅烧 - 氢还原法'制备的含微量稀土氧化物的超细钨复合粉具有更大的烧结活性；采用本发明制备的粉末在 1800~2000 ℃ 下采用常规烧结即可达 98.5% 以上致密度，烧结体 晶粒尺寸为 5~ 10μm ，且组织更为均匀， 具有优异的室温、高温强韧性。 2. Compared with high energy ball milling mechanical alloying, 'heterogeneous precipitation - spray drying - calcination - 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 ~ 10μm, and the structure is more uniform, with excellent room temperature, high temperature and toughness.
3. 本发明采用常规烧结手段制备稀土氧化物弥散强化细晶钨材料，工艺过程简单，适合工程化制备。 3. 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.
具体实施方式 Detailed ways
以下结合实例进一步说明本发明，而非限制本发明 The invention will be further illustrated by the following examples, without limiting the invention.
实施例 1 ： Example 1
以制备成分为 W-0.1wt%Y2O3 的弥散强化细晶钨材料为例。For example, a dispersion-strengthened fine-grained tungsten material having a composition of W-0.1 wt% Y 2 O 3 is prepared.
（ 1 ）首先根据最终所要制备的稀土氧化物质量分数，按质量比例称取可溶性稀土盐和钨酸盐，即称取 1.02g 硝酸钇， 411.27g 偏钨酸铵，分别配制成 50g/L 的稀土盐溶液和 150g/L 的钨盐溶液。 (1) First, according to the mass fraction of the rare earth oxide to be 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.
（ 2 ）首先在硝酸钇溶液中缓慢滴加入浓度为 10 wt% 的氨水，调节 pH 至 7.2 ，并加入 0.2g PEG400 作为反应分散剂，在超声波振动及电动搅拌机搅拌的作用下，使稀土盐与碱反应形成均匀悬浮 Y(OH)3 颗粒胶体；然后将钨盐溶液加入到 Y(OH)3 胶体中，缓慢滴加入浓度为 10 wt% 的草酸，调节 pH 至 6.5 ，并加入 2g PEG400 作为反应分散剂，在超声波振动及电动搅拌机搅拌的作用下使钨酸盐形成钨酸微粒子，并以 Y(OH)3 胶体粒子为核心，沉淀包覆在 Y(OH)3 胶体粒子周围，最终形成共沉淀包覆粒子胶体；(2) First, slowly add 10% by weight of ammonia water to the cerium nitrate solution, adjust the pH to 7.2, and add 0.2g PEG400 as the reaction dispersant. Under the action of ultrasonic vibration and electric mixer stirring, make the rare earth salt and The alkali reacts to form a uniform suspension of Y(OH) 3 particles colloid; then the tungsten salt solution is added to the Y(OH) 3 colloid, the oxalic acid at a concentration of 10 wt% is slowly added dropwise, the pH is adjusted to 6.5, and 2 g of PEG400 is added as a reaction. 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;
（ 3 ）然后，将该胶体在 360 ℃下进行喷雾干燥，喷雾转头转速为 20000 转 / 分，得到钨与稀土氧化钇的复合前驱体粉末。 (3) Then, the colloid was spray-dried at 360 °C, and the spray head rotation speed was 20000 rpm / A composite precursor powder of tungsten and rare earth cerium oxide is obtained.
（ 4 ） 将 复合前驱体 粉末在 350 ℃下煅烧，煅烧时间为 2h ；经解团聚、过筛后，在 78 0 ℃、 H2 气氛下保温 4h ；得到含 0.1wt% Y2O3 的超细钨粉。(4) 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.
（ 5 ）将含 0.1wt% Y2O3 的超细 W 复合粉末模压成形，压坯预烧后再在 1950 ℃ 下烧结 2h ，得到 W-0.1wt%Y2O3 材料，该材料致密度在 99.2% 以上，显微组织细小且均匀，晶粒度在 10μm 以下；材料在 200MW/m2 高热流密度冲击下样品表面不出现开裂。(5) Molding of ultrafine W composite powder containing 0.1wt% Y 2 O 3 , calcining the compact and sintering at 1950 °C for 2 h to obtain W-0.1wt% Y 2 O 3 material, the density of the material Above 99.2%, the microstructure is fine and uniform, and the grain size is below 10 μm; the material does not crack on the surface of the sample under the impact of high heat flux density of 200 MW/m 2 .
实施例 2 ： Example 2:
以制备成分为 W-0.3wt%La2O3 的弥散强化细晶钨材料为例。For example, a dispersion-strengthened fine-grained tungsten material having a composition of W-0.3 wt% La 2 O 3 is prepared.
（ 1 ）首先根据最终所要制备的稀土氧化物质量分数，按质量比例称取可溶性稀土盐和钨酸盐，即称取 1.53g 草酸镧， 410.45g 仲钨酸铵，分别配制成 60g/L 的稀土盐溶液和 200g/L 的钨盐溶液。 (1) First, according to the mass fraction of the rare earth oxide to be 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.
（ 2 ）首先在草酸镧溶液中缓慢滴加入浓度为 10 wt% 的 NaOH ，调节 pH 至 7.3 ，并加入 0.3g N,N- 二甲基甲酰胺作为反应分散剂，在超声波振动及电动搅拌机搅拌的作用下，使稀土盐与碱反应形成均匀悬浮 La(OH)3 颗粒胶体；然后将钨盐溶液加入到 La(OH)3 胶体中，缓慢滴加入浓度为 10 wt% 的 HCl ，调节 pH 至 6.8 ，并加入 1.5g PEG400 作为反应分散剂，在超声波振动及电动搅拌机搅拌的作用下使钨酸盐形成钨酸微粒子，并以 La(OH)3 胶体粒子为核心，沉淀包覆在 La(OH)3 胶体粒子周围，最终形成共沉淀包覆粒子胶体；(2) First, slowly add NaOH at a concentration of 10 wt% to the bismuth oxalate solution, adjust the pH to 7.3, and add 0.3 g of N,N-dimethylformamide as a reaction dispersant, stir in ultrasonic vibration and electric mixer. 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;
（ 3 ）然后，将该胶体在 400 ℃下进行喷雾干燥，喷雾转头转速为 20000 转 / 分，得到钨与稀土氧化镧的复合前驱体粉末。 (3) Then, the colloid was spray-dried at 400 °C, and the spray head rotation speed was 20000 rpm / A composite precursor powder of tungsten and rare earth cerium oxide is obtained.
（ 4 ） 将 复合前驱体 粉末在 350 ℃下煅烧，煅烧时间为 2h ；经解团聚、过筛后，在 78 0 ℃、 H2 气氛下保温 4h ；得到含 0.3wt% La2O3 的超细钨粉。(4) 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.
（ 5 ）将含微量稀土 La2O3 的超细 W 复合粉末模压成形，压坯预烧后再在 1950 ℃ 下烧结 3h ，得到 W-0.3wt%La2O3 材料，该材料致密度在 99.1% 以上，显微组织细小且均匀，晶粒度在 8μm 以下；材料在 200MW/m2 高热流密度冲击下样品表面不出现开裂。(5) Molding an ultrafine W composite powder containing a trace amount of rare earth La 2 O 3 , calcining the compact and sintering at 1950 ° C for 3 h to obtain a W-0.3 wt% La 2 O 3 material, the density of which is More than 99.1%, the microstructure is fine and uniform, and the grain size is below 8μm. The material does not crack on the surface of the sample under the impact of high heat flux density of 200MW/m 2 .
实施例 3 ： Example 3:
以制备成分为 W-0.5wt%CeO2 的弥散强化细晶钨材料为例。For example, a dispersion-strengthened fine-grained tungsten material having a composition of W-0.5 wt% CeO 2 is prepared.
（ 1 ）首先根据最终所要制备的稀土氧化物质量分数，按质量比例称取可溶性稀土盐和钨酸盐，即 2.10g 碳酸铈， 409.6g 钨酸铵，分别配制成 70g/L 的稀土盐溶液和 220g/L 的钨盐溶液。 (1) First, according to the mass fraction of the rare earth oxide to be finally 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.
（ 2 ）首先在碳酸铈溶液中缓慢滴加入浓度为 10 wt% 的 KOH ，调节 pH 至 7.5 ，并加入 0.3g 硬脂酸作为反应分散剂，在超声波振动及电动搅拌机搅拌的作用下，使稀土盐与碱反应形成均匀悬浮 Ce(OH)3 颗粒胶体；然后将钨盐溶液加入到 Ce(OH)3 胶体中，缓慢滴加入浓度为 10 wt% 的 HNO3 ，调节 pH 至 6.5 ，并加入 2.5g 硬脂酸作为反应分散剂，在超声波振动及电动搅拌机搅拌的作用下使钨酸盐形成钨酸微粒子，并以 Ce(OH)3 胶体粒子为核心，沉淀包覆在 Ce(OH)3 胶体粒子周围，最终形成共沉淀包覆粒子胶体；(2) First, slowly add KOH at a concentration of 10 wt% to the cesium carbonate solution, adjust the pH to 7.5, and add 0.3 g of stearic acid as a reaction dispersant. Under the action of ultrasonic vibration and electric mixer stirring, the rare earth is made. The salt reacts with the base to form a uniform suspension of Ce(OH) 3 colloid; then the tungsten salt solution is added to the Ce(OH) 3 colloid, and the concentration of 10 wt% of HNO 3 is slowly added dropwise, the pH is adjusted to 6.5, and 2.5 is added. g Stearic acid as a reaction dispersant, 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;
（ 3 ）然后，将该胶体在 400 ℃下进行喷雾干燥，喷雾转头转速为 25000 转 / 分，得到钨与稀土氧化铈的复合前驱体粉末。 (3) Then, the colloid was spray-dried at 400 °C, and the rotation speed of the spray head was 25,000 rpm. A composite precursor powder of tungsten and rare earth cerium oxide is obtained.
（ 4 ） 将 复合前驱体 粉末在 400 ℃下煅烧，煅烧时间为 2h ；经解团聚、过筛后，在 H2 气氛下两步还原，第一步在 60 0 ℃ 保温 2h ，第二步在 800 ℃ 保温 2h ，得到含 0.5wt% CeO2 的超细钨粉。(4) 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 .
（ 5 ）将含微量稀土 CeO2 的超细 W 复合粉末冷等静压成形，压坯预烧后再在 1950 ℃ 下烧结 4h ，得到 W-0.5wt%CeO2 材料，该材料致密度在 99.3% 以上，显微组织细小且均匀，晶粒度在 8μm 以下；材料在 200MW/m2 高热流密度冲击下样品表面不出现开裂。(5) 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. Above, the microstructure is fine and uniform, and the grain size is below 8 μm; the material does not crack on the surface of the sample under the impact of high heat flux density of 200 MW/m 2 .
实施例 4 ： Example 4:
以制备成分为 W-0.3wt%Y2O3-0.3wt%La2O 3 的弥散强化细晶钨材料为例。For example, 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.
（ 1 ）首先根据最终所要制备的稀土氧化物质量分数，按质量比例称取可溶性稀土盐和钨酸盐，即分别称取 1.52g 硝酸钇、 2.18g 氯化镧， 409.2g 偏钨酸铵，将硝酸钇和氯化镧混合配制成 80g/L 的稀土盐溶液，配置 250g/L 的钨盐溶液。 (1) Firstly, according to the mass fraction of the rare earth oxide to be 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.
（ 2 ）首先在硝酸钇和氯化镧混合溶液中缓慢滴加入浓度为 10 wt% 的氨水，调节 pH 至 7.8 ，并加入 0.4g 十二烷基磺酸钠作为反应分散剂，在超声波振动及电动搅拌机搅拌的作用下，使稀土盐与碱反应形成均匀悬浮 Y(OH)3+ La(OH)3 颗粒胶体；然后将钨盐溶液加入到 Y(OH)3+ La(OH)3 胶体中，缓慢滴加入浓度为 10 wt% 的草酸，调节 pH 至 6.2 ，并加入 3.0g 十二烷基磺酸钠作为反应分散剂，在超声波振动及电动搅拌机搅拌的作用下使钨酸盐形成钨酸微粒子，并以 Y(OH)3+ La(OH)3 胶体粒子为核心，沉淀包覆在 Y(OH)3+ La(OH)3 胶体粒子周围，最终形成共沉淀包覆粒子胶体；(2) First, slowly add 10% by weight of ammonia water to the mixed solution of cerium nitrate and cerium chloride, adjust the pH to 7.8, and add 0.4g of sodium dodecyl sulfonate as the reaction dispersant in ultrasonic vibration and Under the action of electric mixer, the rare earth salt reacts with the base to form a uniform suspension of Y(OH) 3 + La(OH) 3 particles colloid; then the tungsten salt solution is added to the Y(OH) 3 + La(OH) 3 colloid. Slowly add oxalic acid at a concentration of 10 wt%, adjust the pH to 6.2, and add 3.0 g of sodium dodecyl sulfate as a reaction dispersant to form tungstate into tungstic acid under the action of ultrasonic vibration and electric mixer stirring. Microparticles, with Y(OH) 3 + La(OH) 3 colloidal particles as the core, precipitated around the Y(OH) 3 + La(OH) 3 colloidal particles, and finally formed a coprecipitated coated particle colloid;
（ 3 ）然后，将该胶体在 450 ℃下进行喷雾干燥，喷雾转头转速为 25000 转 / 分，得到钨与稀土氧化钇 + 氧化镧的复合前驱体粉末。 (3) Then, the colloid was spray-dried at 450 °C, and the rotation speed of the spray head was 25,000 rpm. A composite precursor powder of tungsten and rare earth cerium oxide + cerium oxide was obtained.
（ 4 ） 将 复合前驱体 粉末在 400 ℃下煅烧，煅烧时间为 3h ；经解团聚、过筛后，在 80 0 ℃、 H2 气氛下保温 3h ；得到含 0.3wt% La2O3-0.3wt%La2O3 的超细钨粉。(4) 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 .
（ 5 ）将超细 W-Y2O3-La2O3 复合钨粉模压成形后，压坯在 1000 ℃ 预烧 2h ，再在 1920 ℃ 下烧结 3h ，得到 W-0.3wt%Y2O3-0.3wt%La2O 3 材料，该材料致密度在 99.4% 以上，显微组织细小且均匀，晶粒度在 6μm 以下；材料在 300MW/m2 高热流密度冲击下样品表面不出现开裂。(5) 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 6μm; the material does not crack on the surface of the sample under the impact of high heat flux density of 300MW/m 2 .
实施例 5 ： Example 5:
以制备成分为 W-0.3wt%Y2O3-0.3wt%La2O 3-0.3wt%CeO2 的弥散强化细晶钨材料为例。For example, 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.
（ 1 ）首先根据最终所要制备的稀土氧化物质量分数，按质量比例称取可溶性稀土盐和钨酸盐，即分别称取 1.85g 硫酸钇、 0.8g 硝酸镧、 1.52g 硝酸铈、 409g 偏钨酸铵，将硫酸钇、硝酸镧和硝酸铈混合配制成 100g/L 的稀土盐溶液，配置 300g/L 的钨盐溶液。 (1) Firstly, according to the mass fraction of the rare earth oxide to be 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.
（ 2 ）首先在硫酸钇、硝酸镧和硝酸铈混合溶液中缓慢滴加入浓度为 10 wt% 的 NaOH ，调节 pH 至 8.0 ，并加入 0.5g 吐温 -20 作为反应分散剂，在超声波振动及电动搅拌机搅拌的作用下，使稀土盐与碱反应形成均匀悬浮 Y(OH)3+ La(OH)3+ Ce(OH)3 颗粒胶体；然后将钨盐溶液加入到 Y(OH)3+ La(OH)3+ Ce(OH)3 胶体中，缓慢滴加入浓度为 10 wt% 的 HCl ，调节 pH 至 6.0 ，并加入 4.0g 吐温 -20 作为反应分散剂，在超声波振动及电动搅拌机搅拌的作用下使钨酸盐形成钨酸微粒子，并以 Y(OH)3+ La(OH)3+ Ce(OH)3 胶体粒子为核心，沉淀包覆在 Y(OH)3+ La(OH)3+ Ce(OH)3 胶体粒子周围，最终形成共沉淀包覆粒子胶体；(2) Firstly, slowly add NaOH with a concentration of 10 wt% in a mixed solution of barium sulfate, barium nitrate and barium nitrate, adjust the pH to 8.0, and add 0.5 g of Tween-20 as a reaction dispersant in ultrasonic vibration and electric Under the action of agitator, the rare earth salt is reacted with a base to form a uniform suspension of Y(OH) 3 + La(OH) 3 + Ce(OH) 3 particles colloid; then the tungsten salt solution is added to Y(OH) 3 + La ( In the OH) 3 + Ce(OH) 3 colloid, slowly add HCl at a concentration of 10 wt%, adjust the pH to 6.0, and add 4.0 g Tween-20 as a reaction dispersant in the ultrasonic vibration and stirring of the electric mixer. 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;
（ 3 ）然后，将该胶体在 450 ℃下进行喷雾干燥，喷雾转头转速为 30000 转 / 分，得到钨与稀土氧化钇 + 氧化镧 + 氧化铈的复合前驱体粉末。 (3) Then, the colloid is spray-dried at 450 °C, and the rotation speed of the spray head is 30,000 rpm / A composite precursor powder of tungsten and rare earth cerium oxide + cerium oxide + cerium oxide was obtained.
（ 4 ） 将 复合前驱体 粉末在 500 ℃下煅烧，煅烧时间为 3h ；经解团聚、过筛后，在 H2 气氛下，第一步在 60 0 ℃ 保温 2h ，第二步在 800 ℃ 保温 4h ，得到含 0.3wt% La2O3-0.3wt%La2O3-0.3wt%CeO 2 的超细钨粉。 （ 5 ）将含微量稀土 Y2O3 、 La2O3 、 CeO2 的超细 W 复合粉末模压成形，压坯预烧后再在 1950 ℃ 下烧结 4h ，得到 W-0.3wt%Y2O3- 0.3wt%La2O3-0.3wt%CeO2 材料，该材料致密度在 99.1% 以上，显微组织细小且均匀，晶粒度在 5μm 以下；材料在 300MW/m2 高热流密度冲击下样品表面不出现开裂。(4) 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. (5) Molding an ultrafine W composite powder containing a trace amount of rare earth Y 2 O 3 , La 2 O 3 , CeO 2 , calcining the compact, and sintering at 1950 ° C for 4 h to obtain W-0.3 wt% Y 2 O 3 - 0.3wt% La 2 O 3 -0.3wt% CeO 2 material, the density of the material is above 99.1%, the microstructure is fine and uniform, the grain size is below 5μm; the material is impacted at 300MW/m 2 high heat flux density No cracking occurred on the surface of the lower sample.

Claims (7)

  1. 一种稀土氧化物弥散强化细晶钨材料的制备方法，其特征在于包括以下步骤：A method for preparing a rare earth oxide dispersion strengthened fine grain tungsten material, comprising the steps of:
    （ 1 ）按稀土氧化物的质量百分数为 0.1 ～ 2% ，其余成分为 W ，称取可溶性稀土盐和钨酸盐，分别配制成 50 ～ 100g/L 的稀土盐溶液和 150~300g/L 的钨酸盐溶液；首先在稀土盐中加入碱控制 pH 在 7~8 ，并加入有机分散剂，搅拌使稀土盐形成均匀悬浮 R(OH)3 颗粒胶体， R 是稀土元素；然后将钨酸盐溶液加入到 R(OH)3 胶体中，加入酸控制 pH 在 6~7 ，并加入有机分散剂，搅拌使钨酸盐形成钨酸微粒子，并以 R(OH)3 胶体粒子为核心，沉淀包覆在 R(OH)3 胶体粒子周围，最终形成共沉淀包覆粒子胶体；再将该胶体在 350~450 ℃喷雾干燥，得到钨与稀土氧化物的复合前驱体粉末； 将 复合前驱体 粉末在 300~600 ℃下煅烧，煅烧时间为 1~4h ，经解团聚、过筛后，在 600~850 ℃ 氢气热还原，还原时间为 2~6h ，制备出含微量稀土氧化物、粒度在 50~500nm 的超细 / 纳米钨粉；所述的稀土氧化物是 Y2O3 、 La2O3 或 CeO2 中的一种或多种；(1) According to the mass percentage of rare earth oxides is 0.1 to 2%, and the remaining components are W, and the soluble rare earth salts and tungstates are weighed and formulated into 50-100 g/L rare earth salt solution and 150-300 g/L, respectively. Tungstate solution; firstly add alkali in the rare earth salt to control the pH between 7 and 8, and add an organic dispersant, stir to form a uniform suspension of R(OH) 3 particles colloid, R is a rare earth element; then tungstate The solution is added to the R(OH) 3 colloid, acid is added to control the pH at 6~7, and the organic dispersant is added, and the tungstate is stirred to form the tungstic acid microparticles, and the R(OH) 3 colloidal particles are used as the core, and the precipitate is packaged. Covering the R(OH) 3 colloidal particles, the coprecipitated coated particle colloid is finally formed; 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 Calcination at 300~600 °C, calcination time is 1~4h, after deagglomeration, sieving, hydrogen reduction at 600~850 °C, reduction time is 2~6h, preparation of trace rare earth oxide, particle size at 50~ 500nm ultrafine/nano tungsten powder; the rare earth oxide is Y 2 O 3 , one or more of La 2 O 3 or CeO 2 ;
    （ 2 ）将（ 1 ）中的含微量稀土氧化物的超细 / 纳米钨粉在 150~300MPa 下 采用模压或冷等静压普通压制成形；(2) The ultrafine/nano tungsten powder containing trace rare earth oxide in (1) is 150~300MPa Forming or cold isostatic pressing;
    （ 3 ）将压制 成形后的压坯在高温烧结炉中进行常规高温烧结，烧结温度为 1800~2000 ℃ ，保温时间为 1 ～ 5h ，得到致密的高性能稀土氧化物超均匀弥散分布强化细晶钨材料。 (3) The compacted compact is subjected to conventional high-temperature sintering in a high-temperature sintering furnace at a sintering temperature of 1800 to 2000 ° C and a holding time of 1 ～ At 5h, a dense high-performance rare earth oxide super-diffused dispersion-enhanced fine-grained tungsten material is obtained.
  2. 根据权利要求 1 所述的稀土氧化物弥散强化细晶钨材料的制备方法，其特征在于：所述的钨酸盐是偏钨酸铵、仲钨酸铵或钨酸铵。According to claim 1 The method for preparing a rare earth oxide dispersion-strengthened fine-grained tungsten material, characterized in that the tungstate is ammonium metatungstate, ammonium paratungstate or ammonium tungstate.
  3. 根据权利要求 1 所述的稀土氧化物弥散强化细晶钨材料的制备方法，其特征在于：所述的稀土盐是 Y 、 La 、 Ce 的硝酸盐、草酸盐、碳酸盐、氯化物或硫酸盐。 The method for preparing a rare earth oxide dispersion-strengthened fine-grained tungsten material according to claim 1, wherein the rare earth salt is Y, La, Ce Nitrate, oxalate, carbonate, chloride or sulfate.
  4. 根据权利要求 1 所述的稀土氧化物弥散强化细晶钨材料的制备方法，其特征在于：所述搅拌转速为 1000~5000 转 / 分。 The method for preparing a rare earth oxide dispersion-strengthened fine-grained tungsten material according to claim 1, wherein the stirring speed is 1000 to 5000 rpm / Minute.
  5. 根据权利要求 1 所述的稀土氧化物弥散强化细晶钨材料的制备方法，其特征在于：所述喷雾干燥喷头转速为 20000~30000 转 / 分。The method for preparing a rare earth oxide dispersion-strengthened fine-grained tungsten material according to claim 1, wherein the spray drying nozzle has a rotational speed of 20,000 to 30,000 Transfer / minute.
  6. 根据权利要求 1 所述的稀土氧化物弥散强化细晶钨材料的制备方法，其特征在于：所述的反应分散剂为硬脂酸、聚乙二醇、尿素、 N,N- 二甲基甲酰胺、 OP 乳化剂、吐温 -20 或十二烷基磺酸钠，反应分散剂质量为稀土盐溶液或钨酸盐溶液质量的 0.1~1.5% 。The method for preparing a rare earth oxide dispersion-strengthened fine-grained tungsten material according to claim 1, wherein 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. .
  7. 根据权利要求 1 所述的稀土氧化物弥散强化细晶钨材料的制备方法，其特征在于：步骤（ 1 ）所述的加入酸控制 pH 值，加入的酸为 HCl 、 HNO3 或草酸；在稀土盐中加入碱控制 pH 值，加入的碱为 NaOH 、 KOH 或氨水。 The method for preparing a rare earth oxide dispersion-strengthened fine-grained tungsten material according to claim 1, wherein the acid added in step (1) controls the pH value, and the added acid is HCl, HNO 3 or oxalic acid; A base is added to the salt to control the pH, and the base added is NaOH, KOH or ammonia.
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