WO2020228709A1 - Method for preparing alloy powder material - Google Patents

Method for preparing alloy powder material Download PDF

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WO2020228709A1
WO2020228709A1 PCT/CN2020/089895 CN2020089895W WO2020228709A1 WO 2020228709 A1 WO2020228709 A1 WO 2020228709A1 CN 2020089895 W CN2020089895 W CN 2020089895W WO 2020228709 A1 WO2020228709 A1 WO 2020228709A1
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alloy
acid
alloy powder
powder material
preparing
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PCT/CN2020/089895
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French (fr)
Chinese (zh)
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刘丽
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刘丽
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C3/00—Removing material from alloys to produce alloys of different constitution separation of the constituents of alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C3/00—Removing material from alloys to produce alloys of different constitution separation of the constituents of alloys
    • C22C3/005—Separation of the constituents of alloys

Definitions

  • the invention relates to the technical field of metal materials, in particular to a method for preparing alloy powder materials.
  • Micro-nano particle size alloy powder due to its special surface effect, quantum size effect, quantum tunneling effect and Coulomb blocking effect, exhibits many unique properties different from traditional materials in optics, electricity, magnetism, catalysis, etc. Therefore, it is widely used in many fields such as optoelectronic devices, wave absorbing materials, and high-efficiency catalysts.
  • the preparation methods of ultra-fine alloy powder are classified into solid phase method, liquid phase method and gas phase method from the state of matter.
  • the solid phase method mainly includes mechanical crushing method, ultrasonic crushing method, thermal decomposition method, explosion method and so on.
  • Liquid phase methods mainly include precipitation method, alkoxide method, carbonyl method, spray thermal drying method, freeze drying method, electrolysis method, chemical coagulation method, etc.
  • the gas phase method mainly includes gas phase reaction method, plasma method, high temperature plasma method, evaporation method, chemical vapor deposition method, etc.
  • Rotating electrode method and gas atomization method are currently the main methods for preparing high-performance alloy powder, but the production efficiency is low, the yield of ultrafine powder is not high, and the energy consumption is relatively large; jet milling method and hydrogenation dehydrogenation method are suitable for large Industrial production in batches, but with strong selectivity to raw metals and alloys. Therefore, it is of great significance to develop new preparation methods for ultrafine alloy powder materials.
  • a preparation method of alloy powder material includes the following steps:
  • (M x T y ) a RE b alloy wherein M is selected from at least one of Fe, Co, Ni, and T is selected from W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti
  • the (MxTy) a RE b alloy The solidification structure of the is composed of a dispersed particle phase with a composition of M x T y and a matrix phase with a composition mainly of RE;
  • the (M x T y ) a RE b alloy is mixed with an acid solution, the matrix phase reacts with the acid solution to become ions into the solution, and the dispersed particle phase separates out, that is, M x T y Composition of alloy powder material.
  • the alloy melt is prepared into the (M x T y ) a RE b alloy by a solidification method, wherein the solidification rate of the alloy melt is 0.001 K/s to 10 7 K/s.
  • the vacuum degree during the melting of the alloy melt is 1 ⁇ 10 -4 Pa to 1.01325 ⁇ 10 5 Pa.
  • the particle shape of the dispersed particle phase includes at least one of a dendritic shape, a spherical shape, a nearly spherical shape, a square shape, a pie shape, and a rod shape, and the particle size of the dispersed particle phase is 2 nm to 100 mm.
  • the acid in the acid solution is at least one of sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, phosphoric acid, acetic acid, oxalic acid, formic acid, carbonic acid, gluconic acid, oleic acid, and polyacrylic acid.
  • the solvent in the acid solution It is water, ethanol, methanol or a mixture of the three in any ratio.
  • the molar concentration of the acid in the acid solution is 0.001 mol/L to 5 mol/L.
  • the reaction time is 0.1 min to 48 h, and the reaction temperature is 0°C to 100°C.
  • the particle size of the M x T y alloy powder material is 2 nm to 100 mm.
  • the following step is further performed: the obtained alloy powder material with a particle size range of 1 ⁇ m to 1 mm is sieved, Plasma spheroidization is performed respectively, and finally alloy powder materials with different particle sizes and spherical shapes are obtained.
  • the particle size of the spherical alloy powder material with different particle diameters is 1 ⁇ m to 1 mm.
  • a (M x T y ) a RE b alloy made of a specific type and content of metal M, metal T and rare earth RE is selected.
  • the solidified structure of the alloy is composed of a dispersed particle phase with a composition of M x T y and a matrix phase with a composition mainly of RE. The structure is conducive to subsequent separation.
  • the matrix phase reacts with the H ions in the acid solution to become ions into the solution, and the composition is a dispersed particle phase of M x T y It is difficult to react with the dilute acid solution, so that it can be dispersed and separated from the (M x T y ) a RE b alloy, and finally the M x T y alloy powder material is obtained.
  • rare earth elements not only have a good "absorbing” effect on oxygen, but also have a good "absorbing” effect on other various impurity elements in the alloy raw materials M and T. Therefore, the dispersed particle phase in the (M x T y ) a RE b alloy and the obtained M x T y alloy powder material tend to have higher purity than the raw materials M and T.
  • the method has low cost and simple operation, and can prepare various alloy powder materials with different morphologies including nanometer, submicrometer, micrometer and millimeter level.
  • the alloy powder material has good application prospects in hydrogen storage, catalysis, powder metallurgy, 3D printing and other fields.
  • Figure 1 is a scanning electron micrograph of CoTi dendrites prepared in Example 1 of the present invention.
  • Fig. 2 is a high magnification photograph of the CoTi dendrites prepared in Example 1 of the present invention
  • FIG. 3 is an energy spectrum diagram of CoTi dendrites prepared in Example 1 of the present invention.
  • the method for preparing alloy powder material provided by the present invention includes the following steps:
  • step S1 the (M x T y ) a RE b alloy is obtained in the following manner:
  • the alloy melt is prepared into the (M x T y ) a RE b alloy by a solidification method, wherein the solidification rate of the alloy melt is 0.001 K/s to 10 7 K/s.
  • step (1) the raw materials required for smelting (M x T y ) a RE b alloy are prepared according to a specific composition and content.
  • step (2) due to the presence of a large amount of rare earth elements in the alloy melt obtained by melting the alloy raw materials, even if oxygen enters the alloy melt during the smelting process, all oxygen will be quickly "absorbed" by the rare earth elements, forming a coating
  • the dense rare earth oxide protective film on the surface of the alloy melt blocks the passage of oxygen from further entering the alloy melt. Therefore, even if the alloy is smelted under low vacuum conditions or even atmospheric conditions, the dispersed particles in the solidified structure of the alloy will still not be contaminated by oxygen. Therefore, when the vacuum degree in the melting process of the alloy melt is 1 ⁇ 10 -4 Pa ⁇ 1.01325 ⁇ 10 5 Pa, the purity of the obtained dispersed particle phase can still be guaranteed.
  • rare earth elements not only have a good "absorbing” effect on oxygen, but also have a good "absorbing” effect on other various impurity elements in the alloy raw materials M and T. Therefore, the dispersed particle phase in the (M x T y ) a RE b alloy tends to have higher purity than the raw materials M and T.
  • the alloy raw materials are metal M, metal T and rare earth RE, each element can be melted to prepare an alloy melt.
  • the alloy raw materials provided are directly (M x T y ) a RE b alloy, the (M x T y ) a RE b alloy can be remelted to obtain an alloy melt.
  • the solidified structure of the alloy melt is composed of a dispersed particle phase composed of M x T y and a matrix phase composed mainly of RE.
  • the dispersed particle phase of the component M x T y is an inert component under the action of dilute acid, and it is difficult to react with acid;
  • the matrix phase mainly composed of RE is an active component, which is very easy to react with acid. Therefore, the solidified structure of the (M x T y ) a RE b alloy facilitates subsequent separation.
  • the solidification method is not limited, and may be methods such as casting, melt stripping, and melt drawing.
  • the particle size and morphology of the finally formed alloy powder material is basically consistent with the particle size and morphology of the M x T y dispersed particle phase in the (M x T y ) a RE b alloy.
  • the particle size of the M x T y dispersed particle phase is related to the solidification rate of the alloy melt during the preparation process.
  • the particle size of the M x T y dispersed particle phase has a negative correlation with the cooling rate of the alloy melt, that is, the greater the solidification rate of the alloy melt, the smaller the particle size of the dispersed particle phase.
  • the solidification rate of the alloy melt may be 0.001 K/s to 10 7 K/s
  • the particle size of the M x T y dispersed particle phase may be 2 nm to 100 mm.
  • the particle shape of the dispersed particle phase is not limited, and may include at least one of a dendritic shape, a spherical shape, a nearly spherical shape, a square shape, a pie shape, and a rod shape.
  • the particle size specifically refers to the diameter of the rod-shaped cross-section.
  • the acid solution is a solution containing H + .
  • (M x T y ) a RE b alloy solidification structure is composed of a dispersed grain phase with a composition of M x T y and a matrix phase with a composition mainly of RE. Therefore, the H + in the dilute acid solution reacts with the rare earth elements in the matrix phase to dissolve the rare earth elements into ions and enter the solution, while the M x T y dispersed particle phase, which is difficult to react with the dilute acid solution, is removed from the original alloy Disperse out of it. After cleaning, the M x T y alloy powder material is obtained.
  • the particle size of the alloy powder material can be nanometer, submicrometer, micrometer, or even millimeter.
  • the acid in the acid solution may be at least one of sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, phosphoric acid, acetic acid, oxalic acid, formic acid, carbonic acid, gluconic acid, oleic acid, and polyacrylic acid, preferably sulfuric acid, hydrochloric acid , At least one of nitric acid, perchloric acid, phosphoric acid, acetic acid, and oxalic acid.
  • the solvent in the acid solution is water, ethanol, methanol or a mixture thereof mixed in any ratio.
  • the concentration of the dilute acid in the acid solution is not specifically limited, as long as it can react with the matrix phase and retain the primary crystal phase.
  • the reaction time is not limited, and the reaction temperature is not limited.
  • the molar concentration of the acid in the acid solution may be 0.001 mol/L to 5 mol/L.
  • the reaction time of this reaction can be 0.1min ⁇ 48h, and the reaction temperature can be 0°C ⁇ 100°C.
  • step S2 if the particle size of the obtained alloy powder material is in the range of 1 ⁇ m to 1 mm, the following steps may be performed: the obtained alloy powder material is sieved, and plasma spheroidization is performed respectively, and finally A spherical alloy powder material with different particle sizes is obtained.
  • the powder material after the screening can be spheroidized by plasma spheroidization.
  • the particle diameter of the spherical alloy powder material with different particle diameters is 1 ⁇ m to 1 mm.
  • the method has low cost and simple operation, and can prepare a variety of alloy powder materials with different morphologies including nanometer, submicrometer, micrometer and millimeter level.
  • the alloy powder material has good application prospects in hydrogen storage, catalysis, powder metallurgy, 3D printing and other fields.
  • This embodiment provides a method for preparing micron-sized CoTi powder, which includes the following steps:
  • the alloy solidification structure includes dispersed dendritic particles composed of CoTi and a matrix phase composed of Gd, and the size of the CoTi dendritic particles ranges from 2 ⁇ m to 40 ⁇ m.
  • the alloy powder material was tested by scanning electron microscopy. As shown in Figure 1 and Figure 2, the alloy powder particles were in dendrite shape.
  • This embodiment provides a method for preparing spherical micron-sized CoTi powder, which includes the following steps:
  • the alloy solidification structure includes dispersed dendritic particles composed of CoTi and a matrix phase composed of Gd, and the size of the CoTi dendritic particles ranges from 2 ⁇ m to 40 ⁇ m.
  • the dendrite size ranges are >26 ⁇ m, 26 ⁇ m-13 ⁇ m, 13 ⁇ m ⁇ Graded CoTi dendritic powder of 6.5 ⁇ m and less than 6.5 ⁇ m.
  • the CoTi dendritic powders with dendrite diameters ranging from 26 ⁇ m to 13 ⁇ m and 13 ⁇ m to 6.5 ⁇ m are selected respectively, and spherical Co 50 Ti with particle sizes ranging from 26 ⁇ m to 13 ⁇ m and 13 ⁇ m to 6.5 ⁇ m are further prepared through mature plasma spheroidization technology. 50 powder.
  • This embodiment provides a method for preparing nano-scale CoHf powder, including the following steps:
  • This embodiment provides a method for preparing spherical micron CoCrMo powder, which includes the following steps:
  • the alloy solidification structure of the Gd 75 alloy sheet includes dispersed dendritic particles composed of Co-Cr-Mo and a matrix phase composed of Gd, and the size of the Co-Cr-Mo dendritic particles ranges from 3 ⁇ m to 50 ⁇ m.
  • Co-Cr-Mo dendritic particles were separated from the solution, washed and dried, and then micron-sized Co-Cr-Mo dendritic powder was obtained, the composition of which was approximately Co 63 Cr 33 Mo 4 , dendritic particles The size range of 3 ⁇ m ⁇ 50 ⁇ m.
  • the dendrite size ranges are> 26 ⁇ m, 26 ⁇ m ⁇ Graded Co-Cr-Mo dendritic powder of 13 ⁇ m, 13 ⁇ m ⁇ 6.5 ⁇ m and less than 6.5 ⁇ m.
  • Co-Cr-Mo dendritic powders with dendrite particle sizes ranging from 26 ⁇ m to 13 ⁇ m and 13 ⁇ m to 6.5 ⁇ m are selected, and the particle size ranges from 26 ⁇ m to 13 ⁇ m and 13 ⁇ m to 6.5 ⁇ m are further prepared by mature plasma spheroidizing technology.
  • Spherical Co 63 Cr 33 Mo 4 powder are further prepared by mature plasma spheroidizing technology.
  • This embodiment provides a method for preparing sub-micron CoTiHf powder, which includes the following steps:
  • This embodiment provides a method for preparing micro-nano CoTiZr powder, which includes the following steps:
  • the alloy structure includes a matrix composed of Y and a nearly spherical dispersed particle phase composed of Co 50 Ti 25 Zr 25 ). The diameter of the dispersed particles ranges from 50-500nm.
  • the obtained Co 50 Ti 25 Zr 25 dispersed particles are separated from the solution, washed and dried to obtain approximately spherical Co 50 Ti 25 Zr 25 micro-nano alloy powder, the diameter of which is in the range of 50-500 nm.

Abstract

The present invention relates to a method for preparing alloy powder material. Using the feature of an alloy solidification structure containing a matrix phase and an inert dispersed particle phase, the matrix phase is removed by reaction with an acid solution, so that the dispersed particle phase is separated to obtain the alloy powder material. The method is simple in process, and can prepare a variety of alloy powder materials with different morphologies including nanometer, submicrometer, micrometer and millimeter level, which has good application prospects in the fields including catalysis, powder metallurgy, and 3D printing.

Description

一种合金粉体材料的制备方法Method for preparing alloy powder material 技术领域Technical field
本发明涉及金属材料技术领域，特别是涉及一种合金粉体材料的制备方法。The invention relates to the technical field of metal materials, in particular to a method for preparing alloy powder materials.
背景技术Background technique
微纳米粒径的合金粉体，由于具有特殊的表面效应、量子尺寸效应，量子隧道效应以及库仑阻塞效应等，在光学、电学、磁学、催化等方面表现出诸多与传统材料不同的奇特性能，因此被广泛地应用于光电子器件、吸波材料、高效催化剂等多个领域。Micro-nano particle size alloy powder, due to its special surface effect, quantum size effect, quantum tunneling effect and Coulomb blocking effect, exhibits many unique properties different from traditional materials in optics, electricity, magnetism, catalysis, etc. Therefore, it is widely used in many fields such as optoelectronic devices, wave absorbing materials, and high-efficiency catalysts.
目前，超细合金粉体的制备方法从物质的状态分有固相法、液相法和气相法。固相法主要有机械粉碎法、超声波粉碎法、热分解法、***法等。液相法主要有沉淀法、醇盐法、羰基法、喷雾热干燥法、冷冻干燥法、电解法、化学凝聚法等。气相法主要有气相反应法、等离子体法、高温等离子体法、蒸发法、化学气相沉积法等。虽然超细合金粉末的制备方法有很多种，但每种方法都有一定的局限性。例如，液相法的缺点是产量低、成本高和工艺复杂等。机械法的缺点是在制取粉末后存在分级困难的问题，且产品的纯度、细度和形貌均难以保证。旋转电极法和气体雾化法是目前制备高性能合金粉末的主要方法，但生产效率低，超细粉末的收得率不高，能耗相对较大；气流磨法、氢化脱氢法适合大批量工业化生产，但对原料金属和合金的选择性较强。因此，开发新的超细合金粉体材料的制备方法，具有重要的意义。At present, the preparation methods of ultra-fine alloy powder are classified into solid phase method, liquid phase method and gas phase method from the state of matter. The solid phase method mainly includes mechanical crushing method, ultrasonic crushing method, thermal decomposition method, explosion method and so on. Liquid phase methods mainly include precipitation method, alkoxide method, carbonyl method, spray thermal drying method, freeze drying method, electrolysis method, chemical coagulation method, etc. The gas phase method mainly includes gas phase reaction method, plasma method, high temperature plasma method, evaporation method, chemical vapor deposition method, etc. Although there are many methods for preparing ultrafine alloy powders, each method has certain limitations. For example, the shortcomings of the liquid phase method are low yield, high cost, and complicated process. The disadvantage of the mechanical method is that it is difficult to classify after preparing the powder, and the purity, fineness and morphology of the product are difficult to guarantee. Rotating electrode method and gas atomization method are currently the main methods for preparing high-performance alloy powder, but the production efficiency is low, the yield of ultrafine powder is not high, and the energy consumption is relatively large; jet milling method and hydrogenation dehydrogenation method are suitable for large Industrial production in batches, but with strong selectivity to raw metals and alloys. Therefore, it is of great significance to develop new preparation methods for ultrafine alloy powder materials.
发明概述Summary of the invention
技术问题technical problem
问题的解决方案The solution to the problem
技术解决方案Technical solutions
基于此，有必要针对上述技术问题，提供一种工艺简单、易于操作的合金粉体材料的制备方法。Based on this, it is necessary to provide a method for preparing alloy powder material with simple process and easy operation in response to the above technical problems.
一种合金粉体材料的制备方法，包括以下步骤：A preparation method of alloy powder material includes the following steps:
提供(M xT y) aRE b合金，其中，M选自Fe、Co、Ni中的至少一种，T选自W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti中的至少一种，RE选自Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的至少一种，x、y以及a、b分别代表对应组成的原子百分比含量，且33％≤x≤75％，x+y＝100％；0.1％≤a≤40％，a+b＝100％，所述(MxTy) aRE b合金的凝固组织由成分为M xT y的弥散颗粒相与成分主要为RE的基体相组成； Provide (M x T y ) a RE b alloy, wherein M is selected from at least one of Fe, Co, Ni, and T is selected from W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti At least one, RE is selected from at least one of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, x, y, and a, b respectively represents the atomic percentage content of the corresponding composition, and 33%≤x≤75%, x+y=100%; 0.1%≤a≤40%, a+b=100%, the (MxTy) a RE b alloy The solidification structure of the is composed of a dispersed particle phase with a composition of M x T y and a matrix phase with a composition mainly of RE;
将所述(M xT y) aRE b合金与酸溶液混合，使所述基体相与所述酸溶液反应变成离子进入溶液，所述弥散颗粒相脱离出来，即得到由M xT y组成的合金粉体材料。 The (M x T y ) a RE b alloy is mixed with an acid solution, the matrix phase reacts with the acid solution to become ions into the solution, and the dispersed particle phase separates out, that is, M x T y Composition of alloy powder material.
进一步地，所述(M xT y) aRE b合金通过以下方式得到： Further, the (M x T y ) a RE b alloy is obtained in the following manner:
按照配比称取合金原料；Weigh the alloy raw materials according to the ratio;
将所述合金原料充分熔化得到合金熔体；Fully melting the alloy raw materials to obtain an alloy melt;
将合金熔体通过凝固方法制备成所述(M xT y) aRE b合金，其中，所述合金熔体的凝固速率为0.001K/s～10 7K/s。 The alloy melt is prepared into the (M x T y ) a RE b alloy by a solidification method, wherein the solidification rate of the alloy melt is 0.001 K/s to 10 7 K/s.
进一步地，所述合金熔体熔炼过程中的真空度为1×10 -4Pa～1.01325×10 5Pa。 Further, the vacuum degree during the melting of the alloy melt is 1×10 -4 Pa to 1.01325×10 5 Pa.
进一步地，所述弥散颗粒相的颗粒形状包括枝晶形、球形、近球形、方块形、饼形、棒形中的至少一种，所述弥散颗粒相的颗粒大小为2nm～100mm。Further, the particle shape of the dispersed particle phase includes at least one of a dendritic shape, a spherical shape, a nearly spherical shape, a square shape, a pie shape, and a rod shape, and the particle size of the dispersed particle phase is 2 nm to 100 mm.
进一步地，所述酸溶液中酸为硫酸、盐酸、硝酸、高氯酸、磷酸、醋酸、草酸、甲酸、碳酸、葡萄糖酸、油酸、聚丙烯酸中的至少一种，所述酸溶液中溶剂为水、乙醇、甲醇或者三者以任意比例混合的混合物。Further, the acid in the acid solution is at least one of sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, phosphoric acid, acetic acid, oxalic acid, formic acid, carbonic acid, gluconic acid, oleic acid, and polyacrylic acid. The solvent in the acid solution It is water, ethanol, methanol or a mixture of the three in any ratio.
进一步地，所述酸溶液中酸的摩尔浓度为0.001mol/L～5mol/L。Further, the molar concentration of the acid in the acid solution is 0.001 mol/L to 5 mol/L.
进一步地，所述(M xT y) aRE b合金与所述酸溶液进行反应的步骤中，反应时间为0.1min～48h，反应温度为0℃～100℃。 Further, in the step of reacting the (M x T y ) a RE b alloy with the acid solution, the reaction time is 0.1 min to 48 h, and the reaction temperature is 0°C to 100°C.
进一步地，所述M xT y合金粉体材料的粒径为2nm～100mm。 Further, the particle size of the M x T y alloy powder material is 2 nm to 100 mm.
进一步地，在将所述(M xT y) aRE b合金与所述酸溶液进行反应的步骤之后还进行以下步骤：将所得的粒径范围为1μm～1mm合金粉体材料进行筛分，并分别进行等离子球化处理，最终得到具有不同粒径且呈球形的合金粉体材料。 Further, after the step of reacting the (M x T y ) a RE b alloy with the acid solution, the following step is further performed: the obtained alloy powder material with a particle size range of 1 μm to 1 mm is sieved, Plasma spheroidization is performed respectively, and finally alloy powder materials with different particle sizes and spherical shapes are obtained.
进一步地，所述具有不同粒径且呈球形的合金粉体材料的颗粒大小为1μm～1mm。Further, the particle size of the spherical alloy powder material with different particle diameters is 1 μm to 1 mm.
本发明所述合金粉体材料的制备方法中，选择特定类别与含量的金属M、金属T与稀土RE制成的(M xT y) aRE b合金。该合金凝固组织由成分为M xT y的弥散颗粒相与成分主要为RE的基体相组成，该组织结构有利于后续分离。具体来说，该(M xT y) aRE b合金在后续与稀酸溶液反应时，基体相与酸溶液中的H离子反应变成离子进入溶液，成分为M xT y的弥散颗粒相则难以与稀酸溶液反应，从而可以从(M xT y) aRE b合金中分散脱离出来，最终得到M xT y合金粉体材料。 In the preparation method of the alloy powder material of the present invention, a (M x T y ) a RE b alloy made of a specific type and content of metal M, metal T and rare earth RE is selected. The solidified structure of the alloy is composed of a dispersed particle phase with a composition of M x T y and a matrix phase with a composition mainly of RE. The structure is conducive to subsequent separation. Specifically, when the (M x T y ) a RE b alloy subsequently reacts with the dilute acid solution, the matrix phase reacts with the H ions in the acid solution to become ions into the solution, and the composition is a dispersed particle phase of M x T y It is difficult to react with the dilute acid solution, so that it can be dispersed and separated from the (M x T y ) a RE b alloy, and finally the M x T y alloy powder material is obtained.
此外，稀土元素不仅对氧具有很好的“吸收”作用，且对合金原料M与T中的其他各类杂质元素也具有很好的“吸收”作用。因此，(M xT y) aRE b合金中的弥散颗粒相与所得M xT y合金粉体材料往往具有相比原材料M与T更高的纯度。 In addition, rare earth elements not only have a good "absorbing" effect on oxygen, but also have a good "absorbing" effect on other various impurity elements in the alloy raw materials M and T. Therefore, the dispersed particle phase in the (M x T y ) a RE b alloy and the obtained M x T y alloy powder material tend to have higher purity than the raw materials M and T.
该方法成本低、操作简单，可以制备包括纳米级、亚微米级、微米级以及毫米级的不同形貌的多种合金粉体材料。该合金粉体材料在储氢、催化、粉末冶金、3D打印等领域具有很好的应用前景。The method has low cost and simple operation, and can prepare various alloy powder materials with different morphologies including nanometer, submicrometer, micrometer and millimeter level. The alloy powder material has good application prospects in hydrogen storage, catalysis, powder metallurgy, 3D printing and other fields.
发明的有益效果The beneficial effects of the invention
对附图的简要说明Brief description of the drawings
附图说明Description of the drawings
图1为本发明实施例1所制备的CoTi枝晶的扫描电镜照片；Figure 1 is a scanning electron micrograph of CoTi dendrites prepared in Example 1 of the present invention;
图2为本发明实施例1所制备的CoTi枝晶的扫描电镜高倍照片；Fig. 2 is a high magnification photograph of the CoTi dendrites prepared in Example 1 of the present invention;
图3为本发明实施例1所制备的CoTi枝晶的能谱图。FIG. 3 is an energy spectrum diagram of CoTi dendrites prepared in Example 1 of the present invention.
发明实施例Invention embodiment
本发明的实施方式Embodiments of the invention
下面结合附图与实施例对本发明作进一步详细描述，需要指出的是，以下所述实施例旨在便于对本发明的理解，而对其不起任何限定作用。The present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be pointed out that the following embodiments are intended to facilitate the understanding of the present invention and do not have any limiting effect on it.
本发明提供的合金粉体材料的制备方法，包括以下步骤：The method for preparing alloy powder material provided by the present invention includes the following steps:
S1，提供(M xT y) aRE b合金，其中，M选自Fe、Co、Ni中的至少一种，T选自W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti 中的至少一种，RE选自Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的至少一种，x、y以及a、b分别代表对应组成的原子百分比含量，且33％≤x≤75％，x+y＝100％；0.1％≤a≤40％，a+b＝100％，所述(MxTy) aRE b合金的凝固组织由成分为M xT y的弥散颗粒相与成分主要为RE的基体相组成； S1, providing (M x T y ) a RE b alloy, wherein M is selected from at least one of Fe, Co, and Ni, and T is selected from W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti At least one of, RE is selected from at least one of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, x, y, and a and b respectively represent the atomic percentage content of the corresponding composition, and 33%≤x≤75%, x+y=100%; 0.1%≤a≤40%, a+b=100%, the (MxTy) a RE The solidification structure of b alloy consists of a dispersed grain phase with a composition of M x T y and a matrix phase with a composition mainly of RE;
S2，将所述(M xT y) aRE b合金与酸溶液混合，使所述基体相与所述酸溶液反应变成离子进入溶液，所述弥散颗粒相脱离出来，即得到由M xT y组成的合金粉体材料。 S2, mixing the (M x T y ) a RE b alloy with an acid solution, so that the matrix phase reacts with the acid solution to become ions into the solution, and the dispersed particle phase is separated, and the resulting M x Alloy powder material composed of Ty .
步骤S1中，所述(M xT y) aRE b合金通过以下方式得到： In step S1, the (M x T y ) a RE b alloy is obtained in the following manner:
(1)按照配比称取合金原料；(1) Weigh the alloy raw materials according to the ratio;
(2)将所述合金原料充分熔化得到合金熔体；(2) Fully melt the alloy raw materials to obtain an alloy melt;
(3)将合金熔体通过凝固方法制备成所述(M xT y) aRE b合金，其中，所述合金熔体的凝固速率为0.001K/s～10 7K/s。 (3) The alloy melt is prepared into the (M x T y ) a RE b alloy by a solidification method, wherein the solidification rate of the alloy melt is 0.001 K/s to 10 7 K/s.
步骤(1)中，按照特定组成与含量配制熔炼(M xT y) aRE b合金所需原料。 In step (1), the raw materials required for smelting (M x T y ) a RE b alloy are prepared according to a specific composition and content.
步骤(2)中，由于合金原料熔化得到的合金熔体中存在大量的稀土元素，所以，在熔炼过程中，氧即使进入该合金熔体也会全部被稀土元素迅速“吸收”，形成覆于该合金熔体的表面的致密氧化稀土保护膜，从而隔断氧进一步进入该合金熔体的通道。因此，即使在低真空条件、甚至是大气环境的条件下熔炼该合金，该合金凝固组织中的弥散颗粒相仍然不会被氧污染。所以，所述合金熔体的熔炼过程中的真空度为1×10 -4Pa～1.01325×10 5Pa时，所获得的弥散颗粒相的纯度仍然能够得到保证。 In step (2), due to the presence of a large amount of rare earth elements in the alloy melt obtained by melting the alloy raw materials, even if oxygen enters the alloy melt during the smelting process, all oxygen will be quickly "absorbed" by the rare earth elements, forming a coating The dense rare earth oxide protective film on the surface of the alloy melt blocks the passage of oxygen from further entering the alloy melt. Therefore, even if the alloy is smelted under low vacuum conditions or even atmospheric conditions, the dispersed particles in the solidified structure of the alloy will still not be contaminated by oxygen. Therefore, when the vacuum degree in the melting process of the alloy melt is 1×10 -4 Pa˜1.01325×10 5 Pa, the purity of the obtained dispersed particle phase can still be guaranteed.
此外，稀土元素不仅对氧具有很好的“吸收”作用，且对合金原料M与T中的其他各类杂质元素也具有很好的“吸收”作用。因此，(M xT y) aRE b合金中的弥散颗粒相往往具有相比原材料M与T更高的纯度。 In addition, rare earth elements not only have a good "absorbing" effect on oxygen, but also have a good "absorbing" effect on other various impurity elements in the alloy raw materials M and T. Therefore, the dispersed particle phase in the (M x T y ) a RE b alloy tends to have higher purity than the raw materials M and T.
可以理解，如果合金原料是金属M、金属T与稀土RE，则可将各元素熔化制备合金熔体。如果提供的合金原料直接为(M xT y) aRE b合金时，则可以将(M xT y) aRE b合金重熔得到合金熔体。当然，也可以将金属M、金属T与稀土RE熔融配制成(M xT y) aRE b合金，再将(M xT y) aRE b合金重熔得到合金熔体。 It can be understood that if the alloy raw materials are metal M, metal T and rare earth RE, each element can be melted to prepare an alloy melt. If the alloy raw materials provided are directly (M x T y ) a RE b alloy, the (M x T y ) a RE b alloy can be remelted to obtain an alloy melt. Of course, it is also possible to melt the metal M, the metal T and the rare earth RE into a (M x T y ) a RE b alloy, and then remelt the (M x T y ) a RE b alloy to obtain an alloy melt.
步骤(3)中，该合金熔体的凝固组织由成分为M xT y的弥散颗粒相与成分主要为RE的基体相组成。其中，成分为M xT y的弥散颗粒相在稀酸作用下为惰性成分，难与酸反应；成分主要为RE的基体相为活性成分，非常容易与酸反应。所以，该(M xT y) aRE b合金的凝固组织有利于后续分离。 In step (3), the solidified structure of the alloy melt is composed of a dispersed particle phase composed of M x T y and a matrix phase composed mainly of RE. Among them, the dispersed particle phase of the component M x T y is an inert component under the action of dilute acid, and it is difficult to react with acid; the matrix phase mainly composed of RE is an active component, which is very easy to react with acid. Therefore, the solidified structure of the (M x T y ) a RE b alloy facilitates subsequent separation.
具体的，所述凝固方法不做限定，可为铸造、熔体甩带、熔体抽拉等方法。最终形成的合金粉体材料的颗粒大小形貌与(M xT y) aRE b合金中所述M xT y弥散颗粒相的颗粒大小形貌基本一致。所述M xT y弥散颗粒相的颗粒大小与制备过程中合金熔体的凝固速率有关。一般来说，M xT y弥散颗粒相的颗粒粒径大小与合金熔体的冷却速率成负相关的关系，即：合金熔体的凝固速率越大，弥散颗粒相的颗粒粒径越小。其中，所述合金熔体的凝固速率可为0.001K/s～10 7K/s，所述M xT y弥散颗粒相的颗粒大小可为2nm～100mm。 Specifically, the solidification method is not limited, and may be methods such as casting, melt stripping, and melt drawing. The particle size and morphology of the finally formed alloy powder material is basically consistent with the particle size and morphology of the M x T y dispersed particle phase in the (M x T y ) a RE b alloy. The particle size of the M x T y dispersed particle phase is related to the solidification rate of the alloy melt during the preparation process. Generally speaking, the particle size of the M x T y dispersed particle phase has a negative correlation with the cooling rate of the alloy melt, that is, the greater the solidification rate of the alloy melt, the smaller the particle size of the dispersed particle phase. Wherein, the solidification rate of the alloy melt may be 0.001 K/s to 10 7 K/s, and the particle size of the M x T y dispersed particle phase may be 2 nm to 100 mm.
所述弥散颗粒相的颗粒形状不限，可包括枝晶形、球形、近球形、方块形、饼形、棒形中的至少一种。当颗粒形状为棒状时，颗粒的大小特指棒状横截面的直径尺寸。The particle shape of the dispersed particle phase is not limited, and may include at least one of a dendritic shape, a spherical shape, a nearly spherical shape, a square shape, a pie shape, and a rod shape. When the particle shape is rod-shaped, the particle size specifically refers to the diameter of the rod-shaped cross-section.
步骤S2中，所述酸溶液为含有H +的溶液。由于(M xT y) aRE b合金凝固组织由成分为M xT y的弥散颗粒相与成分主要为RE的基体相组成。所以，所述稀酸溶液中的H +与基体相中的稀土元素反应，将稀土元素溶解变成离子进入溶液，而难与稀酸溶液反应的M xT y的弥散颗粒相则从原合金中分散脱离出来。经清洗，即得到M xT y合金粉体材料。该合金粉体材料的粒径可以为纳米级，亚微米级、微米级，甚至毫米级。 In step S2, the acid solution is a solution containing H + . Because (M x T y ) a RE b alloy solidification structure is composed of a dispersed grain phase with a composition of M x T y and a matrix phase with a composition mainly of RE. Therefore, the H + in the dilute acid solution reacts with the rare earth elements in the matrix phase to dissolve the rare earth elements into ions and enter the solution, while the M x T y dispersed particle phase, which is difficult to react with the dilute acid solution, is removed from the original alloy Disperse out of it. After cleaning, the M x T y alloy powder material is obtained. The particle size of the alloy powder material can be nanometer, submicrometer, micrometer, or even millimeter.
具体的，所述酸溶液中酸可为硫酸、盐酸、硝酸、高氯酸、磷酸、醋酸、草酸、甲酸、碳酸、葡萄糖酸、油酸、聚丙烯酸中的至少一种，优选为硫酸、盐酸、硝酸、高氯酸、磷酸、醋酸、草酸中的至少一种。所述酸溶液中溶剂为水、乙醇、甲醇或者它们以任意比例混合的混合物。Specifically, the acid in the acid solution may be at least one of sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, phosphoric acid, acetic acid, oxalic acid, formic acid, carbonic acid, gluconic acid, oleic acid, and polyacrylic acid, preferably sulfuric acid, hydrochloric acid , At least one of nitric acid, perchloric acid, phosphoric acid, acetic acid, and oxalic acid. The solvent in the acid solution is water, ethanol, methanol or a mixture thereof mixed in any ratio.
所述酸溶液中稀酸的浓度不做具体限定，只要可与基体相反应并保留初晶相即可。该反应的时间不做限定，反应的温度不做限定。优选的，所述酸溶液中酸的摩尔浓度可为0.001mol/L～5mol/L。该反应的反应时间可为0.1min～48h，反应温度可为0℃～100℃。The concentration of the dilute acid in the acid solution is not specifically limited, as long as it can react with the matrix phase and retain the primary crystal phase. The reaction time is not limited, and the reaction temperature is not limited. Preferably, the molar concentration of the acid in the acid solution may be 0.001 mol/L to 5 mol/L. The reaction time of this reaction can be 0.1min～48h, and the reaction temperature can be 0℃～100℃.
进一步的，在步骤S2之后，如果所得合金粉体材料的颗粒粒径范围为1μm～1mm，还可进行以下步骤：将所得的合金粉体材料进行筛分，并分别进行等离子球化处理，最终得到具有不同粒径且呈球形的合金粉体材料。Further, after step S2, if the particle size of the obtained alloy powder material is in the range of 1 μm to 1 mm, the following steps may be performed: the obtained alloy powder material is sieved, and plasma spheroidization is performed respectively, and finally A spherical alloy powder material with different particle sizes is obtained.
该筛选之后的粉体材料通过等离子球化处理，可实现球化。The powder material after the screening can be spheroidized by plasma spheroidization.
所述具有不同粒径且呈球形的合金粉体材料的颗粒粒径为1μm～1mm。The particle diameter of the spherical alloy powder material with different particle diameters is 1 μm to 1 mm.
因此，方法成本低、操作简单，可以制备包括纳米级、亚微米级、微米级以及毫米级的不同形貌的多种合金粉体材料。该合金粉体材料在储氢、催化、粉末冶金、3D打印等领域具有很好的应用前景。Therefore, the method has low cost and simple operation, and can prepare a variety of alloy powder materials with different morphologies including nanometer, submicrometer, micrometer and millimeter level. The alloy powder material has good application prospects in hydrogen storage, catalysis, powder metallurgy, 3D printing and other fields.
以下将通过各实施例进行进一步的说明。The following will further illustrate through various embodiments.
实施例1：Example 1:
本实施例提供一种微米级CoTi粉的制备方法，包括如下步骤：This embodiment provides a method for preparing micron-sized CoTi powder, which includes the following steps:
(1)选用配方分子式为(Co 50Ti 50) 25Gd 75的合金，按照该配方称取原料，在10 -2Pa真空条件下充分熔炼(Co 50Ti 50) 25Gd 75合金，将该合金熔体倒入内腔横截面尺寸为4mm×6mm的铜模中，以约75K/s的冷却速率铸造制备出尺寸为4mm×6mm×30mm的(Co 50Ti 50) 25Gd 75合金薄板，其合金凝固组织包括由CoTi组成的弥散枝晶颗粒以及由Gd组成的基体相，且CoTi枝晶颗粒的大小范围为2μm～40μm。 (1) Select the alloy with the formula formula (Co 50 Ti 50 ) 25 Gd 75 , weigh the raw materials according to the formula, and fully smelt the (Co 50 Ti 50 ) 25 Gd 75 alloy under the vacuum condition of 10 -2 Pa. The melt is poured into a copper mold with an inner cavity cross-sectional dimension of 4mm×6mm, and a (Co 50 Ti 50 ) 25 Gd 75 alloy sheet with a size of 4mm×6mm×30mm is prepared by casting at a cooling rate of about 75K/s. The alloy solidification structure includes dispersed dendritic particles composed of CoTi and a matrix phase composed of Gd, and the size of the CoTi dendritic particles ranges from 2 μm to 40 μm.
(2)室温下，将0.5克步骤(1)制得的(Co 50Ti 50) 25Gd 75合金薄板没入300mL浓度为0.2mol/L的稀盐酸水溶液中进行反应。反应过程中，由Gd组成的基体相与稀盐酸反应进入溶液，而难与稀盐酸反应的CoTi枝晶颗粒则逐步从基体中脱离分散出来。20min后，将所得CoTi枝晶颗粒与溶液进行分离，经清洗干燥，即得微米级CoTi枝晶粉，该枝晶颗粒的大小范围为5μm～40μm。 (2) At room temperature, 0.5 g of the (Co 50 Ti 50 ) 25 Gd 75 alloy sheet prepared in step (1) was immersed in 300 mL of a 0.2 mol/L dilute hydrochloric acid aqueous solution for reaction. During the reaction process, the matrix phase composed of Gd reacts with dilute hydrochloric acid and enters the solution, while the CoTi dendritic particles that are difficult to react with dilute hydrochloric acid are gradually separated from the matrix and dispersed. After 20 minutes, the obtained CoTi dendritic particles are separated from the solution, washed and dried to obtain micron-sized CoTi dendritic powder, and the size of the dendritic particles ranges from 5 μm to 40 μm.
对该合金粉体材料进行扫描电镜测试，如图1和图2所示，该合金粉体颗粒呈枝晶状。The alloy powder material was tested by scanning electron microscopy. As shown in Figure 1 and Figure 2, the alloy powder particles were in dendrite shape.
如图3所示，该CoTi粉体材料的能谱图上几乎检测不到其它元素的存在，其成分约为Co 50Ti 50。 As shown in Figure 3, almost no other elements can be detected on the energy spectrum of the CoTi powder material, and its composition is about Co 50 Ti 50 .
实施例2：Example 2:
本实施例提供一种球形微米级CoTi粉的制备方法，包括如下步骤：This embodiment provides a method for preparing spherical micron-sized CoTi powder, which includes the following steps:
(1)选用配方分子式为(Co 50Ti 50) 25Gd 75的合金，按照该配方称取原料，在10 -2Pa真空条件下充分熔炼(Co 50Ti 50) 25Gd 75合金，将该合金熔体倒入内腔横截面尺寸为4mm×6mm的铜模中，以约75K/s的冷却速率铸造制备出尺寸为4mm×6mm×30mm的(Co 50Ti 50) 25Gd 75合金薄板，其合金凝固组织包括由CoTi组成的弥散枝晶颗粒以及由Gd组成的基体相，且CoTi枝晶颗粒的大小范围为2μm～40μm。 (1) Select the alloy with the formula formula (Co 50 Ti 50 ) 25 Gd 75 , weigh the raw materials according to the formula, and fully smelt the (Co 50 Ti 50 ) 25 Gd 75 alloy under the vacuum condition of 10 -2 Pa. The melt is poured into a copper mold with an inner cavity cross-sectional dimension of 4mm×6mm, and a (Co 50 Ti 50 ) 25 Gd 75 alloy sheet with a size of 4mm×6mm×30mm is prepared by casting at a cooling rate of about 75K/s. The alloy solidification structure includes dispersed dendritic particles composed of CoTi and a matrix phase composed of Gd, and the size of the CoTi dendritic particles ranges from 2 μm to 40 μm.
(2)室温下，将0.5克步骤(1)制得的(Co 50Ti 50) 25Gd 75合金薄板没入300mL浓度为0.2mol/L的稀盐酸水溶液中进行反应。反应过程中，由Gd组成的基体相与稀盐酸反应进入溶液，而难与稀盐酸反应的CoTi枝晶颗粒则逐步从基体中脱离分散出来。20min后，将所得CoTi枝晶颗粒与溶液进行分离，经清洗干燥，即得微米级CoTi枝晶粉，该枝晶颗粒的大小范围为2μm～40μm。 (2) At room temperature, 0.5 g of the (Co 50 Ti 50 ) 25 Gd 75 alloy sheet prepared in step (1) was immersed in 300 mL of a 0.2 mol/L dilute hydrochloric acid aqueous solution for reaction. During the reaction process, the matrix phase composed of Gd reacts with dilute hydrochloric acid and enters the solution, while the CoTi dendritic particles that are difficult to react with dilute hydrochloric acid are gradually separated from the matrix and dispersed. After 20 minutes, the obtained CoTi dendritic particles are separated from the solution, washed and dried to obtain micron-sized CoTi dendritic powder, and the size of the dendritic particles ranges from 2 μm to 40 μm.
收集0.5千克由步骤(2)制得的微米级CoTi枝晶粉，通过540目、1000目、2000目的筛网进行筛分，得到枝晶粒径范围分别为＞26μm，26μm～13μm，13μm～6.5μm以及小于6.5μm的分级CoTi枝晶粉。分别选择枝晶粒径范围为26μm～13μm与13μm～6.5μm的CoTi枝晶粉，通过成熟的等离子球化处理技术进一步制得粒径范围为26μm～13μm与13μm～6.5μm的球形Co 50Ti 50粉。 Collect 0.5 kg of the micron-sized CoTi dendritic powder prepared in step (2), and sieving through 540 mesh, 1000 mesh, and 2000 mesh sieve. The dendrite size ranges are >26μm, 26μm-13μm, 13μm～ Graded CoTi dendritic powder of 6.5μm and less than 6.5μm. The CoTi dendritic powders with dendrite diameters ranging from 26μm to 13μm and 13μm to 6.5μm are selected respectively, and spherical Co 50 Ti with particle sizes ranging from 26μm to 13μm and 13μm to 6.5μm are further prepared through mature plasma spheroidization technology. 50 powder.
实施例3：Example 3:
本实施例提供一种纳米级CoHf粉的制备方法，包括如下步骤：This embodiment provides a method for preparing nano-scale CoHf powder, including the following steps:
(1)选用配方分子式为(Co 50Hf 50) 25Y 75的合金，按照该配方称取原料，在10 -2Pa真空条件下充分熔炼(Co 50Hf 50) 25Y 75合金，将该合金熔体通过熔体甩带法以10 5-10 6K/s的冷却速率制备厚度为20-30μm的(Co 50Hf 50) 25Y 75合金条带。该合金条带的凝固组织由成分为CoHf的近球形弥散颗粒与成分为Y的基体相组成，且CoHf弥散颗粒的大小范围为10-200nm。 (1) Select the alloy with the formula formula (Co 50 Hf 50 ) 25 Y 75 , weigh the raw materials according to the formula, and fully smelt the (Co 50 Hf 50 ) 25 Y 75 alloy under the vacuum condition of 10 -2 Pa. The melt is used to prepare (Co 50 Hf 50 ) 25 Y 75 alloy strips with a thickness of 20-30 μm at a cooling rate of 10 5 -10 6 K/s through the melt stripping method. The solidified structure of the alloy strip is composed of nearly spherical dispersed particles with a composition of CoHf and a matrix phase with a composition of Y, and the size of the dispersed particles of CoHf is in the range of 10-200 nm.
(2)室温下，将0.5克步骤(1)制得的(Co 50Hf 50) 25Y 75合金条带没入300mL浓度为0.2mol/L的稀硫酸水溶液中进行反应。反应过程中，由Y组成的基体相与稀硫酸反应进入溶液，而难与稀硫酸反应的CoHf纳米颗粒则逐步从基体中脱离分散出来。5min后，将所得CoHf纳米颗粒与溶液进行分离，经清洗干燥，即得纳米级的近球形CoHf粉，其颗粒的大小范围为10-200nm。 (2) At room temperature, 0.5 g of the (Co 50 Hf 50 ) 25 Y 75 alloy strip prepared in step (1) is immersed in 300 mL of a 0.2 mol/L dilute sulfuric acid aqueous solution for reaction. During the reaction, the matrix phase composed of Y reacts with dilute sulfuric acid and enters the solution, while the CoHf nanoparticles that are difficult to react with dilute sulfuric acid are gradually separated from the matrix and dispersed. After 5 minutes, the obtained CoHf nanoparticles are separated from the solution, washed and dried to obtain nano-sized nearly spherical CoHf powder, the size of which is in the range of 10-200 nm.
实施例4：Example 4:
本实施例提供一种球形微米级CoCrMo粉的制备方法，包括如下步骤：This embodiment provides a method for preparing spherical micron CoCrMo powder, which includes the following steps:
(1)选用配方分子式为(Co 63Cr 33Mo 4) 25Gd 75的合金，按照该配方称取原料，在10 -2Pa真空条件下充分熔炼(Co 63Cr 33Mo 4) 25Gd 75合金，将该合金熔体倒入内腔横截面尺寸为4mm×6mm的铜模中，以约75K/s的冷却速率铸造制备出尺寸为4mm×6mm×30mm的(Co 63Cr 33Mo 4) 25Gd 75合金薄板，其合金凝固组织包括由Co-Cr-Mo组成的弥散枝晶颗粒以及由Gd组成的基体相，且Co-Cr-Mo枝晶颗粒的大小范围为3μm～50μm。 (1) Choose the alloy with formula formula (Co 63 Cr 33 Mo 4 ) 25 Gd 75 , weigh the raw materials according to the formula, and fully smelt (Co 63 Cr 33 Mo 4 ) 25 Gd 75 alloy under vacuum conditions of 10 -2 Pa , Pour the alloy melt into a copper mold with a cavity cross-sectional dimension of 4mm×6mm, and cast at a cooling rate of about 75K/s to prepare (Co 63 Cr 33 Mo 4 ) 25 with a size of 4mm×6mm×30mm The alloy solidification structure of the Gd 75 alloy sheet includes dispersed dendritic particles composed of Co-Cr-Mo and a matrix phase composed of Gd, and the size of the Co-Cr-Mo dendritic particles ranges from 3 μm to 50 μm.
(2)室温下，将0.5克步骤(1)制得的(Co 63Cr 33Mo 4) 25Gd 75合金薄板没入300mL浓度为0.2mol/L的稀盐酸水溶液中进行反应。反应过程中，由Gd组成的基体相与稀盐酸反应进入溶液，而难与稀盐酸反应的Co-Cr-Mo枝晶颗粒则逐步从基体中脱离分散出来。20min后，将所得Co-Cr-Mo枝晶颗粒与溶液进行分离，经清洗干燥，即得微米级的Co-Cr-Mo枝晶粉，其成分约为Co 63Cr 33Mo 4，枝晶颗粒的大小范围为3μm～50μm。 (2) At room temperature, 0.5 g of the (Co 63 Cr 33 Mo 4 ) 25 Gd 75 alloy sheet prepared in step (1) was immersed in 300 mL of a 0.2 mol/L dilute hydrochloric acid aqueous solution for reaction. During the reaction, the matrix phase composed of Gd reacts with dilute hydrochloric acid and enters the solution, while the Co-Cr-Mo dendritic particles that are difficult to react with dilute hydrochloric acid are gradually separated from the matrix and dispersed. After 20 minutes, the obtained Co-Cr-Mo dendritic particles were separated from the solution, washed and dried, and then micron-sized Co-Cr-Mo dendritic powder was obtained, the composition of which was approximately Co 63 Cr 33 Mo 4 , dendritic particles The size range of 3μm ~ 50μm.
收集0.5千克由步骤(2)制得的微米级Co-Cr-Mo枝晶粉，通过540目、1000目、2000目的筛网进行筛分，得到枝晶粒径范围分别为＞26μm，26μm～13μm，13μm～6.5μm以及小于6.5μm的分级Co-Cr-Mo枝晶粉。分别选择枝晶粒径范围为26μm～13μm与13μm～6.5μm的Co-Cr-Mo枝晶粉，通过成熟的等离子球化处理技术进一步制得粒径范围为26μm～13μm与13μm～6.5μm的球形Co 63Cr 33Mo 4粉。 Collect 0.5 kg of the micron-sized Co-Cr-Mo dendritic powder prepared in step (2), and sieving through 540 mesh, 1000 mesh, and 2000 mesh sieve. The dendrite size ranges are> 26 μm, 26 μm ~ Graded Co-Cr-Mo dendritic powder of 13μm, 13μm～6.5μm and less than 6.5μm. Co-Cr-Mo dendritic powders with dendrite particle sizes ranging from 26μm to 13μm and 13μm to 6.5μm are selected, and the particle size ranges from 26μm to 13μm and 13μm to 6.5μm are further prepared by mature plasma spheroidizing technology. Spherical Co 63 Cr 33 Mo 4 powder.
实施例5：Example 5:
本实施例提供一种亚微米级的CoTiHf粉的制备方法，包括如下步骤：This embodiment provides a method for preparing sub-micron CoTiHf powder, which includes the following steps:
(1)选用配方分子式为(Co 50Ti 25Hf 25) 20(Gd 50Y 50) 80的合金，按照该配方称取原料，在10 -2Pa真空条件下充分熔炼(Co 50Ti 25Hf 25) 20(Gd 50Y 50) 80合金，将该合金熔体通过熔体甩带法以～10 4K/s的冷却速率制备厚度为200-300μm的(Co 50Ti 25Hf 25) 20(Gd 50Y 50) 80合金条带。该合金条带的凝固组织由成分为Co 50Ti 25Hf 25的近球形弥散颗粒与成分为Gd 50Y 50的基体相组成，且Co 50Ti 25Hf 25弥散颗粒的大小范围为100-800nm。 (1) Select the alloy with formula formula (Co 50 Ti 25 Hf 25 ) 20 (Gd 50 Y 50 ) 80 , weigh the raw materials according to the formula, and fully smelt it under 10 -2 Pa vacuum conditions (Co 50 Ti 25 Hf 25 ) 20 (Gd 50 Y 50 ) 80 alloy, the alloy melt is prepared by melt ribbon spinning at a cooling rate of ~10 4 K/s to prepare (Co 50 Ti 25 Hf 25 ) 20 (Gd 50 Y 50 ) 80 alloy strip. Size range of the alloy strip the solidification structure of a nearly spherical component Co 50 Ti 25 Hf 25 dispersed particles and the matrix component is a Gd 50 Y 50 phase composition, and the Co 50 Ti 25 Hf 25 dispersed particles is 100-800nm.
(2)室温下，将0.5克步骤(1)制得的(Co 50Ti 25Hf 25) 20(Gd 50Y 50) 80合金薄板没入300mL浓度为0.2mol/L的稀硫酸水溶液中进行反应。反应过程中，由GdY组成的基体相与稀硫酸反应进入溶液，而难与稀硫酸反应的亚微米级Co 50Ti 25Hf 25颗粒则逐步从基体中脱离分散出来。10min后，将所得Co 50Ti 25Hf 25亚微米颗粒与溶液进行分离，经清洗干燥，即得近球形的Co 50Ti 25Hf 25亚微米合金粉，颗粒的大小范围为100-800nm。 (2) At room temperature, 0.5 g of the (Co 50 Ti 25 Hf 25 ) 20 (Gd 50 Y 50 ) 80 alloy sheet prepared in step (1) is immersed in 300 mL of a 0.2 mol/L dilute sulfuric acid aqueous solution for reaction. During the reaction process, the matrix phase composed of GdY reacts with dilute sulfuric acid into the solution, and the submicron Co 50 Ti 25 Hf 25 particles that are difficult to react with dilute sulfuric acid are gradually separated from the matrix and dispersed. After 10 minutes, the obtained Co 50 Ti 25 Hf 25 sub-micron particles are separated from the solution, washed and dried to obtain nearly spherical Co 50 Ti 25 Hf 25 sub-micron alloy powder, the particle size range is 100-800 nm.
实施例6：Example 6:
本实施例提供一种微纳米级CoTiZr粉的制备方法，包括如下步骤：This embodiment provides a method for preparing micro-nano CoTiZr powder, which includes the following steps:
(1)选用配方分子式为(Co 50Ti 25Zr 25) 30Y 70的合金，按照该配方称取原料，在10 -2Pa真空条件下电弧熔炼后得到(Co 50Ti 25Zr 25) 30Y 70合金，将该合金通过感应加热重熔后通过铜辊甩带的方法制备厚度约150μm的(Co 50Ti 25Zr 25) 30Y 70合金薄带。其合金组织包括由Y组成的基体以及由Co 50Ti 25Zr 25)组成的近球形弥散颗粒相。弥散颗粒直径大小范围为50-500nm。 (1) Choose the alloy with formula formula (Co 50 Ti 25 Zr 25 ) 30 Y 70 , weigh the raw materials according to the formula, and obtain (Co 50 Ti 25 Zr 25 ) 30 Y after arc melting under 10 -2 Pa vacuum conditions 70 alloy, the alloy is remelted by induction heating, and then a (Co 50 Ti 25 Zr 25 ) 30 Y 70 alloy thin strip with a thickness of about 150 μm is prepared by a copper roll spinning method. The alloy structure includes a matrix composed of Y and a nearly spherical dispersed particle phase composed of Co 50 Ti 25 Zr 25 ). The diameter of the dispersed particles ranges from 50-500nm.
(2)室温下，将0.5克步骤(1)制得的(Co 50Ti 25Zr 25) 30Y 70合金薄带没入300mL浓度为0.2mol/L的盐酸水溶液中进行反应。反应过程中，由活性元素Y组成的基体与盐酸反应进入溶液，而难与稀盐酸反应的Co 50Ti 25Zr 25弥散颗粒相则逐步从基体相中脱离分散出来。10min后，将所得Co 50Ti 25Zr 25弥散颗粒与溶液进行分离，经清洗干燥，即得近球形Co 50Ti 25Zr 25微纳米合金粉，其颗粒的直径大小范围为50-500nm。 (2) At room temperature, 0.5 g of the (Co 50 Ti 25 Zr 25 ) 30 Y 70 alloy ribbon prepared in step (1) was immersed in 300 mL of a 0.2 mol/L hydrochloric acid aqueous solution for reaction. During the reaction process, the matrix composed of active element Y reacts with hydrochloric acid and enters the solution, while the Co 50 Ti 25 Zr 25 dispersed particle phase which is difficult to react with dilute hydrochloric acid is gradually separated from the matrix phase and dispersed. After 10 minutes, the obtained Co 50 Ti 25 Zr 25 dispersed particles are separated from the solution, washed and dried to obtain approximately spherical Co 50 Ti 25 Zr 25 micro-nano alloy powder, the diameter of which is in the range of 50-500 nm.
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, all possible combinations of the technical features in the above-mentioned embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, All should be considered as the scope of this specification.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only express several embodiments of the present invention, and the descriptions are more specific and detailed, but they should not be understood as limiting the scope of the invention patent. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can be made, and these all fall within the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims.

Claims (10)

  1. 一种合金粉体材料的制备方法，其特征在于，包括以下步骤：A preparation method of alloy powder material is characterized in that it comprises the following steps:
    提供(M xT y) aRE b Provide (M x T y ) a RE b
    合金，其中，M选自Fe、Co、Ni中的至少一种，T选自W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti中的至少一种，RE选自Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的至少一种，x、y以及a、b分别代表对应组成的原子百分比含量，且33％≤x≤75％，x+y＝100％；0.1％≤a≤40％，a+b＝100％，所述(M xT y) aRE b合金的凝固组织由成分为M xT y的弥散颗粒相与成分主要为RE的基体相组成； Alloy, wherein M is selected from at least one of Fe, Co, Ni, T is selected from at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti, and RE is selected from Y, La At least one of, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, x, y and a, b respectively represent the atomic percentage content of the corresponding composition, And 33%≤x≤75%, x+y=100%; 0.1%≤a≤40%, a+b=100%, the solidified structure of the (M x T y ) a RE b alloy is composed of M The dispersed particle phase of x T y and the matrix phase composed mainly of RE;
    将所述(M xT y) aRE b合金与酸溶液混合，使所述基体相与所述酸溶液反应变成离子进入溶液，所述弥散颗粒相脱离出来，即得到由M xT y组成的合金粉体材料。 The (M x T y ) a RE b alloy is mixed with an acid solution, the matrix phase reacts with the acid solution to become ions into the solution, and the dispersed particle phase separates out, that is, M x T y Composition of alloy powder material.
  2. 根据权利要求1所述的合金粉体材料的制备方法，其特征在于，所述(M xT y) aRE b合金通过以下方式得到： The method for preparing an alloy powder material according to claim 1, wherein the (M x T y ) a RE b alloy is obtained in the following manner:
    按照配比称取合金原料；Weigh the alloy raw materials according to the ratio;
    将所述合金原料充分熔化得到合金熔体；Fully melting the alloy raw materials to obtain an alloy melt;
    将合金熔体通过凝固方法制备成所述(M xT y) aRE b合金，其中，所述合金熔体的凝固速率为0.001K/s～10 7K/s。 The alloy melt is prepared into the (M x T y ) a RE b alloy by a solidification method, wherein the solidification rate of the alloy melt is 0.001 K/s to 10 7 K/s.
  3. 根据权利要求1所述的合金粉体材料的制备方法，其特征在于，所述合金熔体熔炼过程中的真空度为1×10 -4Pa～1.01325×10 5Pa。 The method for preparing alloy powder materials according to claim 1, wherein the vacuum degree during the melting of the alloy melt is 1×10 -4 Pa to 1.01325×10 5 Pa.
  4. 根据权利要求1所述的金属粉体材料的制备方法，其特征在于，所述弥散颗粒相的颗粒形状包括枝晶形、球形、近球形、方块形、饼形、棒形中的至少一种，所述弥散颗粒相的颗粒大小为2nm～100mm。The method for preparing a metal powder material according to claim 1, wherein the particle shape of the dispersed particle phase includes at least one of a dendritic shape, a spherical shape, a nearly spherical shape, a square shape, a pie shape, and a rod shape. The particle size of the dispersed particle phase is 2nm-100mm.
  5. 根据权利要求1所述的合金粉体材料的制备方法，其特征在于，所述酸溶液中酸为硫酸、盐酸、硝酸、高氯酸、磷酸、醋酸、草酸、甲酸、碳酸、葡萄糖酸、油酸、聚丙烯酸中的至少一种，所述 酸溶液中溶剂为水、乙醇、甲醇或者三者以任意比例混合的混合物。The method for preparing alloy powder materials according to claim 1, wherein the acid in the acid solution is sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, phosphoric acid, acetic acid, oxalic acid, formic acid, carbonic acid, gluconic acid, oil At least one of acid and polyacrylic acid, and the solvent in the acid solution is water, ethanol, methanol, or a mixture of the three in any ratio.
  6. 根据权利要求5所述的合金粉体材料的制备方法，其特征在于，所述酸溶液中酸的摩尔浓度为0.001mol/L～5mol/L。The method for preparing alloy powder materials according to claim 5, wherein the molar concentration of the acid in the acid solution is 0.001 mol/L to 5 mol/L.
  7. 根据权利要求1所述的合金粉体材料的制备方法，其特征在于，所述(M xT y) aR b The method for preparing alloy powder material according to claim 1, wherein the (M x T y ) a R b
    合金与所述酸溶液进行反应的步骤中，反应时间为0.1min～48h，反应温度为0℃～100℃。In the step of reacting the alloy with the acid solution, the reaction time is 0.1 min to 48 h, and the reaction temperature is 0°C to 100°C.
  8. 根据权利要求1所述的合金粉体材料的制备方法，其特征在于，所述M xT y合金粉体材料的粒径为2nm～100mm。 The method for preparing an alloy powder material according to claim 1, wherein the particle size of the M x T y alloy powder material is 2 nm to 100 mm.
  9. 根据权利要求1至8中任一项所述的合金粉体材料的制备方法，其特征在于，在将所述(M xT y) aR b合金与所述酸溶液进行反应的步骤之后还进行以下步骤：将所得的粒径范围为1μm～1mm的合金粉体材料进行筛分，并分别进行等离子球化处理，最终得到具有不同粒径且呈球形的合金粉体材料。 The method for preparing an alloy powder material according to any one of claims 1 to 8, wherein after the step of reacting the (M x T y ) a R b alloy with the acid solution The following steps are carried out: sieving the obtained alloy powder materials with a particle size ranging from 1 μm to 1 mm, and respectively performing plasma spheroidizing treatment, and finally obtaining spherical alloy powder materials with different particle sizes.
  10. 根据权利要求9所述的合金粉体材料的制备方法，其特征在于，所述具有不同粒径且呈球形的合金粉体材料的颗粒大小为1μm～1mm。The method for preparing an alloy powder material according to claim 9, wherein the particle size of the spherical alloy powder material with different particle sizes is 1 μm to 1 mm.
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