WO2022041516A1 - Preparation method and application of noble metal element-containing powder material - Google Patents

Preparation method and application of noble metal element-containing powder material Download PDF

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Publication number
WO2022041516A1
WO2022041516A1 PCT/CN2020/130962 CN2020130962W WO2022041516A1 WO 2022041516 A1 WO2022041516 A1 WO 2022041516A1 CN 2020130962 W CN2020130962 W CN 2020130962W WO 2022041516 A1 WO2022041516 A1 WO 2022041516A1
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powder
phase
alloy
noble metal
dispersed particle
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PCT/CN2020/130962
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French (fr)
Chinese (zh)
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赵远云
刘丽
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赵远云
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Priority to CN202080103275.1A priority Critical patent/CN116056819A/en
Publication of WO2022041516A1 publication Critical patent/WO2022041516A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/06Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/06Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/10Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying using centrifugal force
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper

Definitions

  • the invention relates to the technical field of micro-nano materials, in particular to a preparation method and application of a powder material containing noble metal elements.
  • the preparation methods of ultrafine powder materials with micron, submicron and nanometer particle size are divided into solid phase method, liquid phase method and gas phase method from the state of matter.
  • the solid phase method mainly includes mechanical pulverization method, ultrasonic pulverization method, thermal decomposition method, explosion method, etc.
  • the liquid phase method mainly includes precipitation method, alkoxide method, carbonyl method, spray thermal drying method, freeze drying method, electrolysis method, Chemical condensation methods, etc.
  • gas phase methods mainly include gas phase reaction method, plasma method, high temperature plasma method, evaporation method, chemical vapor deposition method, etc.
  • the disadvantages of the liquid phase method are low yield, high cost and complex process; the disadvantage of the mechanical method is that it is difficult to classify after the powder material is prepared, and the purity, fineness and morphology of the product are difficult to guarantee; Electrode method and gas atomization method are the main methods for preparing high-performance metal and alloy powder at present, but the production efficiency is low, the yield is not high, and the energy consumption is relatively large; jet milling method and hydrogenation dehydrogenation method are suitable for large-scale industrialization production, but with strong selectivity to raw materials and alloys.
  • noble metal powder materials especially noble metal nano-powder materials
  • they are generally prepared by chemical reduction methods.
  • the chemical reduction method is generally difficult to ensure the large-scale preparation of the product and also ensure that the particle size of the obtained noble metal nanopowder can be well controlled.
  • the impurity content of the powder material especially the oxygen content, has a great influence on its performance.
  • the impurity content of metals or alloys is mainly controlled by controlling the purity and vacuum degree of raw materials, which is expensive. Therefore, it is of great significance to develop new preparation methods for high-purity powder materials.
  • a preparation method of a powder material containing noble metal elements comprising the following steps:
  • Step S1 select the initial alloy raw material, and melt the initial alloy raw material according to the initial alloy composition ratio to obtain a uniform initial alloy melt containing the impurity element D;
  • the average composition of the initial alloy melt is mainly Cu a (M x T y ) ) b D d , wherein M includes at least one of noble metal elements Ir, Ru, Re, Os, Tc, Au, Pt, Pd, and Ag, and T includes W, Cr, Mo, V, Ta, Nb, Zr, At least one of Hf, Ti, Fe, D contains at least one of O, H, N, P, S, F, Cl, I, Br; and 60% ⁇ a ⁇ 99.9%, 0.1% ⁇ b ⁇ 40%, 0 ⁇ d ⁇ 5%; 0.1% ⁇ x ⁇ 100%, 0% ⁇ y ⁇ 99.9%; among them, a, b, d, and x, y represent the atomic percentage content of the corresponding constituent elements;
  • step S2 the initial alloy melt is solidified into initial alloy strips;
  • the solidified structure of the initial alloy strip includes a matrix phase and a dispersed particle phase;
  • the melting point of the matrix phase is lower than that of the dispersed particle phase, and the The dispersed particle phase is coated in the matrix phase;
  • the impurity element D in the initial alloy melt is redistributed in the dispersed particle phase and the matrix phase, and is enriched in the matrix phase, so that the dispersed particle phase is purified;
  • the composition of the dispersed particle phase in the initial alloy strip is mainly (M x T y ) x1 D z1 , and the average composition of the matrix phase is mainly Cu x2 D z2 ; and 99% ⁇ x1 ⁇ 100%, 0 ⁇ z1 ⁇ 1 %; 90% ⁇ x2 ⁇ 100%, 0 ⁇ z2 ⁇ 10%; z1 ⁇ d ⁇ z2, 2z1 ⁇ z2; x1, z1, x2, z2 represent the atomic percentage content of the corresponding constituent elements;
  • step S3 the matrix phase in the initial alloy strip is removed, and the dispersed particle phase that cannot be removed at the same time in the process of removing the matrix phase is retained; High-purity target powder materials of precious metal elements.
  • the M includes at least one of noble metal elements Ir, Ru, Re, Os, Tc, Au, Pt, Pd, Ag, and the atomic percentage of elements such as Ir, Ru, Re, Os, Tc in M The content is higher than 50%;
  • the M includes at least one of noble metal elements Ir, Ru, Re, Os, Tc, Au, Pt, Pd, Ag, and the atomic percentage of elements such as Ir, Ru, Re, Os, Tc in M The content is higher than 75%;
  • the M contains at least one of noble metal elements Ir, Ru, Re, Os, Tc,
  • the T includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti, Fe, and W, Cr, Mo, V, Ta, Nb and other elements in T
  • the atomic percentage content is higher than 50%;
  • the T includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti, Fe, and W, Cr, Mo, V, Ta, Nb and other elements in T
  • the atomic percentage content is higher than 75%
  • the T includes at least one of W, Cr, Mo, V, Ta, and Nb;
  • the source of the D impurity element in the initial alloy melt includes: impurities introduced from the initial alloy raw material, and impurities introduced from the atmosphere or the crucible during the smelting process.
  • the impurities introduced into the atmosphere refer to impurities such as O, N, and H in the ambient atmosphere absorbed by the alloy melt.
  • D is an impurity element and includes at least one of O, H, N, P, S, F, Cl, I, and Br; and the total content of these impurity elements is the content of D impurity elements;
  • the raw material is each element or master alloy containing impurity elements, it can be melted according to the proportion to prepare the initial alloy melt. If the supplied raw material is directly the alloy raw material corresponding to the composition of the initial alloy melt, it can be remelted to obtain the initial alloy melt.
  • the combination of Cu and M and Cu and T in the average composition of the initial alloy melt in the step S1 is extremely important. Intermetallic compounds are not formed between them. In this way, the two-phase separation of the Cu-based matrix phase and the M and T-based particle phases during the solidification of the initial alloy melt can be achieved, which is beneficial to the subsequent preparation of M and T-based powder materials containing noble metal elements .
  • the initial alloy strip does not contain an intermetallic compound composed of Cu and M;
  • the initial alloy strip does not contain an intermetallic compound composed of Cu and T;
  • M contains at least one of Au, Pt, Pd, and Ag
  • the The dispersed particle phase whose main component is (M x T y ) x1 D z1 also contains at least one of Ir, Ru, Re, Os, and Tc all belonging to M;
  • T contains at least one of Zr, Hf, Ti, and Fe
  • it is present in a solid solution in a dispersed particle phase whose main component is (M x T y ) x1 D z1
  • the The dispersed particle phase whose main component is (M x T y ) x1 D z1 also contains at least one of W, Cr, Mo, V, Ta, and Nb all belonging to T;
  • the dispersed particle phase containing noble metal elements whose composition is mainly (M x T y ) x1 D z1 does not contain Cu element;
  • the method of solidification of the alloy melt includes strip method and continuous casting method; generally, thinner initial alloy strip can be obtained by strip method; thicker alloy strip can be obtained by continuous casting method .
  • the morphology of the alloy ingot obtained by the ordinary casting method is completely different.
  • the alloy ingot obtained by the ordinary casting method is average in size. There is no obvious difference in length, width and thickness.
  • the thickness of the initial alloy strips ranges from 5 ⁇ m to 10 mm; further, the thickness of the initial alloy strips ranges from 5 ⁇ m to 5 mm; preferably, the thickness of the initial alloy strips ranges from 5 ⁇ m to 1 mm ; As a further preference, the thickness of the initial alloy strip ranges from 5 ⁇ m to 200 ⁇ m; as a further preference, the thickness of the initial alloy strip ranges from 5 ⁇ m to 20 ⁇ m.
  • the thickness of the initial alloy strip is in the order of millimeters, it can also be referred to as an alloy sheet.
  • the width of the cross section of the initial alloy strip is more than 2 times its thickness; further, the length of the initial alloy strip is more than 10 times its thickness; The length is more than 50 times its thickness; preferably, the length of the initial alloy strip is more than 100 times its thickness;
  • the solidification rate of the initial alloy melt is 1K/s ⁇ 10 7 K/s;
  • the particle size of the dispersed particle phase is related to the solidification rate of the initial alloy melt; in general, the particle size of the dispersed particle phase has a negative correlation with the solidification rate of the initial alloy melt, that is, the initial alloy melt. The higher the solidification rate of the melt, the smaller the particle size of the dispersed particle phase.
  • the particle size range of the disperse particle phase is 2nm ⁇ 3mm; further, the particle size range of the disperse particle phase is 2nm ⁇ 500 ⁇ m; preferably, the particle size range of the disperse particle phase is 2nm ⁇ 99 ⁇ m; as a further preference, the particle size range of the dispersed particle phase is 2 nm to 5 ⁇ m; as a further preference, the particle diameter of the dispersed particle phase is in the range of 2 nm to 200 nm; as a further preference, the particle diameter of the dispersed particle phase The range is 2nm to 100nm.
  • the particle shape of the dispersed particle phase is not limited, and may include at least one of dendritic, spherical, nearly spherical, square, pie, and rod-shaped; when the particle shape is rod-shaped, the Size refers to the diameter dimension of the cross-section of the rod.
  • dispersed particles are of nanometer or submicron scale, spherical or nearly spherical particles are obtained with high probability; when the dispersed particles are of micrometer scale and above, dendritic particles are obtained with high probability.
  • the dispersed particle phase solidifies and precipitates from the initial alloy melt.
  • the crystal grains all have a fixed orientation relationship in their crystal growth, so that the precipitated single grains are mainly composed of a single crystal.
  • the volume percentage of the dispersed particles in the entire initial alloy strip is relatively high, in the process of endogenous precipitation of single crystal particles, it is not excluded that two or more particles merge. If two or more single crystal particles are only softly agglomerated, adsorbed to each other, or connected together by only a few parts, and are not sufficiently combined into one particle through normal grain boundaries as in polycrystalline materials, they are still two single crystal particles. . Its characteristic is that after the matrix phase is removed in the subsequent process, these single crystal particles can be easily separated by techniques including ultrasonic dispersion treatment and jet milling. For polycrystalline materials of normal ductile metals or alloys, it is difficult to separate the grain boundaries by techniques including ultrasonic dispersion treatment and jet milling.
  • the number of single crystal particles in the dispersed particles in the initial alloy strip accounts for not less than 60% of the total number of dispersed particles.
  • the number of single crystal particles in the dispersed particles accounts for not less than 90% of the total number of dispersed particles.
  • the volume percentage content of the dispersed particle phase in the initial alloy strip can be determined by the corresponding initial alloy melt composition, dispersed particle phase composition, and matrix phase composition, Combined with element atomic weight, density parameters and other calculations to determine.
  • volume percentage of the dispersed particle phase in its corresponding initial alloy strip is not higher than 50%.
  • z1 ⁇ d ⁇ z2, and 3z1 ⁇ z2 that is, the D impurity content in the dispersed particle phase is lower than the D impurity content in the initial alloy melt, and the D impurity content in the dispersed particle phase is 3%. times are still lower than the D impurity content in the matrix phase;
  • the method for removing the matrix phase in the alloy strip includes acid reaction removal
  • M and T elements generally do not react with a relatively concentrated and high-temperature hydrochloric acid aqueous solution.
  • M contains elements (such as Fe) that can react with concentrated hydrochloric acid alone, when it is solid-dissolved in inert M or T, it is protected by inert M or T and cannot react with concentrated hydrochloric acid. Therefore, the matrix phase in the alloy ribbons can be removed by etching with a relatively concentrated and high temperature aqueous hydrochloric acid solution, while retaining the dispersed particle phase.
  • the concentration of the hydrochloric acid aqueous solution contained in the acid reaction removal method is 2 mol/L to 12 mol/L.
  • the acid reaction removal method includes the reaction temperature of the hydrochloric acid aqueous solution and the alloy strip being 0°C to 100°C.
  • the target powder material is the disperse particle phase dropped from the initial alloy ribbon
  • the composition and particle size of the target powder material are all equivalent to the composition and particle size of the corresponding disperse particle phase.
  • the particle size range of the target powder material containing noble metal elements is 2 nm to 3 mm; preferably, the particle size range of the target powder material containing noble metal elements is 2 nm to 500 ⁇ m; The particle size range of the target powder material containing noble metal elements is 2 nm to 99 ⁇ m; as a further preference, the particle size range of the target powder material containing noble metal elements is 2 nm to 5 ⁇ m; The particle size range of the target powder material of the noble metal element is 2 nm to 200 nm; as a further preference, the particle size range of the target powder material containing the noble metal element is 2 nm to 100 nm.
  • the dispersed particles are separated from the initial alloy strip, which is cleaned and dried to obtain the target powder material containing precious metal elements.
  • composition of the target powder material containing noble metal elements is mainly (M x T y ) x1 D z1 ;
  • the target powder material containing noble metal elements whose composition is mainly (M x T y ) x1 D z1 does not contain Cu element;
  • the composition of the target powder material containing noble metal elements is (M x T y ) x1 D z1 ;
  • the atomic percentage content of D impurity element in the target powder material containing noble metal element is not more than 1%;
  • the atomic percentage content of D impurity element in the target powder material containing noble metal element is not more than 0.5%;
  • the atomic percentage content of D impurity element in the target powder material containing noble metal element is not more than 0.2%;
  • step S3 after sieving the target powder material containing noble metal elements, selecting the target powder material containing noble metal elements with a particle size range of 5 ⁇ m to 200 ⁇ m for plasma spheroidization processing to obtain spherical powder materials containing precious metal elements;
  • the particle size range of the spherical powder material containing noble metal elements is 5 ⁇ m ⁇ 200 ⁇ m.
  • the present invention also relates to the target powder material containing noble metal elements obtained by the above preparation method or the spherical powder material containing noble metal elements in catalytic materials, powder metallurgy, composite materials, wave absorbing materials, sterilization materials, metal injection molding, 3D materials Printing, coating applications.
  • the application of the spherical powder material containing noble metal elements obtained by the above preparation method in the field of metal powder 3D printing is characterized in that the particle size range of the spherical powder material containing noble metal elements is 10 ⁇ m ⁇ 200 ⁇ m.
  • the application of the target powder material containing noble metal elements or the spherical powder material containing noble metal elements obtained by the above preparation method in metal injection molding and powder metallurgy characterized in that the particle size range is 0.1 ⁇ m ⁇ 200 ⁇ m.
  • the application of the target powder material containing noble metal elements obtained by the above preparation method in coatings and catalysts is characterized in that the particle size of the powder material ranges from 2 nm to 5 ⁇ m.
  • the invention also relates to an alloy strip, which is characterized in that it includes endogenous powder and a coating body; the solidified structure of the alloy strip includes a matrix phase and a dispersed particle phase, and the matrix phase is the coating body, and the dispersed particles The phase is the endogenous powder; the melting point of the coating body is lower than the endogenous powder, and the endogenous powder is coated in the coating body;
  • the composition of the endogenous powder in the initial alloy strip is mainly (M x T y ) x1 D z1 , and the average composition of the clad is mainly Cu x2 D z2 ; and 99% ⁇ x1 ⁇ 100%, 0 ⁇ z1 ⁇ 1%; 90% ⁇ x2 ⁇ 100%, 0 ⁇ z2 ⁇ 10%; z1 ⁇ d ⁇ z2, 2z1 ⁇ z2; x1, z1, x2, z2 respectively represent the atomic percentage content of the corresponding constituent elements;
  • the M contains at least one of the noble metal elements Ir, Ru, Re, Os, Tc, Au, Pt, Pd, and Ag; preferably, the M contains the noble metal elements Ir, Ru, Re, Os, Tc , at least one of Au, Pt, Pd, Ag, and the atomic percentage content of Ir, Ru, Re, Os, Tc and other elements in M is higher than 50%; as a further preference, the M contains noble metal elements Ir, At least one of Ru, Re, Os, Tc;
  • the T includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti, and Fe; preferably, the T includes W, Cr, Mo, V, Ta, Nb , at least one of Zr, Hf, Ti, Fe, and the atomic percentage content of elements such as W, Cr, Mo, V, Ta, Nb in T is higher than 50%; as a further preference, the T contains W, At least one of Cr, Mo, V, Ta, Nb;
  • the D is an impurity element and includes at least one of O, H, N, P, S, F, Cl, I, and Br; and the total content of these impurity elements is the content of D impurity elements;
  • the endogenous powder in the alloy strip whose main component is (M x T y ) x1 D z1 does not contain Cu element;
  • the composition of the endogenous powder in the initial alloy strip is (M x T y ) x1 D z1
  • the average composition of the cladding body is Cu x2 D z2 ;
  • the thickness of the alloy strip is in the range of 5 ⁇ m to 10 mm; preferably, the thickness of the alloy strip is in the range of 5 ⁇ m to 5 mm; preferably, the thickness of the alloy strip is in the range of 5 ⁇ m to 1 mm; as a further Preferably, the thickness of the alloy strip is in the range of 5 ⁇ m to 200 ⁇ m; as a further preference, the thickness of the alloy strip is in the range of 5 ⁇ m to 20 ⁇ m.
  • the width of the cross section of the alloy strip is more than 2 times its thickness; further, the length of the initial alloy strip is more than 10 times its thickness; preferably, the length of the initial alloy strip is more than 50 times its thickness; preferably, the length of the initial alloy strip is more than 100 times its thickness.
  • the particle size range of the endogenous powder is 2nm ⁇ 3mm; preferably, the particle size range of the endogenous powder is 2nm ⁇ 500 ⁇ m; preferably, the particle size range of the endogenous powder is 2nm ⁇ 99 ⁇ m ; As a further preference, the particle size range of the endogenous powder is 2nm ⁇ 10 ⁇ m; As a further preference, the particle diameter range of the endogenous powder is 2nm ⁇ 1 ⁇ m; As a further preference, the particle size range of the endogenous powder It is 2nm ⁇ 200nm; as a further preference, the particle size range of the endogenous powder is 2nm ⁇ 100nm.
  • the shape of the endogenous powder includes at least one of dendritic shape, spherical shape, nearly spherical shape, square shape, cake shape, and rod shape.
  • the number of single crystal particles in the endogenous powder in the alloy strip accounts for not less than 60% of the total number of endogenous powders.
  • volume percentage of the endogenous powder in the alloy strip does not exceed 50%.
  • the alloy strip is prepared by step S1 and step S2 in the above-mentioned method for preparing a powder material containing a noble metal element.
  • M, T or D in the solution of the present invention may also contain other elements or impurity elements other than those listed above. As long as the introduction of these elements or the changes in their contents do not cause a "qualitative change" in the solidification process and law of the initial alloy, it does not affect the realization of the above technical solutions of the present invention.
  • the initial alloy strip does not contain intermetallic compounds mainly composed of Cu and M, or Cu and T;
  • the solidified structure of the initial alloy strip includes a matrix phase and a dispersed particle phase; the melting point of the matrix phase is lower than that of the dispersed particle phase, and the dispersed particle phase is coated in the matrix phase;
  • phase separation occurs when the initial alloy melt is solidified, so that endogenous particles of a certain particle size target composition can be formed during the solidification of the initial alloy melt and can be separated by subsequent processes.
  • nano-metal particles can be easily prepared by bottom-up chemical methods, such as chemical reduction, but when the size of the particles increases to hundreds of nanometers or even micrometers, it is difficult to prepare them.
  • Metal particles of tens of microns or hundreds of microns can be easily prepared by top-down physical methods, such as atomization, ball milling, etc., but when the size of the particles is reduced to hundreds of nanometers to several microns, It is also difficult to prepare.
  • the technical scheme of the present invention can easily prepare nano-, sub-micron, micron, and even millimeter-scale target metal powder particles according to the different cooling rates in the solidification process of the initial alloy strip, which overcomes the above technical difficulties and has extremely high performance. Earth advantage.
  • the high-purity target powder materials were obtained from low-purity raw materials, and a new way was pointed out for the preparation of high-purity powder materials from low-purity raw materials, which was of positive significance.
  • the improvement of the purity of the target powder material of the present invention is mainly achieved through the following three mechanisms: 1) The "absorption" effect of the main element Cu of the relative active matrix on the impurity elements of the initial alloy melt.
  • the impurity element D Since Cu in the alloy is a low melting point element, it has a stronger affinity with the impurity element D during the melting and solidification of the alloy melt, which can make the impurity element D in the initial alloy melt enter more In the matrix phase composed of Cu element; 2) During the nucleation and growth of the endogenously precipitated dispersed particle phase, the impurity element D will be discharged into the remaining melt. As long as the endogenous precipitation of the dispersed particle phase is not later than the matrix phase in the solidification process, its impurities will be enriched in the last part of the melt that solidifies, that is, the part of the melt that is mainly composed of the main elements of the matrix phase and solidifies to form the matrix phase. .
  • the impurities related to the crucible entering the melt due to the interaction between the crucible and the melt during the smelting process are generally concentrated in the matrix phase, thereby further ensuring the purity of the dispersed particle phase, which makes the smelting process.
  • the requirements for the crucible in the process are further reduced, which greatly reduces the production cost.
  • the target metal powder mainly composed of single crystal particles can be obtained.
  • single crystal powders can achieve many significant and beneficial effects.
  • each endogenous dispersed particle grows and grows according to a specific atomic arrangement after nucleation from a certain position in the melt.
  • the volume percentage of the dispersed particle phase in the initial alloy strip to not exceed 50%, it is difficult to merge and grow between individual endogenous particles under the condition that each endogenous particle can be dispersed and distributed. Therefore, most of the dispersed and distributed particle phases finally obtained are single crystal phases.
  • the growth direction of each secondary dendrite maintains a certain phase relationship with the growth direction of the main dendrite, which is still a single crystal particle.
  • the grain boundaries generally contain impurity elements discharged from the grain during solidification, so it is difficult to obtain high-purity polycrystalline powder materials.
  • the target metal powder is mainly composed of single crystal particles, its purity must be guaranteed.
  • the atoms on the surface of the single crystal particles have specific arrangements, such as (111) plane arrangement, which will endow the target metal powder with special mechanical, physical and chemical properties, thereby producing beneficial effects.
  • the alloy strip composed of the endogenous powder and the coating body (matrix phase) creatively utilizes the in-situ generated matrix phase to wrap the endogenous powder, thereby maintaining the high purity and high activity of the endogenous powder.
  • metal or alloy powders prepared by traditional chemical methods or physical methods, especially nano-powders with extremely large specific surface areas, are easily oxidized naturally and face the problem of difficulty in powder preservation.
  • the cladding body can not be removed in a hurry, but the cladding can be directly used. The body protects the endogenous metal powder from natural oxidation.
  • This alloy strip composed of endogenous metal powder and cladding can be directly used as raw material for downstream production, so it has the potential to become a special product.
  • the downstream production needs to use high-purity powder, according to the characteristics of the next process, you can choose a suitable time and release the endogenous metal powder from the coating in the alloy strip under a suitable environment, and then as far as possible In a short time, the released endogenous powder enters the next production process, so that the chance of endogenous metal powder being contaminated by impurities such as oxygen is greatly reduced.
  • the endogenous metal powder when the endogenous metal powder is nano-powder, the endogenous metal powder can be compounded with the resin at the same time as the endogenous metal powder is released from the cladding or immediately afterward, thereby preparing the resin-based composite material with the addition of endogenous metal powder with high activity.
  • the solid alloy obtained by solidification in the step S2 is in the shape of a strip, which ensures the uniformity of the product shape and the feasibility of mass production.
  • the alloy strip is a thin alloy strip, it can be prepared by the stripping method. As long as the flow rate of the alloy melt flowing to the rotating roll is kept constant and the rotation speed of the rotating roll is fixed, an alloy thin strip with a uniform thickness can be obtained, and the preparation process It can be carried out continuously, which is beneficial to large-scale production.
  • the alloy strip is a thick alloy strip, it can be prepared by a mature continuous casting method. The principle of continuous casting is similar to that of the strip method, and a continuous and uniform thick strip can also be obtained through the melt.
  • the preparation process can also It is carried out continuously, which is beneficial to large-scale production.
  • the cooling rate is also relatively uniform, and the particle size of the obtained dispersed particles is relatively uniform.
  • the solid alloy obtained by solidification is in the shape of an ingot, according to common sense, the ingot has no uniform thickness, and no obvious length and endpoints, which generally leads to difficulty in dissipating heat from the internal melt, and it is easy to obtain abnormally large internal melts. Green particles, this is only necessary when the large endogenous particles simply need to be collected and purified. Moreover, it is difficult to continuously produce ordinary ingots. Therefore, the present invention obtains alloy strips by solidification, which is suitable for subsequent preparation of powder materials by "dephase method".
  • the preparation method of the present invention has the characteristics of simple process, easy operation and low cost, and can prepare a variety of high-purity powder materials containing noble metal elements including nano-scale, sub-micron-scale and micro-scale.
  • Metallurgy, composite materials, wave absorbing materials, sterilization materials, metal injection molding, 3D printing, coatings and other fields have good application prospects.
  • the present invention also provides a method for preparing metal powder, which comprises the following steps:
  • the solidification structure of the Cu a M b T c master alloy is composed of a matrix phase composed of Cu and a dispersed particle phase composed of MT, and the melting point of the MT dispersed particle phase is higher than that of the Cu matrix phase; preferably, 0.2% ⁇
  • Step 2 The Cu matrix phase in the Cu a M b T c master alloy is removed by the acid solution reaction, while retaining the MT dispersed particle phase that does not react with the acid solution, that is, the target metal composed of the MT dispersed particle phase is obtained. powder.
  • the preparation of ultrafine metal powder can be realized.
  • the rapid solidification technology includes the alloy melt metal rolling strip method, and the solidification rate of the alloy melt is 100K/s ⁇ 1 ⁇ 10 7 K/s.
  • the rapid solidification technology includes an alloy melt atomization pulverization method, and the solidification rate of the alloy melt is 50K/s ⁇ 5 ⁇ 10 5 K/s.
  • the solidification rate when the solidification rate is higher than 5 ⁇ 10 4 K/s, a nanoscale (2nm ⁇ 200nm) dispersed particle phase can be obtained; when the solidification rate is 1 ⁇ 10 3 K/s ⁇ At 5 ⁇ 10 4 K/s, submicron (200nm ⁇ 1000nm) dispersed particles can be obtained; when the solidification rate is lower than 1 ⁇ 10 3 K/s, micron (>1 ⁇ m) dispersed particles can be obtained .
  • the Cu a M b T c master alloy has at least one dimension in the three-dimensional dimension direction ranging from 5 ⁇ m to 500 ⁇ m.
  • the thickness of the master alloy strip is in the range of 5 ⁇ m to 500 ⁇ m; when the powdered master alloy is prepared by the melt atomization powder milling technology, the thickness of the master alloy strip is specified.
  • the atomization and pulverization technology includes at least one of gas atomization, water atomization, water vapor-combined atomization, and vacuum atomization.
  • the shape of the dispersed particle phase in the solidified structure of the master alloy includes at least one of dendritic, spherical, nearly spherical, square, cake, and rod, and the particle size ranges from 2 nm to 100 ⁇ m.
  • the acid solution includes at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, acetic acid, and oxalic acid.
  • the ratio of the acid and the concentration of the acid are to ensure that the Cu matrix can be removed by reaction, and the M-T dispersed particle phase does not react with the acid.
  • the MT dispersed particle phase is mainly composed of extremely acid-resistant elements, and Cu can react significantly with some acids, such as 2 mol/L hydrochloric acid aqueous solution with a concentration higher than 2 mol/L, it can be determined according to the specific composition and ratio of the master alloy.
  • the acid solution ratio and concentration are designed to remove the Cu matrix phase while retaining the MT dispersed particle phase.
  • the particle size range of the target metal powder composed of the dispersed particle phase is 2 nm ⁇ 100 ⁇ m.
  • the shape of the target metal powder includes at least one of dendritic shape, spherical shape, nearly spherical shape, square shape, pie shape, and rod shape.
  • the present invention can obtain nano-scale, sub-micron-scale, and micro-scale dispersed particle phases by controlling the size of the melt solidification rate, and then obtain the target metal powder with the corresponding particle size by removing the matrix phase, which greatly reduces the superfluous particle size. Preparation cost of fine metal powder.
  • the resulting dispersed particle phase is also composed of multiple elements, which makes it easier to prepare the target alloy powder composed of the dispersed particle phase. It is simple and feasible, and greatly expands the composition range and application field of the target alloy powder.
  • the preparation method invented by this alternative solution has the characteristics of simple process, easy operation and low cost, and can prepare various metal powders including nano-scale, sub-micron and micro-scale, and is used in the fields of catalysis, powder metallurgy, composite materials, etc. Has a very good application prospect.
  • the present embodiment provides a preparation method of nano Ru powder, and the preparation method comprises the following steps:
  • the alloy with the atomic ratio formula of Cu 90 Ru 10 was selected, and the raw materials were weighed according to the formula. After the initial alloy raw materials were melted uniformly, Cu 90 with a thickness of 15 ⁇ m was prepared by the copper roller stripping technique at a solidification rate of 10 6 K/s. Ru 10 master alloy strip.
  • the solidified structure of the alloy strip is composed of a matrix phase with a composition of Cu and a large amount of dispersed particles with a composition of Ru, wherein the shape of the Ru particles is nearly spherical, and the particle size ranges from 3 nm to 150 nm.
  • the Cu matrix in the master alloy strip is removed by the reaction of 6 mol/L hydrochloric acid aqueous solution, so that the Ru particles in the master alloy strip that are difficult to react with the hydrochloric acid aqueous solution of this concentration are detached, that is, nano Ru powder is obtained, and its particle size is in the range of 3nm ⁇ 150nm.
  • the present embodiment provides a preparation method of nano Ru powder, and the preparation method comprises the following steps:
  • the alloy with the atomic ratio formula of Cu 95 Ru 5 is selected, and the raw materials are weighed according to the formula. After the initial alloy raw material is melted uniformly, the alloy melt is prepared into granules at a solidification rate of 5 ⁇ 10 4 K/s by gas atomization technology.
  • the solidification structure of the master alloy powder is composed of a matrix phase with a composition of Cu and a large amount of dispersed particles with a composition of Ru, wherein the shape of the Ru dispersed particles is nearly spherical, and the particle size ranges from 50nm to 200nm.
  • the Cu matrix in the master alloy powder is removed by the reaction of 6 mol/L hydrochloric acid aqueous solution, so that the Ru particles in the master alloy powder that are difficult to react with the hydrochloric acid aqueous solution of this concentration are detached, that is, nano Ru powder is obtained, and its particle size ranges from 50 nm to 50 nm. 200nm.
  • the present embodiment provides a preparation method of submicron Ir-Nb powder, and the preparation method comprises the following steps:
  • the alloy with the atomic ratio formula of Cu 70 Ir 15 Nb 15 is selected, the raw materials are weighed according to the formula, and after the initial alloy raw material is melted uniformly, the alloy melt is prepared into granules at a solidification rate of 10 4 K/s by gas atomization technology Ir 50 Nb 50 master alloy powder with diameters ranging from 10 ⁇ m to 150 ⁇ m.
  • the solidification structure of the master alloy powder is composed of a matrix phase with a composition of Cu and a large number of dispersed particle phases with a composition of Ir 50 Nb 50 , wherein the shape of the Ir 50 Nb 50 dispersed particles is nearly spherical, and the particle size ranges from 50nm to 1000nm.
  • the Cu matrix in the master alloy powder is removed by the reaction of the 6 mol/L hydrochloric acid aqueous solution, so that the Ir 50 Nb 50 particles in the master alloy powder that are difficult to react with the aqueous hydrochloric acid solution of this concentration are separated out, that is, the submicron Ir 50 Nb 50 powder is obtained.
  • the particle size ranges from 50nm to 1000nm.
  • This embodiment provides a preparation method of nano Ru-Ir-Os-Fe powder, and the preparation method includes the following steps:
  • An alloy whose atomic ratio formula is Cu 90 Ru 2.5 Ir 2.5 Os 2.5 Fe 2.5 is selected, and the raw materials are weighed according to the formula. After the initial alloy raw material is melted uniformly, it is prepared by copper roller stripping technology at a solidification rate of 10 6 K/s. Cu 90 Ru 2.5 Ir 2.5 Os 2.5 Fe 2.5 master alloy strips with a thickness of 15 ⁇ m.
  • the solidification structure of the alloy strip is composed of a matrix phase with a composition of Cu and a large amount of dispersed particles with a composition of Ru 25 Ir 25 Os 25 Fe 25 , wherein the shape of the Ru 25 Ir 25 Os 25 Fe 25 particles is nearly spherical, and the particle size is The size range is from 3nm to 150nm.
  • the Cu matrix in the master alloy strip is reacted and removed by a 5 mol/L hydrochloric acid aqueous solution, so that the Ru 25 Ir 25 Os 25 Fe 25 particles in the master alloy strip that are difficult to react with the aqueous hydrochloric acid solution of this concentration are separated out, that is, nano Ru 25 is obtained.
  • the Ir 25 Os 25 Fe 25 powder has a particle size range of 3nm to 150nm.
  • the present embodiment provides a preparation method of submicron W-Re powder, and the preparation method comprises the following steps:
  • the alloy with the atomic ratio formula of Cu 90 W 5 Re 5 was selected, and the raw materials were weighed according to the formula. After the initial alloy raw materials were melted uniformly, the copper roller stripping technique was used to prepare the alloy with a thickness of 150 ⁇ m at a solidification rate of 10 4 K/s. Cu 90 W 5 Re 5 master alloy strip.
  • the solidification structure of the alloy strip is composed of a matrix phase with a composition of Cu and a large amount of dispersed particles with a composition of W 50 Re 50 , wherein the shape of the Ru 25 Ir 25 Os 25 Fe 25 particles is nearly spherical, and the particle size range is 50 nm. ⁇ 1000nm.
  • the Cu matrix in the master alloy strip is removed by the reaction of 6 mol/L hydrochloric acid aqueous solution, so that the W 50 Re 50 particles in the master alloy strip that are difficult to react with the hydrochloric acid aqueous solution of this concentration are detached, that is, sub-micron W 50 Re 50 powder is obtained. , and its particle size ranges from 50 nm to 1000 nm.
  • the present embodiment provides a preparation method of micron Ir-Ta-Nb-V powder, and the preparation method comprises the following steps:
  • the alloy whose atomic ratio formula is Cu 80 Ir 5 Ta 5 Nb 5 V 5 is selected, and the raw materials are weighed according to the formula. After the initial alloy raw material is melted uniformly, it is prepared into a thickness of 500 ⁇ m Cu 80 Ir 5 Ta 5 Nb 5 V 5 master alloy strip.
  • the solidification structure of the alloy strip is composed of a matrix phase with a composition of Cu and a large amount of dispersed particles with a composition of Ir 25 Ta 25 Nb 25 V 25 , wherein the shape of the Ir 25 Ta 25 Nb 25 V 25 particles is dendritic, and the particle size is dendritic.
  • the size ranges from 1 ⁇ m to 50 ⁇ m.
  • Ta 25 Nb 25 V 25 powder has a particle size range of 1 ⁇ m to 50 ⁇ m.
  • This embodiment provides a preparation method of nano-Ir-Ta-Nb-Cr-Zr powder, and the preparation method includes the following steps:
  • An alloy whose atomic ratio formula is Cu 75 Ir 6 Ta 6 Nb 6 Cr 6 Zr 1 is selected, the raw materials are weighed according to the formula, and the initial alloy raw materials are melted uniformly, and the solidification rate of 10 6 K/s is carried out by the copper roller stripping technique.
  • a Cu 75 Ir 6 Ta 6 Nb 6 Cr 6 Zr 1 master alloy strip with a thickness of 15 ⁇ m was prepared.
  • the solidification structure of the alloy strip is composed of a matrix phase with a composition of Cu and a large number of dispersed particles with a composition of Ir 24 Ta 24 Nb 24 Cr 24 Zr 4 , wherein the shape of the Ir 24 Ta 24 Nb 24 Cr 24 Zr 4 particles is nearly Spherical, with particle size ranging from 3nm to 150nm.
  • the Cu matrix in the master alloy strip is removed by the reaction of 5 mol/L hydrochloric acid aqueous solution, so that the Ir 24 Ta 24 Nb 24 Cr 24 Zr 4 particles in the master alloy strip that are difficult to react with the hydrochloric acid aqueous solution of this concentration are detached, and the nanometer particles are obtained.
  • the Ir 24 Ta 24 Nb 24 Cr 24 Zr 4 powder has a particle size range of 3nm to 150nm.
  • the present embodiment provides a preparation method of nano-Ir-Nb powder, and the preparation method comprises the following steps:
  • the initial alloy melt was prepared into Cu 69.9 Ir 14.9 Nb 14.9 D 0.3 alloy ribbons with a thickness of ⁇ 20 ⁇ m by copper roll stripping technique at a solidification rate of about ⁇ 10 6 K/s.
  • the solidification structure of the alloy strip is composed of a matrix phase whose atomic percentage composition is mainly Cu 99.6 D 0.4 and a large amount of dispersed particle phase whose composition is mainly Ir 49.97 Nb 49.97 D 0.06 .
  • the Ir 49.97 Nb 49.97 D 0.06 dispersed particles are nearly spherical in shape, and their particle size ranges from 10 nm to 150 nm.
  • the volume percentage of Ir 49.97 Nb 49.97 D 0.06 dispersed particles in the alloy strip is about 37%;
  • the present embodiment provides a preparation method of nano-Ir-Pt powder, and the preparation method comprises the following steps:
  • the initial alloy melt was prepared into Cu 69.85 Ir 19.9 Pt 9.95 D 0.3 alloy strips with a thickness of ⁇ 20 ⁇ m by copper roll stripping technique at a solidification rate of about ⁇ 10 6 K/s.
  • the solidification structure of the alloy strip is composed of a matrix phase whose atomic percentage is mainly Cu 99.6 D 0.4 and a large amount of which is a dispersed particle phase which is mainly Ir 66.62 Pt 33.31 D 0.07 .
  • the Ir 66.62 Pt 33.31 D 0.07 dispersed particles are nearly spherical in shape, and their particle size ranges from 10 nm to 150 nm.
  • the volume percentage of Ir 66.62 Pt 33.31 D 0.07 dispersed particles in the alloy strip is about 34%;
  • the present embodiment provides a preparation method of nano-Ir-Nb powder, and the preparation method comprises the following steps:
  • Select D including O, H, N, P, S, F, Cl, Br, I
  • impurity elements with atomic percentage content of 0.2at.%, 0.5at.%, 0.5at.% Cu, Ir and Nb respectively Raw material, wherein the Ir raw material also contains 2 at.% Rh.
  • the raw materials were melted in a ratio of about 70:15:15 in the molar ratio of Cu:Ir:Nb to obtain a homogeneous initial alloy melt with a composition of Cu 69.9 (Ir 98 Rh 2 ) 14.9 Nb 14.9 D 0.3 in atomic percentage.
  • the initial alloy melt was prepared into Cu 69.9 (Ir 98 Rh 2 ) 14.9 Nb 14.9 D 0.3 alloy ribbons with a thickness of ⁇ 20 ⁇ m by copper roll stripping technique at a solidification rate of about ⁇ 10 6 K/s.
  • the solidification structure of the alloy strip is composed of a matrix phase whose atomic percentage composition is mainly Cu 99.6 D 0.4 and a large amount of dispersed particle phase whose composition is mainly (Ir 98 Rh 2 ) 49.97 Nb 49.97 D 0.06 .
  • the shape of the (Ir 98 Rh 2 ) 49.97 Nb 49.97 D 0.06 dispersed particles is nearly spherical, and the particle size ranges from 10 nm to 150 nm.
  • the volume percentage of (Ir 98 Rh 2 ) 49.97 Nb 49.97 D 0.06 dispersed particles in the alloy strip is about 37%; moreover, the introduction of a small amount of Rh in the alloy melt did not lead to the formation of Cu in the initial alloy strip. It is an intermetallic compound composed of Rh; and it does not affect the structural characteristics of the matrix phase and the dispersed particle phase in the alloy strip, nor does it affect the law of reducing the impurity content in the dispersed particle phase.

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Abstract

A preparation method and application of a noble metal element-containing powder material. According to the preparation method, an initial alloy strip containing a matrix phase and a dispersed particle phase is obtained by means of solidification of an alloy melt, the matrix phase in the initial alloy strip is then removed, and at the same time, the dispersed particle phase containing a noble metal element is retained, thereby obtaining a noble metal element-containing powder material composed of the original dispersed particle phase. The preparation method is simple in process, can be used to prepare noble metal element-containing powder materials having various sizes such as nano-scale, sub-micron level, and micron-level, and has good prospects for application in the fields of catalytic materials, powder metallurgy, composite materials, wave-absorbing materials, sterilization materials, metal injection molding, 3D printing, coating and the like.

Description

一种包含贵金属元素的粉体材料的制备方法及其应用A kind of preparation method of powder material containing noble metal element and application thereof 技术领域technical field
本发明涉及微纳米材料技术领域,特别是涉及一种包含贵金属元素的粉体材料的制备方法及其应用。The invention relates to the technical field of micro-nano materials, in particular to a preparation method and application of a powder material containing noble metal elements.
背景技术Background technique
微米、亚微米、纳米粒径的超细粉末材料的制备方法从物质的状态分有固相法、液相法和气相法。其中,固相法主要有机械粉碎法、超声波粉碎法、热分解法、爆炸法等,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。The preparation methods of ultrafine powder materials with micron, submicron and nanometer particle size are divided into solid phase method, liquid phase method and gas phase method from the state of matter. Among them, the solid phase method mainly includes mechanical pulverization method, ultrasonic pulverization method, thermal decomposition method, explosion method, etc. The liquid phase method mainly includes precipitation method, alkoxide method, carbonyl method, spray thermal drying method, freeze drying method, electrolysis method, Chemical condensation methods, etc., gas phase methods mainly include gas phase reaction method, plasma method, high temperature plasma method, evaporation method, chemical vapor deposition method, etc.
虽然超细粉末材料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材料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金属及合金粉末的主要方法,但生产效率低,收得率不高,且能耗相对较大;气流磨法、氢化脱氢法适合大批量工业化生产,但对原料和合金的选择性较强。Although there are many methods for preparing ultrafine powder materials, each method has certain limitations. For example, the disadvantages of the liquid phase method are low yield, high cost and complex process; the disadvantage of the mechanical method is that it is difficult to classify after the powder material is prepared, and the purity, fineness and morphology of the product are difficult to guarantee; Electrode method and gas atomization method are the main methods for preparing high-performance metal and alloy powder at present, but the production efficiency is low, the yield is not high, and the energy consumption is relatively large; jet milling method and hydrogenation dehydrogenation method are suitable for large-scale industrialization production, but with strong selectivity to raw materials and alloys.
对于贵金属粉体材料,尤其贵金属纳米粉体材料来说,其一般通过化学还原的方法制备。但化学还原法一般难以保证产物大规模制备的同时还保证可以很好地控制所得贵金属纳米粉的粒径。For noble metal powder materials, especially noble metal nano-powder materials, they are generally prepared by chemical reduction methods. However, the chemical reduction method is generally difficult to ensure the large-scale preparation of the product and also ensure that the particle size of the obtained noble metal nanopowder can be well controlled.
此外,粉体材料的杂质含量,尤其是氧含量,对其性能具有极大的影响。目前,主要通过控制原料纯度与真空度的方法来控制金属或合金的杂质含量,成本高昂。因此,开发新的高纯粉体材料的制备方法,具有重要的意义。In addition, the impurity content of the powder material, especially the oxygen content, has a great influence on its performance. At present, the impurity content of metals or alloys is mainly controlled by controlling the purity and vacuum degree of raw materials, which is expensive. Therefore, it is of great significance to develop new preparation methods for high-purity powder materials.
发明内容SUMMARY OF THE INVENTION
基于此,有必要针对上述问题,提供一种工艺简单、易于操作包含贵金属元素的粉体材料的制备方法。Based on this, it is necessary to provide a method for preparing a powder material containing noble metal elements with a simple process and easy operation to address the above problems.
一种包含贵金属元素的粉体材料的制备方法,其特征在于,包括以下步骤:A preparation method of a powder material containing noble metal elements, characterized in that, comprising the following steps:
步骤S1,选择初始合金原料,按照初始合金成分配比将初始合金原料熔化,得到含有杂 质元素D的均匀初始合金熔体;所述初始合金熔体的平均成分主要为Cu a(M xT y) bD d,其中,M包含贵金属元素Ir、Ru、Re、Os、Tc、Au、Pt、Pd、Ag中的至少一种,T包含W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti、Fe中的至少一种,D包含O、H、N、P、S、F、Cl、I、Br中的至少一种;且60%≤a≤99.9%,0.1%≤b≤40%,0≤d≤5%;0.1%≤x≤100%,0%≤y≤99.9%;其中,a、b、d,以及x、y分别代表对应组成元素的原子百分比含量; Step S1, select the initial alloy raw material, and melt the initial alloy raw material according to the initial alloy composition ratio to obtain a uniform initial alloy melt containing the impurity element D; the average composition of the initial alloy melt is mainly Cu a (M x T y ) ) b D d , wherein M includes at least one of noble metal elements Ir, Ru, Re, Os, Tc, Au, Pt, Pd, and Ag, and T includes W, Cr, Mo, V, Ta, Nb, Zr, At least one of Hf, Ti, Fe, D contains at least one of O, H, N, P, S, F, Cl, I, Br; and 60%≤a≤99.9%, 0.1%≤b≤ 40%, 0≤d≤5%; 0.1%≤x≤100%, 0%≤y≤99.9%; among them, a, b, d, and x, y represent the atomic percentage content of the corresponding constituent elements;
步骤S2,将所述初始合金熔体凝固成初始合金条带;所述初始合金条带的凝固组织包括基体相和弥散颗粒相;所述基体相的熔点低于所述弥散颗粒相,所述弥散颗粒相被包覆于所述基体相中;所述初始合金熔体凝固过程中,初始合金熔体中的杂质元素D在弥散颗粒相与基体相中重新分配,并富集于所述基体相中,从而使所述弥散颗粒相得到纯化;In step S2, the initial alloy melt is solidified into initial alloy strips; the solidified structure of the initial alloy strip includes a matrix phase and a dispersed particle phase; the melting point of the matrix phase is lower than that of the dispersed particle phase, and the The dispersed particle phase is coated in the matrix phase; during the solidification of the initial alloy melt, the impurity element D in the initial alloy melt is redistributed in the dispersed particle phase and the matrix phase, and is enriched in the matrix phase, so that the dispersed particle phase is purified;
所述初始合金条带中弥散颗粒相的成分主要为(M xT y) x1D z1,基体相的平均成分主要为Cu x2D z2;且99%≤x1≤100%,0≤z1≤1%;90%≤x2≤100%,0≤z2≤10%;z1≤d≤z2,2z1≤z2;x1、z1、x2、z2分别代表对应组成元素的原子百分比含量; The composition of the dispersed particle phase in the initial alloy strip is mainly (M x T y ) x1 D z1 , and the average composition of the matrix phase is mainly Cu x2 D z2 ; and 99%≤x1≤100%, 0≤z1≤1 %; 90%≤x2≤100%, 0≤z2≤10%; z1≤d≤z2, 2z1≤z2; x1, z1, x2, z2 represent the atomic percentage content of the corresponding constituent elements;
步骤S3,将所述初始合金条带中的基体相去除,并保留基体相去除过程中不能被同时去除的弥散颗粒相;收集脱落出来的弥散颗粒相,即得到由原弥散颗粒组成的包含有贵金属元素的高纯目标粉体材料。In step S3, the matrix phase in the initial alloy strip is removed, and the dispersed particle phase that cannot be removed at the same time in the process of removing the matrix phase is retained; High-purity target powder materials of precious metal elements.
所述步骤S1中,In the step S1,
进一步地,所述M包含贵金属元素Ir、Ru、Re、Os、Tc、Au、Pt、Pd、Ag中的至少一种,且Ir、Ru、Re、Os、Tc等元素在M中的原子百分比含量高于50%;Further, the M includes at least one of noble metal elements Ir, Ru, Re, Os, Tc, Au, Pt, Pd, Ag, and the atomic percentage of elements such as Ir, Ru, Re, Os, Tc in M The content is higher than 50%;
进一步地,所述M包含贵金属元素Ir、Ru、Re、Os、Tc、Au、Pt、Pd、Ag中的至少一种,且Ir、Ru、Re、Os、Tc等元素在M中的原子百分比含量高于75%;Further, the M includes at least one of noble metal elements Ir, Ru, Re, Os, Tc, Au, Pt, Pd, Ag, and the atomic percentage of elements such as Ir, Ru, Re, Os, Tc in M The content is higher than 75%;
作为优选,所述M包含贵金属元素Ir、Ru、Re、Os、Tc中的至少一种,Preferably, the M contains at least one of noble metal elements Ir, Ru, Re, Os, Tc,
进一步地,所述T包含W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti、Fe中的至少一种,且W、Cr、Mo、V、Ta、Nb等元素在T中的原子百分比含量高于50%;Further, the T includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti, Fe, and W, Cr, Mo, V, Ta, Nb and other elements in T The atomic percentage content is higher than 50%;
进一步地,所述T包含W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti、Fe中的至少一种,且W、Cr、Mo、V、Ta、Nb等元素在T中的原子百分比含量高于75%;Further, the T includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti, Fe, and W, Cr, Mo, V, Ta, Nb and other elements in T The atomic percentage content is higher than 75%;
作为优选,所述T包含W、Cr、Mo、V、Ta、Nb中的至少一种;Preferably, the T includes at least one of W, Cr, Mo, V, Ta, and Nb;
进一步地,所述初始合金熔体中的D杂质元素来源包括:初始合金原料引入杂质,熔炼过程中气氛或坩埚引入杂质。其中,气氛引入杂质是指合金熔体吸收的环境气氛中的O、N、H等杂质。Further, the source of the D impurity element in the initial alloy melt includes: impurities introduced from the initial alloy raw material, and impurities introduced from the atmosphere or the crucible during the smelting process. Among them, the impurities introduced into the atmosphere refer to impurities such as O, N, and H in the ambient atmosphere absorbed by the alloy melt.
进一步地,D为杂质元素且包含O、H、N、P、S、F、Cl、I、Br中的至少一种;且这些杂质元素的总含量即为D杂质元素的含量;Further, D is an impurity element and includes at least one of O, H, N, P, S, F, Cl, I, and Br; and the total content of these impurity elements is the content of D impurity elements;
进一步地,如果原料是含有杂质元素的各单质或中间合金,则可将其按照配比熔化制备所述初始合金熔体。如果提供的原料直接为初始合金熔体成分对应合金原料时,则可以将其重熔得到初始合金熔体。Further, if the raw material is each element or master alloy containing impurity elements, it can be melted according to the proportion to prepare the initial alloy melt. If the supplied raw material is directly the alloy raw material corresponding to the composition of the initial alloy melt, it can be remelted to obtain the initial alloy melt.
进一步的,所述步骤S1中初始合金熔体平均成分中Cu与M,以及Cu与T的组合极为重要,其选择原则是确保合金熔体凝固过程中Cu与M之间,以及Cu与T之间都不形成金属间化合物。这样就能实现初始合金熔体凝固过程中以Cu主的基体相和以M及T为主的颗粒相的两相分离,有利于后续制备以M及T为主的包含贵金属元素的粉体材料。Further, the combination of Cu and M and Cu and T in the average composition of the initial alloy melt in the step S1 is extremely important. Intermetallic compounds are not formed between them. In this way, the two-phase separation of the Cu-based matrix phase and the M and T-based particle phases during the solidification of the initial alloy melt can be achieved, which is beneficial to the subsequent preparation of M and T-based powder materials containing noble metal elements .
进一步地,59.9%≤a≤99.8%,0.1%≤b≤40%,0<d≤5%;Further, 59.9%≤a≤99.8%, 0.1%≤b≤40%, 0<d≤5%;
所述步骤S2中,In the step S2,
进一步地,所述初始合金条带中不含有包含Cu与M构成的金属间化合物;Further, the initial alloy strip does not contain an intermetallic compound composed of Cu and M;
进一步地,所述初始合金条带中不含有包含Cu与T构成的金属间化合物;Further, the initial alloy strip does not contain an intermetallic compound composed of Cu and T;
进一步地,当M包含Au、Pt、Pd、Ag中的至少一种时,其以固溶的方式固溶存在于主要成分为(M xT y) x1D z1的弥散颗粒相中,且所述主要成分为(M xT y) x1D z1的弥散颗粒相还同时包含有同属于M的Ir、Ru、Re、Os、Tc中的至少一种; Further, when M contains at least one of Au, Pt, Pd, and Ag, it exists in a solid-solution manner in a dispersed particle phase whose main component is (M x T y ) x1 D z1 , and the The dispersed particle phase whose main component is (M x T y ) x1 D z1 also contains at least one of Ir, Ru, Re, Os, and Tc all belonging to M;
进一步地,当T包含Zr、Hf、Ti、Fe中的至少一种时,其以固溶的方式固溶存在于主要成分为(M xT y) x1D z1的弥散颗粒相中,且所述主要成分为(M xT y) x1D z1的弥散颗粒相还同时包含有同属于T的W、Cr、Mo、V、Ta、Nb中的至少一种; Further, when T contains at least one of Zr, Hf, Ti, and Fe, it is present in a solid solution in a dispersed particle phase whose main component is (M x T y ) x1 D z1 , and the The dispersed particle phase whose main component is (M x T y ) x1 D z1 also contains at least one of W, Cr, Mo, V, Ta, and Nb all belonging to T;
进一步地,所述成分主要为(M xT y) x1D z1的包含贵金属元素的弥散颗粒相中不含有Cu元素; Further, the dispersed particle phase containing noble metal elements whose composition is mainly (M x T y ) x1 D z1 does not contain Cu element;
进一步地,所述合金熔体凝固的方式包括甩带法、连铸法;一般来说,通过甩带法可以获得较薄的初始合金条带;通过连铸法可以获得较厚的合金条带。Further, the method of solidification of the alloy melt includes strip method and continuous casting method; generally, thinner initial alloy strip can be obtained by strip method; thicker alloy strip can be obtained by continuous casting method .
不论是甩带法获得的薄合金条带,还是连铸法获得的厚合金条带,均与普通铸造法获得的合金铸锭形貌完全不同,普通铸造法获得的合金铸锭在尺度上一般没有明显的长度、宽度、厚度区别。Whether it is the thin alloy strip obtained by the stripping method or the thick alloy strip obtained by the continuous casting method, the morphology of the alloy ingot obtained by the ordinary casting method is completely different. The alloy ingot obtained by the ordinary casting method is average in size. There is no obvious difference in length, width and thickness.
进一步地,所述初始合金条带的厚度范围为5μm~10mm;进一步地,所述初始合金条带的厚度范围为5μm~5mm;作为优选,所述初始合金条带的厚度范围为5μm~1mm;作为进一步优选,所述初始合金条带的厚度范围为5μm~200μm;作为进一步优选,所述初始合金条带的厚度范围为5μm~20μm。Further, the thickness of the initial alloy strips ranges from 5 μm to 10 mm; further, the thickness of the initial alloy strips ranges from 5 μm to 5 mm; preferably, the thickness of the initial alloy strips ranges from 5 μm to 1 mm ; As a further preference, the thickness of the initial alloy strip ranges from 5 μm to 200 μm; as a further preference, the thickness of the initial alloy strip ranges from 5 μm to 20 μm.
需要说明的是,当初始合金条带的厚度为毫米级时,其也可以被称为合金薄板。It should be noted that when the thickness of the initial alloy strip is in the order of millimeters, it can also be referred to as an alloy sheet.
进一步地,所述初始合金条带横截面的宽度是其厚度的2倍以上;进一步地,所述初始合金条带的长度是其厚度的10倍以上;作为优选,所述初始合金条带的长度是其厚度的50 倍以上;作为优选,所述初始合金条带的长度是其厚度的100倍以上;Further, the width of the cross section of the initial alloy strip is more than 2 times its thickness; further, the length of the initial alloy strip is more than 10 times its thickness; The length is more than 50 times its thickness; preferably, the length of the initial alloy strip is more than 100 times its thickness;
进一步地,所述初始合金熔体凝固的速率为1K/s~10 7K/s; Further, the solidification rate of the initial alloy melt is 1K/s~10 7 K/s;
进一步地,所述弥散颗粒相的颗粒大小与初始合金熔体的凝固速率有关;一般来说,弥散颗粒相的颗粒粒径大小与初始合金熔体的凝固速率成负相关的关系,即初始合金熔体的凝固速率越大,弥散颗粒相的颗粒粒径就越小。Further, the particle size of the dispersed particle phase is related to the solidification rate of the initial alloy melt; in general, the particle size of the dispersed particle phase has a negative correlation with the solidification rate of the initial alloy melt, that is, the initial alloy melt. The higher the solidification rate of the melt, the smaller the particle size of the dispersed particle phase.
进一步地,所述弥散颗粒相的颗粒粒径范围为2nm~3mm;进一步地,所述弥散颗粒相的粒径范围为2nm~500μm;作为优选,所述弥散颗粒相的粒径范围为2nm~99μm;作为进一步优选,所述弥散颗粒相的粒径范围为2nm~5μm;作为进一步优选,所述弥散颗粒相的粒径范围为2nm~200nm;作为进一步优选,所述弥散颗粒相的粒径范围为2nm~100nm。Further, the particle size range of the disperse particle phase is 2nm~3mm; further, the particle size range of the disperse particle phase is 2nm~500μm; preferably, the particle size range of the disperse particle phase is 2nm~ 99 μm; as a further preference, the particle size range of the dispersed particle phase is 2 nm to 5 μm; as a further preference, the particle diameter of the dispersed particle phase is in the range of 2 nm to 200 nm; as a further preference, the particle diameter of the dispersed particle phase The range is 2nm to 100nm.
进一步地,所述初始合金熔体凝固的速率为10 5K/s~10 7K/s时,可以获得粒径以纳米级尺度为主的弥散颗粒。 Further, when the solidification rate of the initial alloy melt is 10 5 K/s to 10 7 K/s, dispersed particles with particle diameters mainly in nanoscale can be obtained.
进一步地,所述初始合金熔体凝固的速率为10 4K/s~10 5K/s时,可以获得粒径以亚微米级尺度为主的弥散颗粒。 Further, when the solidification rate of the initial alloy melt is 10 4 K/s to 10 5 K/s, dispersed particles with particle diameters mainly in the submicron scale can be obtained.
进一步地,所述初始合金熔体凝固的速率为10 2K/s~10 4K/s时,可以获得粒径以微米级尺度为主的弥散颗粒。 Further, when the solidification rate of the initial alloy melt is 10 2 K/s˜10 4 K/s, dispersed particles with a particle size mainly in the micron scale can be obtained.
进一步地,所述初始合金熔体凝固的速率为1K/s~10 2K/s时,可以获得粒径以毫米级尺度为主的弥散颗粒。 Further, when the solidification rate of the initial alloy melt is 1K/s˜10 2 K/s, dispersed particles with a particle size mainly in the millimeter scale can be obtained.
进一步地,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、棒条形中的至少一种;当颗粒形状为棒条形时,颗粒的大小特指棒条横截面的直径尺寸。Further, the particle shape of the dispersed particle phase is not limited, and may include at least one of dendritic, spherical, nearly spherical, square, pie, and rod-shaped; when the particle shape is rod-shaped, the Size refers to the diameter dimension of the cross-section of the rod.
进一步的,当弥散颗粒为纳米级或亚微米级尺度时,大概率获得球形或近球形颗粒;当弥散颗粒为微米级及以上尺度时,大概率获得枝晶形颗粒。Further, when the dispersed particles are of nanometer or submicron scale, spherical or nearly spherical particles are obtained with high probability; when the dispersed particles are of micrometer scale and above, dendritic particles are obtained with high probability.
进一步地,所述弥散颗粒相从所述初始合金熔体中凝固析出,根据形核长大理论,无论是刚刚形核长大的近球形纳米颗粒,还是充分长大的微米级、毫米级树枝晶颗粒,其晶体生长都具有固定的取向关系,从而使得析出的单个颗粒均主要由一个单晶构成。Further, the dispersed particle phase solidifies and precipitates from the initial alloy melt. According to the nucleation and growth theory, whether it is a nearly spherical nanoparticle that has just nucleated and grown, or a fully grown micron-scale or millimeter-scale tree branch. The crystal grains all have a fixed orientation relationship in their crystal growth, so that the precipitated single grains are mainly composed of a single crystal.
当所述弥散颗粒在整个初始合金条带中体积百分含量较高时,在单晶颗粒的内生析出过程中,不排除有两个或两个以上颗粒合并的情况。如果两个或两个以上单晶颗粒仅仅软团聚、相互吸附、或者仅少许部位接触连接在一起,没有像多晶材料那样通过正常晶界充分结合成一个颗粒,其仍然为两个单晶颗粒。其特点是,在后续过程去除基体相后,这些单晶颗粒可以轻易地通过包括超声分散处理、气流磨碎化等技术等分开。而正常的韧性金属或合金的多晶材料,则难以通过包括超声分散处理、气流磨碎化等技术将晶界分开。When the volume percentage of the dispersed particles in the entire initial alloy strip is relatively high, in the process of endogenous precipitation of single crystal particles, it is not excluded that two or more particles merge. If two or more single crystal particles are only softly agglomerated, adsorbed to each other, or connected together by only a few parts, and are not sufficiently combined into one particle through normal grain boundaries as in polycrystalline materials, they are still two single crystal particles. . Its characteristic is that after the matrix phase is removed in the subsequent process, these single crystal particles can be easily separated by techniques including ultrasonic dispersion treatment and jet milling. For polycrystalline materials of normal ductile metals or alloys, it is difficult to separate the grain boundaries by techniques including ultrasonic dispersion treatment and jet milling.
作为优选,所述初始合金条带中弥散颗粒中的单晶颗粒数目在所有弥散颗粒数目中的占比不低于60%。Preferably, the number of single crystal particles in the dispersed particles in the initial alloy strip accounts for not less than 60% of the total number of dispersed particles.
作为进一步优选,所述弥散颗粒中的单晶颗粒数目在所有弥散颗粒数目中的占比不低于90%。As a further preference, the number of single crystal particles in the dispersed particles accounts for not less than 90% of the total number of dispersed particles.
进一步地,对于某一确定的初始合金条带来说,所述弥散颗粒相在该初始合金条带中的体积百分含量可以通过对应初始合金熔体成分、弥散颗粒相成分、基体相成分,结合元素原子量、密度参数等计算确定。Further, for a certain initial alloy strip, the volume percentage content of the dispersed particle phase in the initial alloy strip can be determined by the corresponding initial alloy melt composition, dispersed particle phase composition, and matrix phase composition, Combined with element atomic weight, density parameters and other calculations to determine.
进一步地,所述弥散颗粒相在其对应的初始合金条带中的体积百分含量不高于50%。Further, the volume percentage of the dispersed particle phase in its corresponding initial alloy strip is not higher than 50%.
进一步地,99%≤x1<100%,0<z1≤1%;90%≤x2<100%,0<z2≤10%;z1<d<z2,2z1<z2;Further, 99%≤x1<100%, 0<z1≤1%; 90%≤x2<100%, 0<z2≤10%; z1<d<z2, 2z1<z2;
进一步地,z1<d<z2,且3z1<z2,即所述弥散颗粒相中D杂质含量低于所述初始合金熔体中的D杂质含量,且所述弥散颗粒相中D杂质含量的3倍仍然低于所述基体相中的D杂质含量;Further, z1<d<z2, and 3z1<z2, that is, the D impurity content in the dispersed particle phase is lower than the D impurity content in the initial alloy melt, and the D impurity content in the dispersed particle phase is 3%. times are still lower than the D impurity content in the matrix phase;
进一步地,99.5%≤x1<100%,0<z1≤0.5%;Further, 99.5%≤x1<100%, 0<z1≤0.5%;
进一步地,99.8%≤x1<100%,0<z1≤0.2%;Further, 99.8%≤x1<100%, 0<z1≤0.2%;
所述步骤S3中,In the step S3,
进一步地,所述将合金条带中基体相去除方法包括酸反应去除;Further, the method for removing the matrix phase in the alloy strip includes acid reaction removal;
因为Cu一般可以通过较浓且温度较高的盐酸水溶液腐蚀去除,而M与T元素一般不与较浓且温度较高的盐酸水溶液反应。即使M中含有元素(如Fe)可以单独与浓盐酸反应,但当其固溶在惰性的M或T中时,受到惰性的M或T的保护,也不能与浓盐酸反应。因此,可以通过较浓且温度较高的盐酸水溶液腐蚀去除合金条带中的基体相,同时保留弥散颗粒相。Because Cu can generally be removed by corrosion with a relatively concentrated and high-temperature hydrochloric acid aqueous solution, while M and T elements generally do not react with a relatively concentrated and high-temperature hydrochloric acid aqueous solution. Even if M contains elements (such as Fe) that can react with concentrated hydrochloric acid alone, when it is solid-dissolved in inert M or T, it is protected by inert M or T and cannot react with concentrated hydrochloric acid. Therefore, the matrix phase in the alloy ribbons can be removed by etching with a relatively concentrated and high temperature aqueous hydrochloric acid solution, while retaining the dispersed particle phase.
进一步地,所述酸反应去除方式中包含盐酸水溶液的浓度为2mol/L~12moll/L。Further, the concentration of the hydrochloric acid aqueous solution contained in the acid reaction removal method is 2 mol/L to 12 mol/L.
进一步地,所述酸反应去除方式中包含盐酸水溶液与合金条带反应的温度为0℃~100℃。Further, the acid reaction removal method includes the reaction temperature of the hydrochloric acid aqueous solution and the alloy strip being 0°C to 100°C.
进一步地,由于目标粉体材料为初始合金条带中脱落下来的弥散颗粒相,因此所述目标粉体材料的成分、颗粒粒径等均与对应的弥散颗粒相的成分、颗粒粒径相当。Further, since the target powder material is the disperse particle phase dropped from the initial alloy ribbon, the composition and particle size of the target powder material are all equivalent to the composition and particle size of the corresponding disperse particle phase.
进一步地,所述包含贵金属元素的目标粉体材料的颗粒粒径范围为2nm~3mm;作为优选,所述包含贵金属元素的目标粉体材料的颗粒粒径范围为2nm~500μm;作为优选,所述包含贵金属元素的目标粉体材料的颗粒粒径范围为2nm~99μm;作为进一步优选,所述包含贵金属元素的目标粉体材料的颗粒粒径范围为2nm~5μm;作为进一步优选,所述包含贵金属元素的目标粉体材料的颗粒粒径范围为2nm~200nm;作为进一步优选,所述包含贵金属元素的目标粉体材料的颗粒粒径范围为2nm~100nm。Further, the particle size range of the target powder material containing noble metal elements is 2 nm to 3 mm; preferably, the particle size range of the target powder material containing noble metal elements is 2 nm to 500 μm; The particle size range of the target powder material containing noble metal elements is 2 nm to 99 μm; as a further preference, the particle size range of the target powder material containing noble metal elements is 2 nm to 5 μm; The particle size range of the target powder material of the noble metal element is 2 nm to 200 nm; as a further preference, the particle size range of the target powder material containing the noble metal element is 2 nm to 100 nm.
进一步地,初始合金条带与酸溶液反应后,弥散颗粒从初始合金条带中脱离出来,对其 清洗、干燥,即得到包含贵金属元素的目标粉体材料。Further, after the initial alloy strip is reacted with the acid solution, the dispersed particles are separated from the initial alloy strip, which is cleaned and dried to obtain the target powder material containing precious metal elements.
进一步地,所述包含贵金属元素的目标粉体材料的成分主要为(M xT y) x1D z1Further, the composition of the target powder material containing noble metal elements is mainly (M x T y ) x1 D z1 ;
进一步地,所述成分主要为(M xT y) x1D z1的包含贵金属元素的目标粉体材料中不含有Cu元素; Further, the target powder material containing noble metal elements whose composition is mainly (M x T y ) x1 D z1 does not contain Cu element;
作为优选,所述包含贵金属元素的目标粉体材料的成分为(M xT y) x1D z1Preferably, the composition of the target powder material containing noble metal elements is (M x T y ) x1 D z1 ;
进一步地,所述包含贵金属元素的目标粉体材料中的D杂质元素的原子百分比含量不超过1%;Further, the atomic percentage content of D impurity element in the target powder material containing noble metal element is not more than 1%;
作为优选,所述包含贵金属元素的目标粉体材料中的D杂质元素的原子百分比含量不超过0.5%;Preferably, the atomic percentage content of D impurity element in the target powder material containing noble metal element is not more than 0.5%;
作为优选,所述包含贵金属元素的目标粉体材料中的D杂质元素的原子百分比含量不超过0.2%;Preferably, the atomic percentage content of D impurity element in the target powder material containing noble metal element is not more than 0.2%;
进一步地,在所述步骤S3之后还进行以下步骤:将所述包含贵金属元素的目标粉体材料筛分后,选择粒径范围为5μm~200μm的包含贵金属元素的目标粉体材料进行等离子球化处理,以得到呈球形的包含贵金属元素的粉体材料;Further, the following step is performed after the step S3: after sieving the target powder material containing noble metal elements, selecting the target powder material containing noble metal elements with a particle size range of 5 μm to 200 μm for plasma spheroidization processing to obtain spherical powder materials containing precious metal elements;
进一步地,所述呈球形的包含贵金属元素的粉体材料的粒径范围为5μm~200μm。Further, the particle size range of the spherical powder material containing noble metal elements is 5 μm˜200 μm.
本发明还涉及上述制备方法得到的包含贵金属元素的目标粉体材料或呈球形的包含贵金属元素的粉体材料在催化材料、粉末冶金、复合材料、吸波材料、杀菌材料、金属注射成型、3D打印、涂料中的应用。The present invention also relates to the target powder material containing noble metal elements obtained by the above preparation method or the spherical powder material containing noble metal elements in catalytic materials, powder metallurgy, composite materials, wave absorbing materials, sterilization materials, metal injection molding, 3D materials Printing, coating applications.
进一步地,如上述制备方法得到的呈球形的包含贵金属元素的粉体材料在金属粉3D打印领域中的应用,其特征在于,所述呈球形的包含贵金属元素的粉体材料的粒径范围为10μm~200μm。Further, the application of the spherical powder material containing noble metal elements obtained by the above preparation method in the field of metal powder 3D printing is characterized in that the particle size range of the spherical powder material containing noble metal elements is 10μm~200μm.
进一步地,如上述制备方法得到的包含贵金属元素的目标粉体材料或呈球形的包含贵金属元素的粉体材料在金属注射成型、粉末冶金中的应用,其特征在于,其粒径范围为0.1μm~200μm。Further, the application of the target powder material containing noble metal elements or the spherical powder material containing noble metal elements obtained by the above preparation method in metal injection molding and powder metallurgy, characterized in that the particle size range is 0.1 μm ~200 μm.
进一步地,如上述制备方法得到的包含贵金属元素的目标粉体材料在涂料、催化剂中的应用,其特征在于,粉体材料的粒径范围为2nm~5μm。Further, the application of the target powder material containing noble metal elements obtained by the above preparation method in coatings and catalysts is characterized in that the particle size of the powder material ranges from 2 nm to 5 μm.
本发明还涉及一种合金条带,其特征在于,包含内生粉与包覆体;所述合金条带的凝固组织包括基体相和弥散颗粒相,基体相即为所述包覆体,弥散颗粒相即为所述内生粉;所述包覆体的熔点低于所述内生粉,所述内生粉被包覆于所述包覆体中;The invention also relates to an alloy strip, which is characterized in that it includes endogenous powder and a coating body; the solidified structure of the alloy strip includes a matrix phase and a dispersed particle phase, and the matrix phase is the coating body, and the dispersed particles The phase is the endogenous powder; the melting point of the coating body is lower than the endogenous powder, and the endogenous powder is coated in the coating body;
所述始合金条带中内生粉的成分主要为(M xT y) x1D z1,包覆体的平均成分主要为Cu x2D z2;且99%≤x1≤100%,0≤z1≤1%;90%≤x2≤100%,0≤z2≤10%;z1≤d≤z2,2z1≤z2;x1、z1、x2、z2分别代表对应组成元素的原子百分比含量; The composition of the endogenous powder in the initial alloy strip is mainly (M x T y ) x1 D z1 , and the average composition of the clad is mainly Cu x2 D z2 ; and 99%≤x1≤100%, 0≤z1≤ 1%; 90%≤x2≤100%, 0≤z2≤10%; z1≤d≤z2, 2z1≤z2; x1, z1, x2, z2 respectively represent the atomic percentage content of the corresponding constituent elements;
作为优选,进一步地,99%≤x1<100%,0<z1≤1%;90%≤x2<100%,0<z2≤10%;z1<d<z2,2z1<z2;Preferably, further, 99%≤x1<100%, 0<z1≤1%; 90%≤x2<100%, 0<z2≤10%; z1<d<z2, 2z1<z2;
进一步地,z1<d<z2,且3z1<z2,Further, z1<d<z2, and 3z1<z2,
作为优选,99.5%≤x1<100%,0<z1≤0.5%;Preferably, 99.5%≤x1<100%, 0<z1≤0.5%;
作为进一步优选,99.8%≤x1<100%,0<z1≤0.2%;As a further preference, 99.8%≤x1<100%, 0<z1≤0.2%;
进一步地,所述M包含贵金属元素Ir、Ru、Re、Os、Tc、Au、Pt、Pd、Ag中的至少一种;作为优选,所述M包含贵金属元素Ir、Ru、Re、Os、Tc、Au、Pt、Pd、Ag中的至少一种,且Ir、Ru、Re、Os、Tc等元素在M中的原子百分比含量高于50%;作为进一步优选,所述M包含贵金属元素Ir、Ru、Re、Os、Tc中的至少一种;Further, the M contains at least one of the noble metal elements Ir, Ru, Re, Os, Tc, Au, Pt, Pd, and Ag; preferably, the M contains the noble metal elements Ir, Ru, Re, Os, Tc , at least one of Au, Pt, Pd, Ag, and the atomic percentage content of Ir, Ru, Re, Os, Tc and other elements in M is higher than 50%; as a further preference, the M contains noble metal elements Ir, At least one of Ru, Re, Os, Tc;
进一步地,所述T包含W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti、Fe中的至少一种;作为优选,所述T包含W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti、Fe中的至少一种,且W、Cr、Mo、V、Ta、Nb等元素在T中的原子百分比含量高于50%;作为进一步优选,所述T包含W、Cr、Mo、V、Ta、Nb中的至少一种;Further, the T includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti, and Fe; preferably, the T includes W, Cr, Mo, V, Ta, Nb , at least one of Zr, Hf, Ti, Fe, and the atomic percentage content of elements such as W, Cr, Mo, V, Ta, Nb in T is higher than 50%; as a further preference, the T contains W, At least one of Cr, Mo, V, Ta, Nb;
其中,所述D为杂质元素且包含O、H、N、P、S、F、Cl、I、Br中的至少一种;且这些杂质元素的总含量即为D杂质元素的含量;Wherein, the D is an impurity element and includes at least one of O, H, N, P, S, F, Cl, I, and Br; and the total content of these impurity elements is the content of D impurity elements;
进一步的,所述主要成分为(M xT y) x1D z1的合金条带中的内生粉中不含有Cu元素; Further, the endogenous powder in the alloy strip whose main component is (M x T y ) x1 D z1 does not contain Cu element;
作为优选,所述始合金条带中内生粉的成分为(M xT y) x1D z1,包覆体的平均成分为Cu x2D z2Preferably, the composition of the endogenous powder in the initial alloy strip is (M x T y ) x1 D z1 , and the average composition of the cladding body is Cu x2 D z2 ;
进一步地,所述合金条带的厚度范围为5μm~10mm;作为优选,所述合金条带的厚度范围为5μm~5mm;作为优选,所述合金条带的厚度范围为5μm~1mm;作为进一步优选,所述合金条带的厚度范围为5μm~200μm;作为进一步优选,所述合金条带的厚度范围为5μm~20μm。Further, the thickness of the alloy strip is in the range of 5 μm to 10 mm; preferably, the thickness of the alloy strip is in the range of 5 μm to 5 mm; preferably, the thickness of the alloy strip is in the range of 5 μm to 1 mm; as a further Preferably, the thickness of the alloy strip is in the range of 5 μm to 200 μm; as a further preference, the thickness of the alloy strip is in the range of 5 μm to 20 μm.
进一步地,所述合金条带横截面的宽度是其厚度的2倍以上;进一步地,所述初始合金条带的长度是其厚度的10倍以上;作为优选,所述初始合金条带的长度是其厚度的50倍以上;作为优选,所述初始合金条带的长度是其厚度的100倍以上。Further, the width of the cross section of the alloy strip is more than 2 times its thickness; further, the length of the initial alloy strip is more than 10 times its thickness; preferably, the length of the initial alloy strip is more than 50 times its thickness; preferably, the length of the initial alloy strip is more than 100 times its thickness.
进一步地,所述内生粉的粒径范围为2nm~3mm;作为优选,所述内生粉的粒径范围为2nm~500μm;作为优选,所述内生粉的粒径范围为2nm~99μm;作为进一步优选,所述内生粉的粒径范围为2nm~10μm;作为进一步优选,所述内生粉的粒径范围为2nm~1μm;作为进一步优选,所述内生粉的粒径范围为2nm~200nm;作为进一步优选,所述内生粉的粒径范围 为2nm~100nm。Further, the particle size range of the endogenous powder is 2nm~3mm; preferably, the particle size range of the endogenous powder is 2nm~500μm; preferably, the particle size range of the endogenous powder is 2nm~99μm ; As a further preference, the particle size range of the endogenous powder is 2nm~10μm; As a further preference, the particle diameter range of the endogenous powder is 2nm~1μm; As a further preference, the particle size range of the endogenous powder It is 2nm~200nm; as a further preference, the particle size range of the endogenous powder is 2nm~100nm.
进一步地,所述内生粉的形状包括枝晶形、球形、近球形、方块形、饼形、棒条形中的至少一种。Further, the shape of the endogenous powder includes at least one of dendritic shape, spherical shape, nearly spherical shape, square shape, cake shape, and rod shape.
进一步地,所述合金条带中内生粉中的单晶颗粒数目在所有内生粉数目中的占比不低于60%。Further, the number of single crystal particles in the endogenous powder in the alloy strip accounts for not less than 60% of the total number of endogenous powders.
进一步地,所述内生粉在所述合金条带中的体积百分含量不超过50%。Further, the volume percentage of the endogenous powder in the alloy strip does not exceed 50%.
进一步地,所述合金条带通过上述所述一种包含贵金属元素的粉体材料的制备方法中的步骤S1与步骤S2制备。Further, the alloy strip is prepared by step S1 and step S2 in the above-mentioned method for preparing a powder material containing a noble metal element.
需要说明的是,本发明所述方案中所述M、T或者D中还可以含有上述所列元素之外的其它元素或杂质元素。只要这些元素的引入或者含量的变化不引起初始合金凝固过程与规律发生“质变”的结果,都不影响本发明上述技术方案的实现。It should be noted that M, T or D in the solution of the present invention may also contain other elements or impurity elements other than those listed above. As long as the introduction of these elements or the changes in their contents do not cause a "qualitative change" in the solidification process and law of the initial alloy, it does not affect the realization of the above technical solutions of the present invention.
具体来说,所述初始合金凝固过程与规律不发生“质变”的结果,是指所述M、T或者D中含有上述所列元素之外的其它元素或杂质元素时,下述1)-3)所列事实过程与规律仍然存在:Specifically, the result that the initial alloy solidification process and law does not undergo "qualitative change" means that when the M, T or D contains other elements or impurity elements other than those listed above, the following 1)- 3) The listed factual processes and laws still exist:
1)所述初始合金条带中不含有主要由Cu与M,或Cu与T构成的金属间化合物;1) The initial alloy strip does not contain intermetallic compounds mainly composed of Cu and M, or Cu and T;
2)所述初始合金条带的凝固组织包括基体相和弥散颗粒相;所述基体相的熔点低于所述弥散颗粒相,所述弥散颗粒相被包覆于所述基体相中;2) The solidified structure of the initial alloy strip includes a matrix phase and a dispersed particle phase; the melting point of the matrix phase is lower than that of the dispersed particle phase, and the dispersed particle phase is coated in the matrix phase;
3)当初始合金熔体中D杂质含量不为0时,所述弥散颗粒相中D杂质含量低于所述初始合金熔体中的D杂质含量,且所述弥散颗粒相中D杂质含量的2倍仍然低于所述基体相中的D杂质含量。3) When the D impurity content in the initial alloy melt is not 0, the D impurity content in the dispersed particle phase is lower than the D impurity content in the initial alloy melt, and the D impurity content in the dispersed particle phase is less than 2 times is still lower than the D impurity content in the matrix phase.
本发明所述技术方案具有以下有益效果:The technical scheme of the present invention has the following beneficial effects:
首先,通过巧妙的合金设计,使得初始合金熔体凝固的时候发生相的分离,使得一定粒径目标成分的内生颗粒可以在初始合金熔体凝固过程中形成,并可以通过后续过程分离。一般来说,通过自下而上的化学方法,如化学还原,可以比较容易地制备纳米金属颗粒,但当颗粒的尺度增加到数百纳米甚至微米级时,则难以制备。通过自上而下的物理方法,如雾化法、球磨法等,可以比较容易地制备数十微米或者数百微米的金属颗粒,但当颗粒的尺度降低到数百纳米到几个微米时,则也很难制备。本发明的技术方案可以根据初始合金条带凝固过程中冷速的不同,非常容易地制备纳米级,亚微米级、微米级、甚至毫米级的目标金属粉颗粒,突破了上述技术难点,具有极大地优势。First, through ingenious alloy design, phase separation occurs when the initial alloy melt is solidified, so that endogenous particles of a certain particle size target composition can be formed during the solidification of the initial alloy melt and can be separated by subsequent processes. Generally speaking, nano-metal particles can be easily prepared by bottom-up chemical methods, such as chemical reduction, but when the size of the particles increases to hundreds of nanometers or even micrometers, it is difficult to prepare them. Metal particles of tens of microns or hundreds of microns can be easily prepared by top-down physical methods, such as atomization, ball milling, etc., but when the size of the particles is reduced to hundreds of nanometers to several microns, It is also difficult to prepare. The technical scheme of the present invention can easily prepare nano-, sub-micron, micron, and even millimeter-scale target metal powder particles according to the different cooling rates in the solidification process of the initial alloy strip, which overcomes the above technical difficulties and has extremely high performance. Earth advantage.
其次,实现了通过低纯原料获得高纯目标粉体材料,并为低纯原料制备高纯粉体材料指 出了一条新的途径,具有积极意义。本发明目标粉体材料纯度的提高主要通过以下三个机制实现:1)相对活性基体主元素Cu对初始合金熔体杂质元素的“吸收”作用。由于合金中Cu为低熔点元素,在合金熔体熔化及凝固过程中其与杂质元素D之间具有更强的亲和力,这可以使得初始合金熔体中的杂质元素D会更多地进入主要由Cu元素组成的基体相中;2)内生析出的弥散颗粒相形核长大过程中,杂质元素D会被排入剩余熔体中。只要凝固过程中内生析出的弥散颗粒相不晚于基体相析出,其杂质都会富集于最后凝固的那部分熔体,即主要由基体相主元素组成并凝固形成基体相的那部分熔体。3)由于基体相的存在,熔炼过程中由于坩埚与熔体相互作用从而进入熔体的与坩埚相关的杂质也一般集中在基体相中,从而进一步保证了弥散颗粒相的纯度,这就使得熔炼过程中对坩埚的要求进一步降低,极大地降低了生产成本。Secondly, the high-purity target powder materials were obtained from low-purity raw materials, and a new way was pointed out for the preparation of high-purity powder materials from low-purity raw materials, which was of positive significance. The improvement of the purity of the target powder material of the present invention is mainly achieved through the following three mechanisms: 1) The "absorption" effect of the main element Cu of the relative active matrix on the impurity elements of the initial alloy melt. Since Cu in the alloy is a low melting point element, it has a stronger affinity with the impurity element D during the melting and solidification of the alloy melt, which can make the impurity element D in the initial alloy melt enter more In the matrix phase composed of Cu element; 2) During the nucleation and growth of the endogenously precipitated dispersed particle phase, the impurity element D will be discharged into the remaining melt. As long as the endogenous precipitation of the dispersed particle phase is not later than the matrix phase in the solidification process, its impurities will be enriched in the last part of the melt that solidifies, that is, the part of the melt that is mainly composed of the main elements of the matrix phase and solidifies to form the matrix phase. . 3) Due to the existence of the matrix phase, the impurities related to the crucible entering the melt due to the interaction between the crucible and the melt during the smelting process are generally concentrated in the matrix phase, thereby further ensuring the purity of the dispersed particle phase, which makes the smelting process. The requirements for the crucible in the process are further reduced, which greatly reduces the production cost.
第三,可以获得以单晶颗粒为主的目标金属粉。相比多晶粉末,单晶粉末可以获得诸多显著且有益效果。在所述初始合金熔体凝固过程中,每一个内生弥散颗粒都是从熔体中某个位置形核后按照特定的原子排列方式长大生成。通过控制弥散颗粒相在初始合金条带中的体积百分含量不超过50%,确保每个内生颗粒可以弥散分布的情况下,各个内生颗粒之间难以发生合并长大。因此,最终获得的各个弥散分布的颗粒相大多都是单晶相。即使尺度大到数十微米或毫米级的枝晶颗粒,其每个次级枝晶的生长方向都与主枝晶的生长方向保持一定的位相关系,其仍然属于单晶颗粒。对于多晶材料来说,其晶界一般容易含有凝固过程中从晶内排出来的杂质元素,因此很难获得高纯的多晶粉体材料。而当目标金属粉主要由单晶颗粒组成时,其纯度必然能得到保障。而且,单晶颗粒表面原子具有特定的排列方式,如(111)面排列等,这些特定的排列方式会赋予目标金属粉特殊的力学、物理、化学性能,从而产生有益的效果。Third, the target metal powder mainly composed of single crystal particles can be obtained. Compared with polycrystalline powders, single crystal powders can achieve many significant and beneficial effects. During the solidification of the initial alloy melt, each endogenous dispersed particle grows and grows according to a specific atomic arrangement after nucleation from a certain position in the melt. By controlling the volume percentage of the dispersed particle phase in the initial alloy strip to not exceed 50%, it is difficult to merge and grow between individual endogenous particles under the condition that each endogenous particle can be dispersed and distributed. Therefore, most of the dispersed and distributed particle phases finally obtained are single crystal phases. Even if the size of dendrite particles is as large as tens of microns or millimeters, the growth direction of each secondary dendrite maintains a certain phase relationship with the growth direction of the main dendrite, which is still a single crystal particle. For polycrystalline materials, the grain boundaries generally contain impurity elements discharged from the grain during solidification, so it is difficult to obtain high-purity polycrystalline powder materials. When the target metal powder is mainly composed of single crystal particles, its purity must be guaranteed. Moreover, the atoms on the surface of the single crystal particles have specific arrangements, such as (111) plane arrangement, which will endow the target metal powder with special mechanical, physical and chemical properties, thereby producing beneficial effects.
第四,所述由内生粉与包覆体(基体相)构成的合金条带,创造性地利用原位生成的基体相包裹内生粉,保持了内生粉的高纯度与高活性。具体来说,无论传统化学方法还是物理方法所制备的金属或合金粉,尤其是比表面积极大的纳米粉,极易自然氧化,都面临粉末的保存困难问题。针对这一问题,本发明所涉及技术方案在制备出由内生金属粉与包覆体(基体相)构成的合金条带之后,可以并不急于将包覆体去除,而是直接利用包覆体保护内生金属粉不被自然氧化。这种由内生金属粉与包覆体构成的合金条带可以直接作为下游生产的原料,因此有成为一类特殊产品的潜力。当下游生产需要使用高纯粉体时,可以根据下一工序的特点,选择合适的时机并在合适的环境下将内生金属粉从合金条带中的包覆体中释放,再在尽可能短的时间使释放出来的内生粉进入下一生产流程,从而使内生金属粉受到氧等杂质污染的机会大大减少。例如,当内生金属粉为纳米粉时,可以在内生金属粉从包覆体中释放 的同时或者随后马上与树脂复合,从而制备具有高活性的内生金属粉添加的树脂基复合材料。Fourth, the alloy strip composed of the endogenous powder and the coating body (matrix phase) creatively utilizes the in-situ generated matrix phase to wrap the endogenous powder, thereby maintaining the high purity and high activity of the endogenous powder. Specifically, metal or alloy powders prepared by traditional chemical methods or physical methods, especially nano-powders with extremely large specific surface areas, are easily oxidized naturally and face the problem of difficulty in powder preservation. In order to solve this problem, after the alloy strip composed of endogenous metal powder and cladding body (matrix phase) is prepared in the technical solution of the present invention, the cladding body can not be removed in a hurry, but the cladding can be directly used. The body protects the endogenous metal powder from natural oxidation. This alloy strip composed of endogenous metal powder and cladding can be directly used as raw material for downstream production, so it has the potential to become a special product. When the downstream production needs to use high-purity powder, according to the characteristics of the next process, you can choose a suitable time and release the endogenous metal powder from the coating in the alloy strip under a suitable environment, and then as far as possible In a short time, the released endogenous powder enters the next production process, so that the chance of endogenous metal powder being contaminated by impurities such as oxygen is greatly reduced. For example, when the endogenous metal powder is nano-powder, the endogenous metal powder can be compounded with the resin at the same time as the endogenous metal powder is released from the cladding or immediately afterward, thereby preparing the resin-based composite material with the addition of endogenous metal powder with high activity.
第五,所述步骤S2中通过凝固获得的固态合金为条带状,其保证了产品形状的均一性与大规模生产的可行性。当合金条带为薄合金条带时,可以通过甩带法制备,只要维持合金熔体流向旋转辊的流量固定,旋转辊的转速固定,就可以获得厚度均一的合金薄带,而且该制备过程可以连续进行,利于大规模生产。当合金条带为厚合金条带时,可以通过成熟的连铸法制备,连铸的原理与甩带法的原理相似,也可以通过熔体获得连续且厚度均一的厚带,制备过程也可以连续进行,利于大规模生产。当合金条带厚度均一时,冷速也较为均匀,获得弥散颗粒粒度也较为均匀。相比而言,如果凝固获得的固态合金为铸锭状时,根据常识,铸锭没有均一的厚度,也没有明显的长度及端点,一般会导致内部熔体散热困难,容易获得异常大的内生颗粒,只有单纯需要对大的内生颗粒进行收集并对其提纯的时候才需要这样操作。而且普通铸锭难以连续生产。因此,本发明通过凝固获得合金条带,适合后续通过“去相法”进行粉体材料的制备。Fifth, the solid alloy obtained by solidification in the step S2 is in the shape of a strip, which ensures the uniformity of the product shape and the feasibility of mass production. When the alloy strip is a thin alloy strip, it can be prepared by the stripping method. As long as the flow rate of the alloy melt flowing to the rotating roll is kept constant and the rotation speed of the rotating roll is fixed, an alloy thin strip with a uniform thickness can be obtained, and the preparation process It can be carried out continuously, which is beneficial to large-scale production. When the alloy strip is a thick alloy strip, it can be prepared by a mature continuous casting method. The principle of continuous casting is similar to that of the strip method, and a continuous and uniform thick strip can also be obtained through the melt. The preparation process can also It is carried out continuously, which is beneficial to large-scale production. When the thickness of the alloy strip is uniform, the cooling rate is also relatively uniform, and the particle size of the obtained dispersed particles is relatively uniform. In contrast, if the solid alloy obtained by solidification is in the shape of an ingot, according to common sense, the ingot has no uniform thickness, and no obvious length and endpoints, which generally leads to difficulty in dissipating heat from the internal melt, and it is easy to obtain abnormally large internal melts. Green particles, this is only necessary when the large endogenous particles simply need to be collected and purified. Moreover, it is difficult to continuously produce ordinary ingots. Therefore, the present invention obtains alloy strips by solidification, which is suitable for subsequent preparation of powder materials by "dephase method".
因此,本发明的制备方法具有工艺简单、易于操作、成本低的特点,可以制备包括纳米级、亚微米级、以及微米级的多种包含贵金属元素的高纯粉体材料,在催化材料、粉末冶金、复合材料、吸波材料、杀菌材料、金属注射成型、3D打印、涂料等领域具有很好的应用前景。Therefore, the preparation method of the present invention has the characteristics of simple process, easy operation and low cost, and can prepare a variety of high-purity powder materials containing noble metal elements including nano-scale, sub-micron-scale and micro-scale. Metallurgy, composite materials, wave absorbing materials, sterilization materials, metal injection molding, 3D printing, coatings and other fields have good application prospects.
作为备选方案,本发明还提供一种金属粉末的制备方法,其包括以下步骤:As an alternative solution, the present invention also provides a method for preparing metal powder, which comprises the following steps:
步骤一:选择成分为Cu aM bT c的初始合金,M选自Ir、Ru、Re、Os、Tc中的至少一种,T选自W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti、Fe中的至少一种;a、b、c代表对应组成元素的原子百分比含量,且50%≤a≤99.9%,0.1%≤b≤50%,0≤c≤49.9%,a+b+c=100%;按照初始合金成分配比将初始合金原料熔化,得到均匀的合金熔体,然后通过快速凝固技术将合金熔体凝固成Cu aM bT c中间合金;所述Cu aM bT c中间合金凝固组织由成分为Cu的基体相以及成分为M-T的弥散颗粒相组成,且M-T弥散颗粒相的熔点高于Cu基体相的熔点;作为优选,0.2%≤b≤50%,c=0,a+b+c=100%; Step 1: Select an initial alloy with a composition of Cu a M b T c , M is selected from at least one of Ir, Ru, Re, Os, Tc, T is selected from W, Cr, Mo, V, Ta, Nb, Zr , at least one of Hf, Ti, Fe; a, b, c represent the atomic percentage content of the corresponding constituent elements, and 50%≤a≤99.9%, 0.1%≤b≤50%, 0≤c≤49.9%, a+b+c=100%; the initial alloy raw material is melted according to the initial alloy composition ratio to obtain a uniform alloy melt, and then the alloy melt is solidified into a Cu a M b T c master alloy by rapid solidification technology; The solidification structure of the Cu a M b T c master alloy is composed of a matrix phase composed of Cu and a dispersed particle phase composed of MT, and the melting point of the MT dispersed particle phase is higher than that of the Cu matrix phase; preferably, 0.2%≤b≤ 50%, c=0, a+b+c=100%;
步骤二:将所述Cu aM bT c中间合金中的Cu基体相通过酸溶液反应去除,同时保留不与该酸溶液反应的M-T弥散颗粒相,即得到由M-T弥散颗粒相组成的目标金属粉末。 Step 2: The Cu matrix phase in the Cu a M b T c master alloy is removed by the acid solution reaction, while retaining the MT dispersed particle phase that does not react with the acid solution, that is, the target metal composed of the MT dispersed particle phase is obtained. powder.
通过上述技术方案,可以实现超细金属粉末的制备。中间合金熔体凝固速率越高,所获得的中间合金凝固组织中弥散颗粒相就越小。因此,本发明可以通过控制凝固速率的大小分别获得纳米级、亚微米级、以及微米级的弥散颗粒相,然后通过去除Cu基体相获得相应粒径大小的目标金属粉末,极大地降低了超细金属粉末的制备成本。Through the above technical solution, the preparation of ultrafine metal powder can be realized. The higher the solidification rate of the master alloy melt, the smaller the dispersed particle phase in the obtained master alloy solidified structure. Therefore, the present invention can obtain nano-scale, sub-micron-scale and micro-scale dispersed particle phases by controlling the size of the solidification rate, and then obtain the target metal powder with the corresponding particle size by removing the Cu matrix phase, which greatly reduces the ultra-fine particle size. Manufacturing cost of metal powder.
进一步地,所述快速凝固技术包括合金熔体金属辊甩带法,且所述合金熔体的凝固速率 为100K/s~1×10 7K/s。 Further, the rapid solidification technology includes the alloy melt metal rolling strip method, and the solidification rate of the alloy melt is 100K/s˜1×10 7 K/s.
进一步地,所述快速凝固技术包括合金熔体雾化制粉法,且所述合金熔体的凝固速率为50K/s~5×10 5K/s。 Further, the rapid solidification technology includes an alloy melt atomization pulverization method, and the solidification rate of the alloy melt is 50K/s˜5×10 5 K/s.
进一步地,针对所述初始合金成分,当凝固速率高于5×10 4K/s时,可以获得纳米级(2nm~200nm)的弥散颗粒相;当凝固速率为1×10 3K/s~5×10 4K/s时,可以获得亚微米级(200nm~1000nm)的弥散颗粒相;当凝固速率低于1×10 3K/s时,可以获得微米级(>1μm)的弥散颗粒相。 Further, for the initial alloy composition, when the solidification rate is higher than 5×10 4 K/s, a nanoscale (2nm~200nm) dispersed particle phase can be obtained; when the solidification rate is 1×10 3 K/s~ At 5×10 4 K/s, submicron (200nm~1000nm) dispersed particles can be obtained; when the solidification rate is lower than 1×10 3 K/s, micron (>1μm) dispersed particles can be obtained .
进一步地,所述Cu aM bT c中间合金在三维尺度方向上至少有一维的尺度范围为5μm~500μm。当采取金属辊甩带法制备条带状中间合金时,特指中间合金条带的厚度范围为5μm~500μm;当采取熔体雾化制粉技术制备粉末状中间合金时,特指中间合金粉末的直径范围为5μm~500μm; Further, the Cu a M b T c master alloy has at least one dimension in the three-dimensional dimension direction ranging from 5 μm to 500 μm. When the strip-shaped master alloy is prepared by the metal roll stripping method, the thickness of the master alloy strip is in the range of 5 μm to 500 μm; when the powdered master alloy is prepared by the melt atomization powder milling technology, the thickness of the master alloy strip is specified. The diameter range of 5μm ~ 500μm;
进一步地,所述雾化制粉技术包括气雾化、水雾化、水汽-联合雾化、真空雾化中的至少一种。Further, the atomization and pulverization technology includes at least one of gas atomization, water atomization, water vapor-combined atomization, and vacuum atomization.
进一步地,所述中间合金凝固组织中弥散颗粒相的形状包括枝晶形、球形、近球形、方块形、饼形、棒形中的至少一种,且其颗粒大小范围为2nm~100μm。Further, the shape of the dispersed particle phase in the solidified structure of the master alloy includes at least one of dendritic, spherical, nearly spherical, square, cake, and rod, and the particle size ranges from 2 nm to 100 μm.
进一步地,所述酸溶液包括盐酸、硫酸、硝酸、磷酸、高氯酸、乙酸、草酸中的至少一种。所述酸的配比以及酸的浓度以确保Cu基体能够被反应去除,同时M-T弥散颗粒相不与该酸反应为准。由于M-T弥散颗粒相主要由极耐酸的元素组成,而Cu可以与某些酸,如与浓度高于的2mol/L盐酸水溶液明显反应,因此可以依据中间合金的具体组成与配比,通过合适的酸溶液配比与浓度设计实现Cu基体相的去除,同时保留M-T弥散颗粒相。当M-T中含有Fe时,由于极耐酸的M类或其它T类元素的保护作用,Fe难以与酸反应被去除。因此,制备含有Fe时M-T金属粉末也是可行的。Further, the acid solution includes at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, acetic acid, and oxalic acid. The ratio of the acid and the concentration of the acid are to ensure that the Cu matrix can be removed by reaction, and the M-T dispersed particle phase does not react with the acid. Since the MT dispersed particle phase is mainly composed of extremely acid-resistant elements, and Cu can react significantly with some acids, such as 2 mol/L hydrochloric acid aqueous solution with a concentration higher than 2 mol/L, it can be determined according to the specific composition and ratio of the master alloy. The acid solution ratio and concentration are designed to remove the Cu matrix phase while retaining the MT dispersed particle phase. When Fe is contained in M-T, it is difficult for Fe to react with acid to be removed due to the protective effect of extremely acid-resistant M-type or other T-type elements. Therefore, it is also feasible to prepare M-T metal powders containing Fe.
进一步地,所述由弥散颗粒相组成的目标金属粉末的粒径范围为2nm~100μm。Further, the particle size range of the target metal powder composed of the dispersed particle phase is 2 nm˜100 μm.
进一步地,所述目标金属粉末的形状包括枝晶形、球形、近球形、方块形、饼形、棒形中的至少一种。Further, the shape of the target metal powder includes at least one of dendritic shape, spherical shape, nearly spherical shape, square shape, pie shape, and rod shape.
以下进一步详细说明本发明的技术特点:Describe the technical characteristics of the present invention in further detail below:
首先,本发明可以通过控制熔体凝固速率的大小分别获得纳米级、亚微米级、以及微米级的弥散颗粒相,然后通过去除基体相获得相应粒径大小的目标金属粉,极大地降低了超细金属粉的制备成本。First, the present invention can obtain nano-scale, sub-micron-scale, and micro-scale dispersed particle phases by controlling the size of the melt solidification rate, and then obtain the target metal powder with the corresponding particle size by removing the matrix phase, which greatly reduces the superfluous particle size. Preparation cost of fine metal powder.
其次,当所述Cu aM bT c合金中M-T为多种元素的组合时,所得弥散颗粒相也为多种元素组成,这就使得制备由弥散颗粒相组成的目标合金粉末变得更为简便可行,极大地扩展了目 标合金粉末的成分范围与应用领域。 Secondly, when the MT in the Cu a M b T c alloy is a combination of multiple elements, the resulting dispersed particle phase is also composed of multiple elements, which makes it easier to prepare the target alloy powder composed of the dispersed particle phase. It is simple and feasible, and greatly expands the composition range and application field of the target alloy powder.
因此,本备选方案发明的制备方法具有工艺简单、易于操作、成本低的特点,可以制备包括纳米级、亚微米级以及微米级的多种金属粉末,在催化、粉末冶金、复合材料等领域具有很好的应用前景。Therefore, the preparation method invented by this alternative solution has the characteristics of simple process, easy operation and low cost, and can prepare various metal powders including nano-scale, sub-micron and micro-scale, and is used in the fields of catalysis, powder metallurgy, composite materials, etc. Has a very good application prospect.
具体实施方式detailed description
以下,将通过以下具体实施例对所述高纯金属粉的制备方法做进一步的说明。Hereinafter, the preparation method of the high-purity metal powder will be further described by the following specific examples.
实施例1Example 1
本实施例提供一种纳米Ru粉的制备方法,该制备方法包括如下步骤:The present embodiment provides a preparation method of nano Ru powder, and the preparation method comprises the following steps:
选用原子比配方为Cu 90Ru 10的合金,按照配方称取原料,将该初始合金原料熔化均匀后,通过铜辊甩带技术以10 6K/s的凝固速率制备成厚度为15μm的Cu 90Ru 10中间合金条带。该合金条带的凝固组织由成分为Cu的基体相与大量成分为Ru的弥散颗粒相组成,其中Ru颗粒的形状为近球形,粒径大小范围为3nm~150nm。 The alloy with the atomic ratio formula of Cu 90 Ru 10 was selected, and the raw materials were weighed according to the formula. After the initial alloy raw materials were melted uniformly, Cu 90 with a thickness of 15 μm was prepared by the copper roller stripping technique at a solidification rate of 10 6 K/s. Ru 10 master alloy strip. The solidified structure of the alloy strip is composed of a matrix phase with a composition of Cu and a large amount of dispersed particles with a composition of Ru, wherein the shape of the Ru particles is nearly spherical, and the particle size ranges from 3 nm to 150 nm.
通过6mol/L的盐酸水溶液将中间合金条带中的Cu基体反应去除,使得中间合金条带中难以与该浓度盐酸水溶液反应的Ru颗粒脱离出来,即得到纳米Ru粉,其粒径大小范围为3nm~150nm。The Cu matrix in the master alloy strip is removed by the reaction of 6 mol/L hydrochloric acid aqueous solution, so that the Ru particles in the master alloy strip that are difficult to react with the hydrochloric acid aqueous solution of this concentration are detached, that is, nano Ru powder is obtained, and its particle size is in the range of 3nm~150nm.
实施例2Example 2
本实施例提供一种纳米Ru粉的制备方法,该制备方法包括如下步骤:The present embodiment provides a preparation method of nano Ru powder, and the preparation method comprises the following steps:
选用原子比配方为Cu 95Ru 5的合金,按照配方称取原料,将该初始合金原料熔化均匀后,通过气雾化技术将合金熔体以5×10 4K/s的凝固速率制备成粒径范围为5μm-100μm的Cu 95Ru 5中间合金粉末。该中间合金粉末的凝固组织由成分为Cu的基体相与大量成分为Ru的弥散颗粒相组成,其中Ru弥散颗粒的形状为近球形,粒径大小范围为50nm~200nm。 The alloy with the atomic ratio formula of Cu 95 Ru 5 is selected, and the raw materials are weighed according to the formula. After the initial alloy raw material is melted uniformly, the alloy melt is prepared into granules at a solidification rate of 5×10 4 K/s by gas atomization technology. Cu 95 Ru 5 master alloy powder with diameters ranging from 5 μm to 100 μm. The solidification structure of the master alloy powder is composed of a matrix phase with a composition of Cu and a large amount of dispersed particles with a composition of Ru, wherein the shape of the Ru dispersed particles is nearly spherical, and the particle size ranges from 50nm to 200nm.
通过6mol/L的盐酸水溶液将中间合金粉末中的Cu基体反应去除,使得中间合金粉末中难以与该浓度盐酸水溶液反应的Ru颗粒脱离出来,即得到纳米Ru粉,其粒径大小范围为50nm~200nm。The Cu matrix in the master alloy powder is removed by the reaction of 6 mol/L hydrochloric acid aqueous solution, so that the Ru particles in the master alloy powder that are difficult to react with the hydrochloric acid aqueous solution of this concentration are detached, that is, nano Ru powder is obtained, and its particle size ranges from 50 nm to 50 nm. 200nm.
实施例3Example 3
本实施例提供一种亚微米Ir-Nb粉的制备方法,该制备方法包括如下步骤:The present embodiment provides a preparation method of submicron Ir-Nb powder, and the preparation method comprises the following steps:
选用原子比配方为Cu 70Ir 15Nb 15的合金,按照配方称取原料,将该初始合金原料熔化均匀后,通过气雾化技术将合金熔体以10 4K/s的凝固速率制备成粒径范围为10μm-150μm的 Ir 50Nb 50中间合金粉末。该中间合金粉末的凝固组织由成分为Cu的基体相与大量成分为Ir 50Nb 50的弥散颗粒相组成,其中Ir 50Nb 50弥散颗粒的形状为近球形,粒径大小范围为50nm~1000nm。 The alloy with the atomic ratio formula of Cu 70 Ir 15 Nb 15 is selected, the raw materials are weighed according to the formula, and after the initial alloy raw material is melted uniformly, the alloy melt is prepared into granules at a solidification rate of 10 4 K/s by gas atomization technology Ir 50 Nb 50 master alloy powder with diameters ranging from 10 μm to 150 μm. The solidification structure of the master alloy powder is composed of a matrix phase with a composition of Cu and a large number of dispersed particle phases with a composition of Ir 50 Nb 50 , wherein the shape of the Ir 50 Nb 50 dispersed particles is nearly spherical, and the particle size ranges from 50nm to 1000nm.
通过6mol/L的盐酸水溶液将中间合金粉末中的Cu基体反应去除,使得中间合金粉末中难以与该浓度盐酸水溶液反应的Ir 50Nb 50颗粒脱离出来,即得到亚微米Ir 50Nb 50粉,其粒径大小范围为50nm~1000nm。 The Cu matrix in the master alloy powder is removed by the reaction of the 6 mol/L hydrochloric acid aqueous solution, so that the Ir 50 Nb 50 particles in the master alloy powder that are difficult to react with the aqueous hydrochloric acid solution of this concentration are separated out, that is, the submicron Ir 50 Nb 50 powder is obtained. The particle size ranges from 50nm to 1000nm.
实施例4Example 4
本实施例提供一种纳米Ru-Ir-Os-Fe粉的制备方法,该制备方法包括如下步骤:This embodiment provides a preparation method of nano Ru-Ir-Os-Fe powder, and the preparation method includes the following steps:
选用原子比配方为Cu 90Ru 2.5Ir 2.5Os 2.5Fe 2.5的合金,按照配方称取原料,将该初始合金原料熔化均匀后,通过铜辊甩带技术以10 6K/s的凝固速率制备成厚度为15μm的Cu 90Ru 2.5Ir 2.5Os 2.5Fe 2.5中间合金条带。该合金条带的凝固组织由成分为Cu的基体相与大量成分为Ru 25Ir 25Os 25Fe 25的弥散颗粒相组成,其中Ru 25Ir 25Os 25Fe 25颗粒的形状为近球形,粒径大小范围为3nm~150nm。 An alloy whose atomic ratio formula is Cu 90 Ru 2.5 Ir 2.5 Os 2.5 Fe 2.5 is selected, and the raw materials are weighed according to the formula. After the initial alloy raw material is melted uniformly, it is prepared by copper roller stripping technology at a solidification rate of 10 6 K/s. Cu 90 Ru 2.5 Ir 2.5 Os 2.5 Fe 2.5 master alloy strips with a thickness of 15 μm. The solidification structure of the alloy strip is composed of a matrix phase with a composition of Cu and a large amount of dispersed particles with a composition of Ru 25 Ir 25 Os 25 Fe 25 , wherein the shape of the Ru 25 Ir 25 Os 25 Fe 25 particles is nearly spherical, and the particle size is The size range is from 3nm to 150nm.
通过5mol/L的盐酸水溶液将中间合金条带中的Cu基体反应去除,使得中间合金条带中难以与该浓度盐酸水溶液反应的Ru 25Ir 25Os 25Fe 25颗粒脱离出来,即得到纳米Ru 25Ir 25Os 25Fe 25粉,其粒径大小范围为3nm~150nm。 The Cu matrix in the master alloy strip is reacted and removed by a 5 mol/L hydrochloric acid aqueous solution, so that the Ru 25 Ir 25 Os 25 Fe 25 particles in the master alloy strip that are difficult to react with the aqueous hydrochloric acid solution of this concentration are separated out, that is, nano Ru 25 is obtained. The Ir 25 Os 25 Fe 25 powder has a particle size range of 3nm to 150nm.
实施例5Example 5
本实施例提供了一种亚微米W-Re粉的制备方法,该制备方法包括如下步骤:The present embodiment provides a preparation method of submicron W-Re powder, and the preparation method comprises the following steps:
选用原子比配方为Cu 90W 5Re 5的合金,按照配方称取原料,将该初始合金原料熔化均匀后,通过铜辊甩带技术以10 4K/s的凝固速率制备成厚度为150μm的Cu 90W 5Re 5中间合金条带。该合金条带的凝固组织由成分为Cu的基体相与大量成分为W 50Re 50的弥散颗粒相组成,其中Ru 25Ir 25Os 25Fe 25颗粒的形状为近球形,粒径大小范围为50nm~1000nm。 The alloy with the atomic ratio formula of Cu 90 W 5 Re 5 was selected, and the raw materials were weighed according to the formula. After the initial alloy raw materials were melted uniformly, the copper roller stripping technique was used to prepare the alloy with a thickness of 150 μm at a solidification rate of 10 4 K/s. Cu 90 W 5 Re 5 master alloy strip. The solidification structure of the alloy strip is composed of a matrix phase with a composition of Cu and a large amount of dispersed particles with a composition of W 50 Re 50 , wherein the shape of the Ru 25 Ir 25 Os 25 Fe 25 particles is nearly spherical, and the particle size range is 50 nm. ~1000nm.
通过6mol/L的盐酸水溶液将中间合金条带中的Cu基体反应去除,使得中间合金条带中难以与该浓度盐酸水溶液反应的W 50Re 50颗粒脱离出来,即得到亚微米W 50Re 50粉,其粒径大小范围为50nm~1000nm。 The Cu matrix in the master alloy strip is removed by the reaction of 6 mol/L hydrochloric acid aqueous solution, so that the W 50 Re 50 particles in the master alloy strip that are difficult to react with the hydrochloric acid aqueous solution of this concentration are detached, that is, sub-micron W 50 Re 50 powder is obtained. , and its particle size ranges from 50 nm to 1000 nm.
实施例6Example 6
本实施例提供了一种微米Ir-Ta-Nb-V粉的制备方法,该制备方法包括如下步骤:The present embodiment provides a preparation method of micron Ir-Ta-Nb-V powder, and the preparation method comprises the following steps:
选用原子比配方为Cu 80Ir 5Ta 5Nb 5V 5的合金,按照配方称取原料,将该初始合金原料熔化 均匀后,通过铜辊甩带技术以500K/s的凝固速率制备成厚度为500μm的Cu 80Ir 5Ta 5Nb 5V 5中间合金条带。该合金条带的凝固组织由成分为Cu的基体相与大量成分为Ir 25Ta 25Nb 25V 25的弥散颗粒相组成,其中Ir 25Ta 25Nb 25V 25颗粒的形状为枝晶形,粒径大小范围为1μm~50μm。 The alloy whose atomic ratio formula is Cu 80 Ir 5 Ta 5 Nb 5 V 5 is selected, and the raw materials are weighed according to the formula. After the initial alloy raw material is melted uniformly, it is prepared into a thickness of 500 μm Cu 80 Ir 5 Ta 5 Nb 5 V 5 master alloy strip. The solidification structure of the alloy strip is composed of a matrix phase with a composition of Cu and a large amount of dispersed particles with a composition of Ir 25 Ta 25 Nb 25 V 25 , wherein the shape of the Ir 25 Ta 25 Nb 25 V 25 particles is dendritic, and the particle size is dendritic. The size ranges from 1 μm to 50 μm.
通过6mol/L的盐酸水溶液将中间合金条带中的Cu基体反应去除,使得中间合金条带中难以与该浓度盐酸水溶液反应的Ir 25Ta 25Nb 25V 25颗粒脱离出来,即得到微米Ir 25Ta 25Nb 25V 25粉,其粒径大小范围为1μm~50μm。 The Cu matrix in the master alloy strip is reacted and removed by a 6 mol/L hydrochloric acid aqueous solution, so that the Ir 25 Ta 25 Nb 25 V 25 particles in the master alloy strip that are difficult to react with the aqueous hydrochloric acid solution of this concentration are detached, and the micron Ir 25 is obtained. Ta 25 Nb 25 V 25 powder has a particle size range of 1 μm to 50 μm.
实施例7Example 7
本实施例提供了一种纳米Ir-Ta-Nb-Cr-Zr粉的制备方法,该制备方法包括如下步骤:This embodiment provides a preparation method of nano-Ir-Ta-Nb-Cr-Zr powder, and the preparation method includes the following steps:
选用原子比配方为Cu 75Ir 6Ta 6Nb 6Cr 6Zr 1的合金,按照配方称取原料,将该初始合金原料熔化均匀后,通过铜辊甩带技术以10 6K/s的凝固速率制备成厚度为15μm的Cu 75Ir 6Ta 6Nb 6Cr 6Zr 1中间合金条带。该合金条带的凝固组织由成分为Cu的基体相与大量成分为Ir 24Ta 24Nb 24Cr 24Zr 4的弥散颗粒相组成,其中Ir 24Ta 24Nb 24Cr 24Zr 4颗粒的形状为近球形,粒径大小范围为3nm~150nm。 An alloy whose atomic ratio formula is Cu 75 Ir 6 Ta 6 Nb 6 Cr 6 Zr 1 is selected, the raw materials are weighed according to the formula, and the initial alloy raw materials are melted uniformly, and the solidification rate of 10 6 K/s is carried out by the copper roller stripping technique. A Cu 75 Ir 6 Ta 6 Nb 6 Cr 6 Zr 1 master alloy strip with a thickness of 15 μm was prepared. The solidification structure of the alloy strip is composed of a matrix phase with a composition of Cu and a large number of dispersed particles with a composition of Ir 24 Ta 24 Nb 24 Cr 24 Zr 4 , wherein the shape of the Ir 24 Ta 24 Nb 24 Cr 24 Zr 4 particles is nearly Spherical, with particle size ranging from 3nm to 150nm.
通过5mol/L的盐酸水溶液将中间合金条带中的Cu基体反应去除,使得中间合金条带中难以与该浓度盐酸水溶液反应的Ir 24Ta 24Nb 24Cr 24Zr 4颗粒脱离出来,即得到纳米Ir 24Ta 24Nb 24Cr 24Zr 4粉,其粒径大小范围为3nm~150nm。 The Cu matrix in the master alloy strip is removed by the reaction of 5 mol/L hydrochloric acid aqueous solution, so that the Ir 24 Ta 24 Nb 24 Cr 24 Zr 4 particles in the master alloy strip that are difficult to react with the hydrochloric acid aqueous solution of this concentration are detached, and the nanometer particles are obtained. The Ir 24 Ta 24 Nb 24 Cr 24 Zr 4 powder has a particle size range of 3nm to 150nm.
实施例8Example 8
本实施例提供一种纳米Ir-Nb粉的制备方法,该制备方法包括如下步骤:The present embodiment provides a preparation method of nano-Ir-Nb powder, and the preparation method comprises the following steps:
选用D(包含O、H、N、P、S、F、Cl、Br、I)杂质元素的原子百分比含量分别为0.2at.%、0.5at.%、0.5at.%的Cu,Ir与Nb原料,按照Cu:Ir:Nb的摩尔比约为70:15:15的比例将原料熔化,得到原子百分比成分主要为Cu 69.9Ir 14.9Nb 14.9D 0.3的均匀初始合金熔体。 Select D (including O, H, N, P, S, F, Cl, Br, I) impurity elements with atomic percentage content of 0.2at.%, 0.5at.%, 0.5at.% Cu, Ir and Nb respectively The raw material is melted according to the molar ratio of Cu:Ir:Nb about 70:15:15 to obtain a homogeneous initial alloy melt whose atomic percentage composition is mainly Cu 69.9 Ir 14.9 Nb 14.9 D 0.3 .
通过铜辊甩带技术以约~10 6K/s的凝固速率将初始合金熔体制备成厚度为~20μm的Cu 69.9Ir 14.9Nb 14.9D 0.3合金条带。该合金条带的凝固组织由原子百分比成分主要为Cu 99.6D 0.4的基体相与大量成分主要为Ir 49.97Nb 49.97D 0.06的弥散颗粒相组成。其中Ir 49.97Nb 49.97D 0.06弥散颗粒的形状为近球形,其粒径大小范围为10nm~150nm。Ir 49.97Nb 49.97D 0.06弥散颗粒在合金条带中的体积百分含量约为37%; The initial alloy melt was prepared into Cu 69.9 Ir 14.9 Nb 14.9 D 0.3 alloy ribbons with a thickness of ˜20 μm by copper roll stripping technique at a solidification rate of about ˜10 6 K/s. The solidification structure of the alloy strip is composed of a matrix phase whose atomic percentage composition is mainly Cu 99.6 D 0.4 and a large amount of dispersed particle phase whose composition is mainly Ir 49.97 Nb 49.97 D 0.06 . The Ir 49.97 Nb 49.97 D 0.06 dispersed particles are nearly spherical in shape, and their particle size ranges from 10 nm to 150 nm. The volume percentage of Ir 49.97 Nb 49.97 D 0.06 dispersed particles in the alloy strip is about 37%;
通过4mol/L的盐酸水溶液在40℃下与Cu 69.9Ir 14.9Nb 14.9D 0.3合金条带,合金条带中的Cu基体被腐蚀去掉,从而得到Ir 49.97Nb 49.97D 0.06弥散颗粒,其粒径大小范围为10nm~150nm。且纳米Ir 49.97Nb 49.97D 0.06中O、H、N、P、S、F、Cl、Br、I的总含量为0.06at.%。 Through 4 mol/L hydrochloric acid aqueous solution at 40 ℃ and Cu 69.9 Ir 14.9 Nb 14.9 D 0.3 alloy strips, the Cu matrix in the alloy strips is corroded and removed, so as to obtain Ir 49.97 Nb 49.97 D 0.06 dispersed particles, the particle size of which is The range is 10nm to 150nm. And the total content of O, H, N, P, S, F, Cl, Br, and I in the nano Ir 49.97 Nb 49.97 D 0.06 is 0.06 at.%.
实施例9Example 9
本实施例提供一种纳米Ir-Pt粉的制备方法,该制备方法包括如下步骤:The present embodiment provides a preparation method of nano-Ir-Pt powder, and the preparation method comprises the following steps:
选用D(包含O、H、N、P、S、F、Cl、Br、I)杂质元素的原子百分比含量分别为0.2at.%、0.5at.%、0.5at.%的Cu,Ir与Pt原料,按照Cu:Ir:Pt的摩尔比约为70:20:10的比例将原料熔化,得到原子百分比成分主要为Cu 69.85Ir 19.9Pt 9.95D 0.3的均匀初始合金熔体。 Select D (including O, H, N, P, S, F, Cl, Br, I) impurity elements with atomic percentage content of 0.2at.%, 0.5at.%, 0.5at.% Cu, Ir and Pt respectively The raw material is melted according to the molar ratio of Cu:Ir:Pt about 70:20:10 to obtain a homogeneous initial alloy melt whose atomic percentage composition is mainly Cu 69.85 Ir 19.9 Pt 9.95 D 0.3 .
通过铜辊甩带技术以约~10 6K/s的凝固速率将初始合金熔体制备成厚度为~20μm的Cu 69.85Ir 19.9Pt 9.95D 0.3合金条带。该合金条带的凝固组织由原子百分比成分主要为Cu 99.6D 0.4的基体相与大量成分主要为Ir 66.62Pt 33.31D 0.07的弥散颗粒相组成。其中Ir 66.62Pt 33.31D 0.07弥散颗粒的形状为近球形,其粒径大小范围为10nm~150nm。Ir 66.62Pt 33.31D 0.07弥散颗粒在合金条带中的体积百分含量约为34%; The initial alloy melt was prepared into Cu 69.85 Ir 19.9 Pt 9.95 D 0.3 alloy strips with a thickness of ~20 μm by copper roll stripping technique at a solidification rate of about ~10 6 K/s. The solidification structure of the alloy strip is composed of a matrix phase whose atomic percentage is mainly Cu 99.6 D 0.4 and a large amount of which is a dispersed particle phase which is mainly Ir 66.62 Pt 33.31 D 0.07 . The Ir 66.62 Pt 33.31 D 0.07 dispersed particles are nearly spherical in shape, and their particle size ranges from 10 nm to 150 nm. The volume percentage of Ir 66.62 Pt 33.31 D 0.07 dispersed particles in the alloy strip is about 34%;
通过4mol/L的盐酸水溶液在40℃下与Cu 69.85Ir 19.9Pt 9.95D 0.3合金条带,合金条带中的Cu基体被腐蚀去掉,从而得到Ir 66.62Pt 33.31D 0.07弥散颗粒,其粒径大小范围为10nm~150nm。且纳米Ir 66.62Pt 33.31D 0.07中O、H、N、P、S、F、Cl、Br、I的总含量为0.07at.%。 Through 4 mol/L hydrochloric acid aqueous solution at 40 ℃ and Cu 69.85 Ir 19.9 Pt 9.95 D 0.3 alloy strip, the Cu matrix in the alloy strip is corroded and removed, so as to obtain Ir 66.62 Pt 33.31 D 0.07 dispersed particles, the particle size of which is The range is 10nm to 150nm. And the total content of O, H, N, P, S, F, Cl, Br, and I in the nano Ir 66.62 Pt 33.31 D 0.07 is 0.07 at.%.
实施例10Example 10
本实施例提供一种纳米Ir-Nb粉的制备方法,该制备方法包括如下步骤:The present embodiment provides a preparation method of nano-Ir-Nb powder, and the preparation method comprises the following steps:
选用D(包含O、H、N、P、S、F、Cl、Br、I)杂质元素的原子百分比含量分别为0.2at.%、0.5at.%、0.5at.%的Cu,Ir与Nb原料,其中Ir原料中还含有2at.%的Rh。按照Cu:Ir:Nb的摩尔比约为70:15:15的比例将原料熔化,得到原子百分比成分主要为Cu 69.9(Ir 98Rh 2) 14.9Nb 14.9D 0.3的均匀初始合金熔体。 Select D (including O, H, N, P, S, F, Cl, Br, I) impurity elements with atomic percentage content of 0.2at.%, 0.5at.%, 0.5at.% Cu, Ir and Nb respectively Raw material, wherein the Ir raw material also contains 2 at.% Rh. The raw materials were melted in a ratio of about 70:15:15 in the molar ratio of Cu:Ir:Nb to obtain a homogeneous initial alloy melt with a composition of Cu 69.9 (Ir 98 Rh 2 ) 14.9 Nb 14.9 D 0.3 in atomic percentage.
通过铜辊甩带技术以约~10 6K/s的凝固速率将初始合金熔体制备成厚度为~20μm的Cu 69.9(Ir 98Rh 2) 14.9Nb 14.9D 0.3合金条带。该合金条带的凝固组织由原子百分比成分主要为Cu 99.6D 0.4的基体相与大量成分主要为(Ir 98Rh 2) 49.97Nb 49.97D 0.06的弥散颗粒相组成。其中(Ir 98Rh 2) 49.97Nb 49.97D 0.06弥散颗粒的形状为近球形,其粒径大小范围为10nm~150nm。(Ir 98Rh 2) 49.97Nb 49.97D 0.06弥散颗粒在合金条带中的体积百分含量约为37%;而且,合金熔体中少量Rh的引入,并没有导致初始合金条带中生成由Cu与Rh构成的金属间化合物;且不影响合金条带中基体相与弥散颗粒相的结构特征,也不影响弥散颗粒相中杂质含量的降低的规律。 The initial alloy melt was prepared into Cu 69.9 (Ir 98 Rh 2 ) 14.9 Nb 14.9 D 0.3 alloy ribbons with a thickness of ˜20 μm by copper roll stripping technique at a solidification rate of about ˜10 6 K/s. The solidification structure of the alloy strip is composed of a matrix phase whose atomic percentage composition is mainly Cu 99.6 D 0.4 and a large amount of dispersed particle phase whose composition is mainly (Ir 98 Rh 2 ) 49.97 Nb 49.97 D 0.06 . The shape of the (Ir 98 Rh 2 ) 49.97 Nb 49.97 D 0.06 dispersed particles is nearly spherical, and the particle size ranges from 10 nm to 150 nm. The volume percentage of (Ir 98 Rh 2 ) 49.97 Nb 49.97 D 0.06 dispersed particles in the alloy strip is about 37%; moreover, the introduction of a small amount of Rh in the alloy melt did not lead to the formation of Cu in the initial alloy strip. It is an intermetallic compound composed of Rh; and it does not affect the structural characteristics of the matrix phase and the dispersed particle phase in the alloy strip, nor does it affect the law of reducing the impurity content in the dispersed particle phase.
通过4mol/L的盐酸水溶液在40℃下与Cu 69.9(Ir 98Rh 2) 14.9Nb 14.9D 0.3合金条带,合金条带中的Cu基体被腐蚀去掉,从而得到(Ir 98Rh 2) 49.97Nb 49.97D 0.06弥散颗粒,其粒径大小范围为 10nm~150nm。且纳米(Ir 98Rh 2) 49.97Nb 49.97D 0.06中O、H、N、P、S、F、Cl、Br、I的总含量为0.06at.%。 By 4 mol/L hydrochloric acid aqueous solution at 40 ℃ and Cu 69.9 (Ir 98 Rh 2 ) 14.9 Nb 14.9 D 0.3 alloy strips, the Cu matrix in the alloy strips was etched away, thereby obtaining (Ir 98 Rh 2 ) 49.97 Nb 49.97 D 0.06 disperse particles with a particle size range of 10nm to 150nm. And the total content of O, H, N, P, S, F, Cl, Br, and I in nano (Ir 98 Rh 2 ) 49.97 Nb 49.97 D 0.06 is 0.06 at.%.
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-described embodiments can be combined arbitrarily. For the sake of brevity, all possible combinations of the technical features in the above-described embodiments are not described. However, as long as there is no contradiction between the combinations of these technical features, All should be regarded as the scope described in 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 represent several embodiments of the present invention, and the descriptions thereof are specific and detailed, but should not be construed as a limitation on 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 also be made, which all belong to 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 (17)

  1. 一种包含贵金属元素的粉体材料的制备方法,其特征在于,包括以下步骤:A preparation method of a powder material containing noble metal elements, characterized in that, comprising the following steps:
    步骤一,选择初始合金原料,按照初始合金成分配比将初始合金原料熔化,得到含有杂质元素D的均匀初始合金熔体;所述初始合金熔体的平均成分主要为Cu a(M xT y) bD d,其中,M包含贵金属元素Ir、Ru、Re、Os、Tc、Au、Pt、Pd、Ag中的至少一种,T包含W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti、Fe中的至少一种,D包含O、H、N、P、S、F、Cl、I、Br中的至少一种;且60%≤a≤99.9%,0.1%≤b≤40%,0≤d≤5%;0.1%≤x≤100%,0%≤y≤99.9%;其中,a、b、d,以及x、y分别代表对应组成元素的原子百分比含量; In step 1, the initial alloy raw material is selected, and the initial alloy raw material is melted according to the initial alloy composition ratio to obtain a uniform initial alloy melt containing impurity element D; the average composition of the initial alloy melt is mainly Cu a (M x T y ) ) b D d , wherein M includes at least one of noble metal elements Ir, Ru, Re, Os, Tc, Au, Pt, Pd, and Ag, and T includes W, Cr, Mo, V, Ta, Nb, Zr, At least one of Hf, Ti, Fe, D contains at least one of O, H, N, P, S, F, Cl, I, Br; and 60%≤a≤99.9%, 0.1%≤b≤ 40%, 0≤d≤5%; 0.1%≤x≤100%, 0%≤y≤99.9%; among them, a, b, d, and x, y represent the atomic percentage content of the corresponding constituent elements;
    步骤二,将所述初始合金熔体凝固成初始合金条带;所述初始合金条带的凝固组织包括基体相和弥散颗粒相;所述基体相的熔点低于所述弥散颗粒相,所述弥散颗粒相被包覆于所述基体相中;所述初始合金熔体凝固过程中,初始合金熔体中的杂质元素D在弥散颗粒相与基体相中重新分配,并富集于所述基体相中,从而使所述弥散颗粒相得到纯化;In step 2, the initial alloy melt is solidified into an initial alloy strip; the solidified structure of the initial alloy strip includes a matrix phase and a dispersed particle phase; the melting point of the matrix phase is lower than that of the dispersed particle phase, and the The dispersed particle phase is coated in the matrix phase; during the solidification of the initial alloy melt, the impurity element D in the initial alloy melt is redistributed in the dispersed particle phase and the matrix phase, and is enriched in the matrix phase, so that the dispersed particle phase is purified;
    所述初始合金条带中弥散颗粒相的成分主要为(M xT y) x1D z1,基体相的平均成分主要为Cu x2D z2;且99%≤x1≤100%,0≤z1≤1%;90%≤x2≤100%,0≤z2≤10%;z1≤d≤z2,2z1≤z2;x1、z1、x2、z2分别代表对应组成元素的原子百分比含量; The composition of the dispersed particle phase in the initial alloy strip is mainly (M x T y ) x1 D z1 , and the average composition of the matrix phase is mainly Cu x2 D z2 ; and 99%≤x1≤100%, 0≤z1≤1 %; 90%≤x2≤100%, 0≤z2≤10%; z1≤d≤z2, 2z1≤z2; x1, z1, x2, z2 represent the atomic percentage content of the corresponding constituent elements;
    步骤三,将所述初始合金条带中的基体相去除,并保留基体相去除过程中不能被同时去除的弥散颗粒相;收集脱落出来的弥散颗粒相,即得到由原弥散颗粒组成的包含有贵金属元素的高纯目标粉体材料。In step 3, the matrix phase in the initial alloy strip is removed, and the dispersed particle phase that cannot be removed at the same time in the process of removing the matrix phase is retained; High-purity target powder materials of precious metal elements.
  2. 根据权利要求1所述的包含贵金属元素的粉体材料的制备方法,其特征在于,所述初始合金熔体中的D杂质元素来源包括:初始合金原料引入杂质,熔炼过程中气氛或坩埚引入杂质。The method for preparing a powder material containing noble metal elements according to claim 1, wherein the source of D impurity element in the initial alloy melt comprises: impurities introduced from the initial alloy raw material, impurities introduced from the atmosphere or crucible during the smelting process .
  3. 根据权利要求1所述的包含贵金属元素的粉体材料的制备方法,其特征在于,所述M包含贵金属元素Ir、Ru、Re、Os、Tc、Au、Pt、Pd、Ag中的至少一种,且Ir、Ru、Re、Os、Tc等元素在M中的原子百分比含量高于50%;所述T包含W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti、Fe中的至少一种,且W、Cr、Mo、V、Ta、Nb等元素在T中的原子百分比含量高于50%。The method for preparing a powder material containing a noble metal element according to claim 1, wherein the M contains at least one of the noble metal elements Ir, Ru, Re, Os, Tc, Au, Pt, Pd, and Ag , and the atomic percentage content of Ir, Ru, Re, Os, Tc and other elements in M is higher than 50%; the T includes W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti, Fe At least one, and the atomic percentage content of W, Cr, Mo, V, Ta, Nb and other elements in T is higher than 50%.
  4. 根据权利要求1所述的包含贵金属元素的粉体材料的制备方法,其特征在于,所述初始合金条带中不含有包含Cu与M构成的金属间化合物,也不含有包含Cu与T构成的金属间化合物。The method for preparing a powder material containing a noble metal element according to claim 1, wherein the initial alloy strip does not contain an intermetallic compound composed of Cu and M, nor does it contain an intermetallic compound composed of Cu and T. intermetallic compounds.
  5. 根据权利要求1所述的包含贵金属元素的粉体材料的制备方法,其特征在于,所述初始合金条带中弥散颗粒的单晶颗粒数目在所有弥散颗粒数目中的占比不低于60%。The method for preparing a powder material containing noble metal elements according to claim 1, wherein the number of single crystal particles of dispersed particles in the initial alloy strip accounts for not less than 60% of the total number of dispersed particles .
  6. 根据权利要求1所述的包含贵金属元素的粉体材料的制备方法,其特征在于,所述将合金条带中基体相去除方法包括酸反应去除。The method for preparing a powder material containing noble metal elements according to claim 1, wherein the method for removing the matrix phase in the alloy strip comprises acid reaction removal.
  7. 根据权利要求1所述的包含贵金属元素的粉体材料的制备方法,其特征在于,所述包含贵金属元素的目标粉体材料的颗粒粒径范围为2nm~3mm。The method for preparing a powder material containing a noble metal element according to claim 1, wherein the particle size range of the target powder material containing a noble metal element is 2 nm to 3 mm.
  8. 根据权利要求1所述的包含贵金属元素的粉体材料的制备方法,其特征在于,在所述步骤三之后还进行以下步骤:将所述包含贵金属元素的目标粉体材料筛分后,选择粒径范围为5μm~200μm的粉体材料进行等离子球化处理,得到呈球形的包含贵金属元素的粉体材料。The method for preparing a powder material containing noble metal elements according to claim 1, characterized in that after step 3, the following step is further performed: after sieving the target powder material containing noble metal elements, selecting particles Plasma spheroidization is performed on powder materials with a diameter ranging from 5 μm to 200 μm to obtain spherical powder materials containing noble metal elements.
  9. 根据权利要求1-8任一项所述的包含贵金属元素的目标粉体材料或呈球形的包含贵金属元素的粉体材料在催化材料、粉末冶金、复合材料、吸波材料、杀菌材料、磁性材料、金属注射成型、3D打印、涂料中的应用。The target powder material containing noble metal elements or the spherical powder material containing noble metal elements according to any one of claims 1-8 is used in catalytic materials, powder metallurgy, composite materials, wave absorbing materials, bactericidal materials, magnetic materials , metal injection molding, 3D printing, coating applications.
  10. 一种合金条带,其特征在于,包含内生粉与包覆体;所述合金条带的凝固组织包括基体相和弥散颗粒相,基体相即为所述包覆体,弥散颗粒相即为所述内生粉;所述包覆体的熔点低于所述内生粉的熔点,所述内生粉被包覆于所述包覆体中;所述始合金条带中内生粉的成分主要为(M xT y) x1D z1,包覆体的平均成分主要为Cu x2D z2;且99%≤x1≤100%,0≤z1≤1%;90%≤x2≤100%,0≤z2≤10%;z1≤d≤z2,2z1≤z2;x1、z1、x2、z2分别代表对应组成元素的原子百分比含量;其中,所述M包含Ir、Ru、Re、Os、Tc、Au、Pt、Pd、Ag中的至少一种;T包含W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti、Fe中的至少一种;D包含O、H、N、P、S、F、Cl、I、Br中的至少一种。 An alloy strip is characterized in that it includes endogenous powder and a coating body; the solidification structure of the alloy strip includes a matrix phase and a dispersed particle phase, the matrix phase is the coating body, and the dispersed particle phase is the endogenous powder; the melting point of the coating body is lower than the melting point of the endogenous powder, and the endogenous powder is coated in the coating body; the composition of the endogenous powder in the initial alloy strip is mainly is (M x T y ) x1 D z1 , the average composition of the clad is mainly Cu x2 D z2 ; and 99%≤x1≤100%, 0≤z1≤1%; 90%≤x2≤100%, 0≤ z2≤10%; z1≤d≤z2, 2z1≤z2; x1, z1, x2, z2 respectively represent the atomic percentage content of the corresponding constituent elements; wherein, the M includes Ir, Ru, Re, Os, Tc, Au, At least one of Pt, Pd, Ag; T includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti, Fe; D includes O, H, N, P, S, At least one of F, Cl, I, and Br.
  11. 一种金属粉末的制备方法,其特征在于,包括以下步骤:A preparation method of metal powder is characterized in that, comprises the following steps:
    步骤一:选择成分为Cu aM bD c的初始合金,M选自Ir、Ru、Re、Os、Tc中的至少一种,D选自W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti、Fe中的至少一种;a、b、c代表对应组成元素的原子百分比含量,且50%≤a≤99.9%,0.1%≤b≤50%,0≤c≤49.9%,a+b+c=100%;按照初始合金成分配比将初始合金原料熔化,得到均匀的合金熔体,然后通过快速凝固技术将合金熔体凝固成Cu aM bD c中间合金;所述Cu aM bD c中间合金凝固组织由成分为Cu的基体相以及成分为M-D的弥散颗粒相组成,且M-D弥散颗粒相的熔点高于Cu基体相的熔点; Step 1: Select an initial alloy with a composition of Cu a M b D c , M is selected from at least one of Ir, Ru, Re, Os, Tc, D is selected from W, Cr, Mo, V, Ta, Nb, Zr , at least one of Hf, Ti, Fe; a, b, c represent the atomic percentage content of the corresponding constituent elements, and 50%≤a≤99.9%, 0.1%≤b≤50%, 0≤c≤49.9%, a+b+c=100%; the initial alloy raw material is melted according to the initial alloy composition ratio to obtain a uniform alloy melt, and then the alloy melt is solidified into a Cu a M b D c master alloy by rapid solidification technology; The solidification structure of Cu a M b D c master alloy is composed of a matrix phase with Cu composition and a dispersed particle phase with MD composition, and the melting point of the MD dispersed particle phase is higher than that of the Cu matrix phase;
    步骤二:将所述Cu aM bD c中间合金中的Cu基体相通过酸溶液反应去除,同时保留不与该酸溶液反应的M-D弥散颗粒相,即得到由M-D弥散颗粒相组成的目标金属粉末。 Step 2: The Cu matrix phase in the Cu a M b D c master alloy is removed by the acid solution reaction, while the MD dispersed particle phase that does not react with the acid solution is retained, that is, the target metal composed of the MD dispersed particle phase is obtained. powder.
  12. 根据权利要求11所述的金属粉末的制备方法,其特征在于,所述快速凝固技术包括合金熔体金属辊甩带法,且所述合金熔体的凝固速率为100K/s~1×10 7K/s。 The method for preparing metal powder according to claim 11, wherein the rapid solidification technology comprises an alloy melt metal roll stripping method, and the solidification rate of the alloy melt is 100K/s~1×10 7 K/s.
  13. 根据权利要求11所述的金属粉末的制备方法,其特征在于,所述快速凝固技术包括合金熔体雾化制粉法,且所述合金熔体的凝固速率为50K/s~5×10 5K/s。 The method for preparing metal powder according to claim 11, wherein the rapid solidification technology comprises an alloy melt atomization powder making method, and the solidification rate of the alloy melt is 50K/s~5×10 5 K/s.
  14. 根据权利要求11所述的金属粉末的制备方法,其特征在于,所述Cu aM bD c中间合金在三维尺度方向上至少有一维的尺度范围为5μm~500μm。 The method for preparing metal powder according to claim 11, wherein the Cu a M b D c master alloy has at least one dimension in the three-dimensional dimension direction ranging from 5 μm to 500 μm.
  15. 根据权利要求11所述的金属粉末的制备方法,其特征在于,所述中间合金凝固组织中弥散颗粒相的形状包括枝晶形、球形、近球形、方块形、饼形、棒条形中的至少一种,且其颗粒大小范围为2nm~100μm。The method for preparing metal powder according to claim 11, wherein the shape of the dispersed particle phase in the solidified structure of the master alloy comprises at least one of dendritic, spherical, nearly spherical, square, pie, and rod shapes. One, and its particle size ranges from 2 nm to 100 μm.
  16. 根据权利要求11所述的金属粉末的制备方法,其特征在于,所述酸溶液包括盐酸、硫酸、硝酸、磷酸、高氯酸、乙酸、草酸中的至少一种。The method for preparing metal powder according to claim 11, wherein the acid solution comprises at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, acetic acid, and oxalic acid.
  17. 根据权利要求11所述的金属粉末的制备方法,其特征在于,所述由弥散颗粒相组成的目标金属粉末的粒径范围为2nm~100μm;所述目标金属粉末的形状包括包括枝晶形、球形、近球形、方块形、饼形、棒条形中的至少一种。The method for preparing metal powder according to claim 11, wherein the target metal powder composed of dispersed particle phases has a particle size range of 2 nm to 100 μm; the shape of the target metal powder includes dendritic, spherical, , at least one of nearly spherical shape, square shape, pie shape and rod shape.
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