WO2022036906A1 - Preparation method for high-purity powder material, application of high-purity powder material, and alloy ribbon - Google Patents

Preparation method for high-purity powder material, application of high-purity powder material, and alloy ribbon Download PDF

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WO2022036906A1
WO2022036906A1 PCT/CN2020/130954 CN2020130954W WO2022036906A1 WO 2022036906 A1 WO2022036906 A1 WO 2022036906A1 CN 2020130954 W CN2020130954 W CN 2020130954W WO 2022036906 A1 WO2022036906 A1 WO 2022036906A1
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alloy
powder
phase
composition
purity
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PCT/CN2020/130954
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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 CN202080103274.7A priority Critical patent/CN116056818A/en
Publication of WO2022036906A1 publication Critical patent/WO2022036906A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • B22D11/0611—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by a single casting wheel, e.g. for casting amorphous metal strips or wires
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/065—Spherical particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/30—Acidic compositions for etching other metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/32—Alkaline compositions
    • C23F1/40—Alkaline compositions for etching other metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition

Definitions

  • the invention relates to the technical field of metal materials, in particular to a preparation method and application of a high-purity powder material and an alloy strip.
  • the preparation methods of ultrafine powder are divided into solid phase method, liquid phase method and gas phase method according to the state of matter.
  • the solid-phase methods mainly include mechanical pulverization, ultrasonic pulverization, thermal decomposition, and explosion methods.
  • Liquid phase methods mainly include precipitation method, alkoxide method, carbonyl method, spray thermal drying method, freeze drying method, electrolysis method, chemical coagulation method, etc.
  • the gas phase method mainly includes gas phase reaction method, plasma method, high temperature plasma method, evaporation method, chemical vapor deposition method, etc.
  • Rotating electrode method and atomization method are the main methods for preparing high-performance metal and alloy powder at present, but the production efficiency is low, the yield of ultrafine powder is not high, and the energy consumption is relatively large; jet milling method and hydrogenation dehydrogenation method are suitable for Large-scale industrial production, but strong selectivity to raw metals and alloys.
  • the impurity content of the powder 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 high-purity powder material characterized in that, comprising the following steps:
  • Step S1 select an 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 an impurity element T, wherein T includes O, H, N, P, S, F, Cl, At least one of I, Br, and the average composition of the initial alloy melt includes any one of the following combinations (1)-(4):
  • the average composition of the initial alloy melt is mainly A a (M x D y ) b T d , wherein A includes Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, At least one of Tb, Dy, Ho, Er, Tm, Yb, Lu, M includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti, D includes Fe, Co, At least one of Ni, wherein x, y; a, b, and d all represent the atomic percentage content of the corresponding constituent elements, and 24.9% ⁇ a ⁇ 99.4%, 0.5% ⁇ b ⁇ 75%, 0 ⁇ d ⁇ 10 %; preferably, 24.9% ⁇ a ⁇ 59.9%, 40% ⁇ b ⁇ 75%, 0 ⁇ d ⁇ 10%;
  • the average composition of the initial alloy melt is mainly A a M b T d , wherein A includes Mg, Ca, Li, Na, K, Cu, Y, La, Ce, Pr, Nd, Pm , at least one of Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, M includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti ; where a, b, d represent the atomic percentage content of the corresponding constituent elements, and 24.9% ⁇ a ⁇ 99.4%, 0.5% ⁇ b ⁇ 75%, 0 ⁇ d ⁇ 10%;
  • A includes Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, One of Tb, Dy, Ho, Er, Tm, Yb, Lu;
  • M includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, and Ti
  • A includes Cu
  • the average composition of the initial alloy melt is mainly A a M b T d , wherein A includes Zn, Mg, Sn, Pb, Ga, In, Al, La, Ge, Cu, K, Na , at least one of Li, M includes at least one of B, Bi, Fe, Ni, Cu, Ag, Si, Ge, Cr, V, wherein a, b, d represent the atomic percentage content of the corresponding constituent elements, And 24.9% ⁇ a ⁇ 59.9%, 40% ⁇ b ⁇ 75%, 0 ⁇ d ⁇ 10%;
  • M contains B A contains at least one of Sn, Ge, Cu, and Zn; when M contains Bi, A contains at least one of Sn, Ga, and Al;
  • M contains at least one of Fe, Ni, Cu, and Ag
  • A contains at least one of La, In, Na, K, Li, Pb, and Mg
  • M contains Fe, Ni
  • M contains at least one of La, In, Na, K, Li, and Mg
  • A contains at least one of Cu and Ag
  • M contains at least one of Si and Ge
  • A contains at least one of Zn, Sn, Pb, Ga, In, and Al;
  • M contains at least one of Cr and V
  • A contains Zn
  • Combination (4) When the average composition of the initial alloy melt is mainly A a M b Al c T d , A contains Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy , at least one of Ho, Er, Tm, Yb, Lu; M includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti; Al is aluminum; wherein a, b, c and d respectively represent the atomic percentage content of the corresponding constituent elements, and 29.8% ⁇ a ⁇ 64.8%, 35% ⁇ b ⁇ 70%, 0.1% ⁇ c ⁇ 25%, 0 ⁇ d ⁇ 10%;
  • the average composition of the initial alloy melt is any one of the above combinations (1)-(4);
  • 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 T 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 D y ) x1 T z1
  • the average composition of the matrix phase is mainly A x2 T z2 ; and 98.5% ⁇ x1 ⁇ 100%, 0 ⁇ z1 ⁇ 1.5%;80% ⁇ x2 ⁇ 100%,0 ⁇ z2 ⁇ 20%;z1 ⁇ d ⁇ z2,2z1 ⁇ z2; x1, z1, x2 and z2 respectively represent the atomic percentage content of the corresponding constituent elements;
  • the dispersed particle phase whose composition is mainly (M x D y ) x1 T z1 does not contain A element.
  • the composition of the dispersed particle phase in the initial alloy strip is (M x D y ) x1 T z1
  • the average composition of the matrix phase is is A x2 T z2 ;
  • the composition of the dispersed particle phase in the initial alloy strip is mainly M x1 T z1
  • the average composition of the matrix phase is mainly A x2 T z2 ; and 98.5% ⁇ x1 ⁇ 100%, 0 ⁇ z1 ⁇ 1.5%;80% ⁇ x2 ⁇ 100%,0 ⁇ z2 ⁇ 20%;z1 ⁇ d ⁇ z2,2z1 ⁇ z2; x1, z1, x2 and z2 respectively represent the atomic percentage content of the corresponding constituent elements;
  • the dispersed particle phase with the main composition M x1 T z1 does not contain A element.
  • the composition of the dispersed particle phase in the initial alloy strip is M x1 T z1
  • the average composition of the matrix phase is M x1 T z1 .
  • the composition is A x2 T z2 ;
  • the composition of the dispersed particle phase in the initial alloy strip is mainly M x1 Al y1 T z1
  • the average composition of the matrix phase is mainly A x2 Al y2 T z2 ; and 77.8% ⁇ x1 ⁇ 99.8%, 0.1% ⁇ y1 ⁇ 22%, 0 ⁇ z1 ⁇ 1.5%; 69.8% ⁇ x2 ⁇ 99.7%, 0.2% ⁇ y2 ⁇ 30%, 0 ⁇ z2 ⁇ 20% , z1 ⁇ d ⁇ z2, 2z1 ⁇ z2, y1 ⁇ y2, x1, y1, z1, x2, y2, z2 respectively represent the atomic percentage content of the corresponding constituent elements;
  • the dispersed particle phase whose composition is mainly M x1 Aly1 T z1 does not contain A element.
  • the composition of the dispersed particle phase in the initial alloy strip is M x1 Al y1 T z1
  • the average composition of the matrix phase is A x2 Al y2 T z2 ;
  • 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, and the shedding dispersed particle phase is collected, that is, a high-purity particle composed of the original dispersed particles is obtained.
  • Target powder material 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, and the shedding dispersed particle phase is collected, that is, a high-purity particle composed of the original dispersed particles is obtained.
  • the source of the T 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.
  • T is an impurity element and contains 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 T 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 initial alloy raw material includes an M-T raw material containing an impurity element T.
  • M is Ti and T contains O
  • the M-T raw material includes Ti-O raw material containing O impurities.
  • the combination of A and M in the average composition of the initial alloy melt in the step S1 is extremely important, and the selection principle is to ensure that no intermetallic compound is formed between A and M during the solidification of the alloy melt; or even if M and other Element (D) can form a high melting point intermetallic compound, but still no intermetallic compound is formed between A and M.
  • the two-phase separation of the matrix phase dominated by A and the particle phase dominated by M can be realized during the solidification of the initial alloy melt, which is beneficial to the subsequent preparation of powder materials dominated by M.
  • the initial alloy strip does not contain intermetallic compounds comprising A and M;
  • 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 50 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 twice the thickness.
  • the length of the initial alloy strip is more than 10 times its thickness.
  • the length of the initial alloy strip is more than 50 times its thickness.
  • the length of the initial alloy strip is more than 100 times its thickness.
  • the solidification rate of the initial alloy melt is 1 K/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.
  • the matrix phase can obtain a higher volume percentage content through a smaller atomic percentage content.
  • the atomic percentage composition of the initial alloy strip of La 25 Fe 75 (for the convenience of calculation, the existence of impurities is not considered), the weight percentages of La and Fe are 45.33wt% and 54.67wt%, respectively, and the combined densities of the two are 6.2 g/cm 3 and 7.8 g/cm 3 , the volume percentages of La and Fe in the initial alloy strip with the atomic percentage composition La 25 Fe 75 can be calculated to be 51 vol.% and 49 vol.%, respectively. This shows that even though the atomic percent content of Fe in the La-Fe alloy is as high as 75 at.%, its volume percent content is still lower than 50 vol.%, which is favorable for the dispersion distribution of Fe particles in the initial alloy strips.
  • volume percentage content of the dispersed particle phase in its corresponding initial alloy strip is not higher than 50% vol.%.
  • the atomic percentage content z1 of the T impurity element in the dispersed particles is less than the atomic percentage content of the T impurity element in the M-T raw material.
  • 0 ⁇ z1 ⁇ d ⁇ z2, 3z1 ⁇ z2, and 0 ⁇ z1 ⁇ 1.5% that is, the T impurity content in the dispersed particle phase is lower than the T impurity content in the initial alloy melt, and the 3 times the T impurity content in the dispersed particle phase is still lower than the T impurity content in the matrix phase;
  • the present invention adopts the atomic percentage content to express the T impurity content.
  • the composition of each element is characterized by the atomic percentage content of the element, and the increase or decrease of element content, such as the increase or decrease of impurity elements, can be accurately expressed through the concept of material quantity. If the mass percentage content (or ppm concept) of elements is used to characterize the content of each element, it is easy to produce wrong conclusions due to the difference in atomic weight of each element. For example, an alloy whose atomic percent content is Ti 45 Gd 45 O 10 contains 100 atoms, and the atomic percent content of O is 10 at %.
  • the 100 atoms are divided into two parts: Ti 45 O 4 (the atomic percentage composition is Ti 91.8 O 8.2 ) and Gd 45 O 6 (the atomic percentage composition is Gd 88.2 O 11.8 ), and the atomic percentage content of oxygen in Gd 45 O 6 is increased to 11.8at%, the atomic percentage of oxygen in Ti 45 O 4 is reduced to 8.2at%, which can accurately express that O is enriched in Gd.
  • the mass percent content of O is used to measure, the mass percent content of O in Ti 45 Gd 45 O 10 is 1.70 wt %, and the mass percent content of O in Ti 45 O 4 and Gd 45 O 6 is 2.9 wt. % and 2.9 wt % respectively. 1.34wt.%, it would lead to the wrong conclusion that the O content in Ti 45 O 4 is significantly increased compared to that in Gd 45 O 6 .
  • the method for removing the matrix phase from the alloy strip includes at least one of acid reaction removal, alkali reaction removal, and vacuum volatilization removal.
  • composition and concentration of the acid solution and the alkali solution are not specifically limited, as long as the matrix phase can be removed and the dispersed particle phase can be retained at the same time.
  • the temperature and vacuum degree of the vacuum treatment are not specifically limited, as long as the matrix phase can be removed and the dispersed particle phase can be retained at the same time.
  • the method for removing the matrix phase in the initial alloy strip includes the natural oxidation of the matrix phase-powdering and exfoliation removal.
  • the matrix phase is an element that is easily oxidized naturally with oxygen, such as La, Ce, etc.
  • the matrix phase can be separated from the dispersed particle phase through the natural oxidation-pulverization process of the matrix phase, and then supplemented by other technical means, Such as magnetic separation, it is possible to separate, for example, the magnetically dispersed particle phase from the natural oxides of the matrix phase.
  • 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 is 2 nm to 3 mm; preferably, the particle size range of the target powder material is 2 nm to 500 ⁇ m; The diameter range is 2nm ⁇ 99 ⁇ m; as a further preference, the particle diameter range of the target powder material is 2nm ⁇ 5 ⁇ m; as a further preference, the particle diameter range of the target powder material is 2nm ⁇ 200nm; as a further preference , the particle size of the target powder material ranges from 2 nm to 100 nm.
  • the dispersed particles are separated from the initial alloy strip, cleaned and dried to obtain a high-purity target powder material.
  • the composition of the high-purity target powder material is mainly (M x D y ) x1 T z1 ;
  • the dispersed particles whose composition is mainly (M x D y ) x1 T z1 do not contain A element;
  • the composition of the high-purity target powder material is (M x D y ) x1 T z1 ;
  • the composition of the high-purity target powder material is mainly M x1 T z1 ;
  • the dispersed particles whose composition is mainly M x1 T z1 do not contain A element;
  • the composition of the high-purity target powder material is M x1 T z1 ;
  • the composition of the high-purity target powder material is mainly M x1 Aly1 T z1 .
  • the dispersed particles whose composition is mainly M x1 Aly1 T z1 do not contain A element;
  • the composition of the high-purity target powder material is M x1 Aly1 T z1 .
  • the atomic percentage content of the T impurity element in the target metal powder does not exceed 1.5%
  • the atomic percentage content of the T impurity element in the target metal powder does not exceed 0.75%.
  • step S3 after sieving the high-purity powder material, select a high-purity powder material with a particle size ranging from 5 ⁇ m to 200 ⁇ m for plasma spheroidization, so as to obtain a spherical shape. of high-purity powder materials;
  • the invention also relates to the application of the high-purity powder material or spherical high-purity powder material obtained by the above preparation method in catalytic materials, powder metallurgy, composite materials, wave absorbing materials, sterilization materials, metal injection molding, 3D printing, and coatings.
  • the application of the spherical high-purity powder material obtained by the above preparation method in the field of metal powder 3D printing is characterized in that the particle size of the spherical high-purity powder material ranges from 10 ⁇ m to 200 ⁇ m.
  • the application of the high-purity powder material obtained by the above preparation method in metal injection molding and powder metallurgy is characterized in that the particle size of the high-purity powder material ranges from 0.1 ⁇ m to 200 ⁇ m.
  • the application of the high-purity powder material obtained by the above preparation method in a coating is characterized in that the particle size of the high-purity 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 chemical composition and structure of the alloy strip includes any one of the following four combinations:
  • the composition of the endogenous powder in the alloy strip is mainly (M x D y ) x1 T z1 , and the average composition of the clad is mainly A x2 T z2 ; and 98.5% ⁇ x1 ⁇ 100%, 0 ⁇ z1 ⁇ 1.5%; 80% ⁇ x2 ⁇ 100%, 0 ⁇ z2 ⁇ 20%;z1 ⁇ d ⁇ z2,2z1 ⁇ z2; x1, z1, x2, z2 respectively represent the atomic percentage content of the corresponding constituent elements; among them, A contains At least one of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, M includes W, Cr, Mo, V, Ta, Nb , at least one of Zr, Hf, Ti, D includes at least one of Fe, Co, Ni; T includes at least one of O, H, N, P, S, F, Cl, I, Br; x and y
  • the endogenous powder whose composition is mainly (M x D y ) x1 T z1 in the alloy strip does not contain A element.
  • the composition of the endogenous powder in the alloy strip is (M x D y ) x1 T z1 , and the average composition of the cladding body is A x2 T z2 ;
  • composition of the endogenous powder in the alloy strip is mainly M x1 T z1
  • the average composition of the clad is mainly A x2 T z2 ; and 98.5% ⁇ x1 ⁇ 100%, 0 ⁇ z1 ⁇ 1.5%; 80 % ⁇ x2 ⁇ 100%, 0 ⁇ z2 ⁇ 20%;z1 ⁇ d ⁇ z2,2z1 ⁇ z2; x1, z1, x2, z2 represent the atomic percentage content of the corresponding constituent elements respectively; among them, A contains Mg, Ca, Li , at least one of Na, K, Cu, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, M includes W, Cr, At least one of Mo, V, Ta, Nb, Zr, Hf, Ti; T includes at least one of O, H, N, P, S, F, Cl, I, Br;
  • A includes Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, One of Tb, Dy, Ho, Er, Tm, Yb, Lu;
  • M includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, and Ti
  • A includes Cu
  • the inner powder whose composition is mainly M x1 T z1 in the alloy strip does not contain A element;
  • the composition of the endogenous powder in the alloy strip is M x1 T z1
  • the average composition of the cladding body is A x2 T z2 ;
  • composition of the endogenous powder in the alloy strip is mainly M x1 T z1
  • the average composition of the clad is mainly A x2 T z2 ; and 98.5% ⁇ x1 ⁇ 100%, 0 ⁇ z1 ⁇ 1.5%
  • x1, z1, x2, and z2 represent the atomic percentage content of the corresponding constituent elements, respectively
  • A contains Zn, Mg, Sn , at least one of Pb, Ga, In, Al, La, Ge, Cu, K, Na, Li
  • M includes at least one of B, Bi, Fe, Ni, Cu, Ag, Si, Ge, Cr, V A sort of;
  • M contains B A contains at least one of Sn, Ge, Cu, and Zn; when M contains Bi, A contains at least one of Sn, Ga, and Al;
  • M contains at least one of Fe, Ni, Cu, and Ag
  • A contains at least one of La, In, Na, K, Li, Pb, and Mg
  • M contains Fe, Ni
  • M contains at least one of La, In, Na, K, Li, and Mg
  • A contains at least one of Cu and Ag
  • M contains at least one of Si and Ge
  • A contains at least one of Zn, Sn, Pb, Ga, In, and Al;
  • M contains at least one of Cr and V
  • A contains Zn
  • the endogenous powder whose composition is mainly M x1 T z1 in the alloy strip does not contain A element.
  • the composition of the endogenous powder in the alloy strip is M x1 T z1
  • the average composition of the cladding body is A x2 T z2 ;
  • the composition of the endogenous powder in the alloy strip is mainly M x1 A y1 T z1
  • the average composition of the clad is mainly A x2 A y2 T z2 ; and 77.8% ⁇ x1 ⁇ 99.8%, 0.1% ⁇ y1 ⁇ 22%, 0 ⁇ z1 ⁇ 1.5%; 69.8% ⁇ x2 ⁇ 99.7%, 0.2% ⁇ y2 ⁇ 30%, 0 ⁇ z2 ⁇ 20%, z1 ⁇ d ⁇ z2, 2z1 ⁇ z2, y1 ⁇ y2, x1, y1, z1, x2, y2, and z2 respectively represent the atomic percentage content of the corresponding constituent elements; among them, A includes Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm , at least one of Yb, Lu; M includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti; Al is aluminum;
  • the inner powder whose composition is mainly M x1 Al y1 T z1 in the alloy strip does not contain A element;
  • the composition of the endogenous powder in the alloy strip is M x1 Aly1 T z1
  • the average composition of the clad is A x2 A y2 T z2 ;
  • the chemical composition and structure of the alloy strip is any one of the above four combinations in 1)-4);
  • the thickness of the alloy strips ranges from 5 ⁇ m to 50 mm; preferably, the thickness of the alloy strips ranges from 5 ⁇ m to 5 mm; preferably, the thickness of the alloy strips ranges from 5 ⁇ m to 1 mm; 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%.
  • A, M, D or T 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 A and M, or A and D;
  • 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;
  • the T impurity content in the initial alloy melt is not 0, the T impurity content in the dispersed particle phase is lower than the T impurity content in the initial alloy melt, and the T impurity content in the dispersed particle phase is less than 2 times is still lower than the T impurity content 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 material can be obtained from the low-purity raw material, and a new way is pointed out for the preparation of the high-purity powder material from the low-purity raw material, which is 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 highly active matrix main elements (such as RE rare earth elements) on impurity elements in the initial alloy melt.
  • the matrix element is generally a highly active, low melting point element, it has a strong affinity with the impurity element T during the melting and solidification of the alloy melt, which can make the impurity element T in the initial alloy melt more It enters into the matrix phase mainly composed of the main elements of the matrix phase, or forms slag with the main elements of the matrix in the melt state, and separates and removes it from the alloy melt; 2) During the nucleation and growth of the endogenously precipitated dispersed particle , the impurity element T will be discharged into the remaining melt.
  • 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 second phase matrix, which further reduces the target powder material.
  • the impurity content of the smelting process further reduces the requirements for the crucible, 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, and it 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 the (111) plane arrangement, which will endow the target metal powder with special mechanical, physical and chemical properties, thereby producing beneficial effects.
  • step S1 combination (4) when the average composition of the initial alloy melt is as described in step S1 combination (4), a metal or alloy material containing W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti and other elements is realized solid solution of Al element.
  • the addition of Al element plays a very important role.
  • the most widely used titanium alloy is Ti6Al4V alloy.
  • the Ti6Al4V alloy powder is generally obtained by smelting the Ti6Al4V alloy melt, and then using the atomization powder technology.
  • M at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti and other elements
  • the Al in M-based Al-containing dispersed particles is protected by inert M element and will not be easily removed by acid reaction (eg Ti6Al4V alloy has good Acid corrosion resistance), which makes it possible to prepare Al-containing titanium alloy powder by removing the matrix phase by acid reaction.
  • the alloy strip composed of the endogenous powder and the coating body (matrix phase) creatively uses the in-situ generated matrix phase to wrap the endogenous powder, and maintains 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 technical solution of the present invention does not rush to remove the cladding body after preparing the alloy strip composed of the endogenous metal powder and the cladding body (matrix phase), but directly uses the cladding body Protect 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 nanopowder, the endogenous metal powder can be compounded with the resin at the same time as the endogenous metal powder is released from the cladding body or immediately afterward, so as to prepare 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 including nano-scale, sub-micron-scale and micro-scale, and can be used in catalytic materials, powder metallurgy, composite materials , absorbing materials, sterilization materials, magnetic materials, metal injection molding, 3D printing, coatings and other fields have good application prospects.
  • the present invention also provides a method for preparing high-purity metal powder, which comprises the following steps:
  • Step 1 select the initial alloy, melt the initial alloy raw material according to the initial alloy composition ratio to obtain a uniform alloy melt, and then prepare the alloy melt into alloy strips by rapid solidification technology;
  • A is selected from Mg, Ca, Li, Na, K, Zn, Pb, Sn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu , at least one of Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
  • the solidified structure of the A a M b alloy strip does not contain intermetallic compounds composed of A and M, and its solidified structure is composed of the matrix phase with the composition A and the dispersed particle phase with the composition M;
  • the solidified structure of the belt does not contain intermetallic compounds composed of La and Fe, and its solidified structure is composed of a matrix phase composed of La and a dispersed particle phase composed of Fe;
  • composition ratio of the initial alloy is A a M b Al c
  • A is selected from Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb , at least one of Lu, Al is aluminum
  • the impurity elements in the alloy melt and the impurity elements introduced during the solidification process are enriched in the matrix phase, so that the dispersed particle phase is purified;
  • Step 2 The matrix phase in the alloy strip is removed and the dispersed particle phase is retained, and the impurity elements enriched in the matrix phase are removed accordingly, that is, a high-purity target metal powder composed of dispersed particles is obtained.
  • ultrafine and low impurity content metal powder can be prepared.
  • the higher the solidification rate of the alloy melt the smaller the dispersed particle phase in the solidified structure of the obtained alloy strip. 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 matrix phase, which greatly reduces the ultra-fine metal powder. cost of powder preparation.
  • the matrix phase is generally composed of elements with low melting point and high activity
  • the impurity elements are enriched in the matrix phase during the alloy smelting and rapid solidification process, so that the dispersed particle phase can be purified and protected. Preparation of high-purity target metal powder.
  • the matrix phase of the present invention is mainly composed of large atomic elements, even if the matrix phase contains less than 50 atomic percent, its volume percent content in the alloy strip can be much higher than its atomic percent content.
  • the volume percentage content of La matrix can still reach 51%.
  • the volume percentage content of the matrix phase in the alloy strip is not less than 44%.
  • the rapid solidification technology includes an alloy melt metal roll stripping method, and the solidification rate of the alloy melt is 50K/s ⁇ 10 7 K/s.
  • the solidification rate is higher than 10 5 K/s, nano-scale dispersed particles can be obtained; when the solidification rate is 10 3 K/s ⁇ 10 5 K/s, sub-micron dispersed particles can be obtained; when solidified When the rate is lower than 10 3 K/s, the micron-scale dispersed particle phase can be obtained.
  • the thickness of the alloy strip is 5 ⁇ m ⁇ 5 mm.
  • the shape of the dispersed particle phase includes at least one of dendritic shape, spherical shape, nearly spherical shape, square shape, cake shape, and rod shape, and the particle size ranges from 2 nm to 200 ⁇ m.
  • the impurity elements in the alloy melt and the impurity elements introduced in the solidification process include at least one of H, O, N, S, P, F, Cl, I, and Br.
  • the method for removing the matrix phase from the alloy strip includes at least one of acid reaction removal, alkali reaction removal, and vacuum volatilization removal.
  • the composition and concentration of the acid solution and the alkali solution are not specifically limited, as long as the matrix phase can be removed and the dispersed particle phase can be retained at the same time.
  • the method for removing the matrix phase in the alloy strip includes the natural oxidation of the matrix phase-powdering and exfoliation removal.
  • the particle size range of the high-purity target metal powder composed of the dispersed particle phase is 2 nm ⁇ 200 ⁇ m.
  • the shape of the high-purity target metal powder includes spherical, nearly spherical, dendritic, rod-shaped, and lath-shaped.
  • the total content of H, O, N, S, P, F, Cl, I, and Br in the high-purity target metal powder is less than 2000 ppm.
  • 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 impurity elements in the melt are easy to combine with the matrix so as to be enriched with the matrix phase. Therefore, even if non-high-purity raw materials and ordinary crucibles are used, or other gas impurity elements enter the melt during the smelting process, the dispersed particle phase and target metal powder with low impurity content can be obtained, which greatly reduces the high-purity powder. production cost of bulk material.
  • the resulting disperse grain phase is also composed of multiple elements, which makes the preparation of a disperse grain phase composed of The target alloy powder becomes more convenient and feasible, which greatly expands the composition range and application field of the target alloy powder.
  • the matrix phase in the alloy strip is a low melting point and high activity component
  • the matrix phase can be removed by at least one of the following three methods, and the dispersed particle phase can be retained: 1. ) The matrix phase is removed by etching with an acid solution or an alkaline solution, while the dispersed particle phase is retained; 2) For the highly volatile matrix phase, the matrix phase is removed by vacuum evaporation, while the dispersed particle phase is retained; 3) For the highly volatile matrix phase, the matrix phase is removed by vacuum evaporation.
  • the matrix phase that is easy to be naturally oxidized such as the matrix phase whose main component is rare earth elements, can also be converted into pulverized oxide powder by the natural oxidation-pulverization of the matrix phase elements, and then further The dispersed particle phase is separated from the pulverized product of the matrix to obtain the target metal powder.
  • 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 including nano-, sub-micro and micro-scale, and is used in catalysis, powder metallurgy, composite materials, sterilization, etc. , metal injection molding, 3D printing, and other fields of additive manufacturing have good application prospects.
  • the present embodiment provides a preparation method of nano-CrV powder, and the preparation method comprises the following steps:
  • the alloy with the atomic ratio formula of Zn 54 Cr 23 V 23 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 20 ⁇ m at a solidification rate of 10 6 K/s.
  • Zn 54 Cr 23 V 23 alloy strip The solidification structure of the alloy strip is composed of a matrix phase with a composition of Zn and a large amount of dispersed particles with a composition of Cr 50 V 50 , wherein the shape of the Cr 50 V 50 particles is nearly spherical, and the particle size ranges from 3nm to 200nm.
  • the volume content of Cr 50 V 50 particles in the alloy strip is about 42%; impurity elements are enriched in the Zn matrix during solidification.
  • the Zn in the alloy strip is volatilized and removed by the method of vacuum heat treatment, so that the Cr 50 V 50 particles that are difficult to volatilize in the alloy strip are detached, and the nano-Cr 50 V 50 powder is obtained, and its particle size ranges from 3nm to 200nm. And the total content of H, O, N, S, P, F, Cl, I, and Br in the nano-Cr 50 V 50 powder is less than 1500 ppm.
  • the present embodiment provides a preparation method of nano-CrV powder, and the preparation method comprises the following steps:
  • the alloy with the atomic ratio formula of Zn 54 Cr 23 V 23 was selected, and the raw materials were weighed according to the formula. After the initial alloy raw material was melted uniformly, it was prepared into a thickness of 20 ⁇ m by the copper roller stripping technology at a solidification rate of about 10 6 K/s. Zn 54 Cr 23 V 23 alloy strips.
  • the solidification structure of the alloy strip is composed of a matrix phase with a composition of Zn and a large amount of dispersed particles with a composition of Cr 50 V 50 , wherein the shape of the Cr 50 V 50 particles is nearly spherical, and the particle size ranges from 3nm to 200nm.
  • the volume content of Cr 50 V 50 particles in the alloy strip is about 42%; impurity elements are enriched in the Zn matrix during solidification.
  • the Zn in the alloy strip is dissolved and removed by the sodium hydroxide alkali solution, so that the Cr 50 V 50 particles in the alloy strip that are difficult to react with the alkali solution are detached, that is, the nano Cr 50 V 50 powder is obtained. It is 3nm to 200nm, and the total content of H, O, N, S, P, F, Cl, I, and Br in the nano-Cr 50 V 50 powder is less than 1500 ppm.
  • the present embodiment provides a preparation method of nano-Ti powder, and the preparation method comprises the following steps:
  • the alloy with the atomic ratio formula of Ce 30 Ti 70 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 Ce with a thickness of 15 ⁇ m at a solidification rate of about 10 7 K/s. 30 Ti 70 alloy strip.
  • the solidified structure of the alloy strip is composed of a matrix phase with a composition of Ce and a large amount of dispersed particle phases with a composition of Ti, wherein the shape of the Ti particles is nearly spherical, and the particle size ranges from 3nm to 150nm.
  • the volume content of Ti particles in the alloy strip is about 55%; impurity elements are enriched in the Ce matrix during solidification.
  • the Ce matrix in the alloy strip is dissolved and removed by the hydrochloric acid solution, so that the Ti particles in the alloy strip that are difficult to react with the acid solution are separated, and the nano-Ti powder is obtained, and the particle size of the nano-Ti powder ranges from 3 nm to 150 nm.
  • the total content of H, O, N, S, P, F, Cl, I and Br in the powder is less than 1500ppm.
  • This embodiment provides a preparation method of nano-Ti-Zr-Hf-Nb-Ta powder, and the preparation method includes the following steps:
  • the solidification structure of the alloy strip is composed of a matrix phase with a composition of Ce and a large number of dispersed particles with a composition of Ti 20 Zr 20 Hf 20 Nb 20 Ta 20 , wherein the shape of the Ti 20 Zr 20 Hf 20 Nb 20 Ta 20 particles is approximately Spherical, with particle size ranging from 3nm to 150nm.
  • the volume content of Ti 20 Zr 20 Hf 20 Nb 20 Ta 20 particles in the alloy strip is about 50%; impurity elements are enriched in the Ce matrix during solidification.
  • the Ce matrix in the alloy strip is dissolved and removed by the hydrochloric acid solution, so that the Ti 20 Zr 20 Hf 20 Nb 20 Ta 20 particles in the alloy strip that are difficult to react with the acid solution are separated out, that is, nano-Ti 20 Zr 20 Hf 20 Nb is obtained.
  • 20 Ta 20 powder its particle size range is 3nm ⁇ 150nm, and the total content of H, O, N, S, P, F, Cl, I, Br in the nano Ti 20 Zr 20 Hf 20 Nb 20 Ta 20 powder is low at 1500ppm.
  • This embodiment provides a preparation method of nano-submicron Ti-Nb powder, and the preparation method includes the following steps:
  • the alloy whose atomic ratio formula is Ce 50 (Ti 50 Nb 50 ) 50 weigh the raw material according to the formula, and after the initial alloy raw material is melted uniformly, it is prepared by copper roller stripping technology with a solidification rate of about 10 4 K/s.
  • the solidification structure of the alloy strip is composed of a matrix phase with a composition of Ce and a large number of dispersed particle phases with a composition of Ti 50 Nb 50 , wherein the shape of the Ti 50 Nb 50 particles is nearly spherical, and the particle size ranges from 50 nm to 1 ⁇ m.
  • the volume content of Ti 50 Nb 50 particles in the alloy strip is about 34%; impurity elements are enriched in the Ce matrix during solidification.
  • the Ce matrix in the alloy strip is dissolved and removed by the hydrochloric acid solution, so that the Ti 50 Nb 50 particles in the alloy strip that are difficult to react with the acid solution are detached, that is, the nano-submicron Ti 50 Nb 50 powder is obtained.
  • the diameter range is from 50 nm to 1 ⁇ m, and the total content of H, O, N, S, P, F, Cl, I, and Br in the Ti 50 Nb 50 powder is less than 1500 ppm.
  • the present embodiment provides a preparation method of micron Ti-Co powder, and the preparation method comprises the following steps:
  • the alloy whose atomic ratio formula is Gd 50 (Ti 50 Co 50 ) 50 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 3mm strip of Gd50 ( Ti50Co50 ) 50 alloy.
  • the solidification structure of the alloy strip is composed of a matrix phase with a composition of Gd and a large number of dispersed particle phases with a composition of Ti 50 Co 50 , wherein the shape of the Ti 50 Co 50 particles is dendrite, and the particle size ranges from 1 ⁇ m to 100 ⁇ m.
  • the volume content of Ti 50 Co 50 particles in the alloy strip is about 30%; impurity elements are enriched in the Gd matrix during solidification.
  • the Gd matrix in the alloy strip is dissolved and removed by the dilute hydrochloric acid solution, so that the Ti 50 Co 50 particles in the alloy strip that are difficult to react with the dilute acid solution are detached, that is, the micron-scale Ti 50 Co 50 powder is obtained.
  • the size ranges from 1 ⁇ m to 100 ⁇ m, and the total content of H, O, N, S, P, F, Cl, I, and Br in the Ti 50 Co 50 powder is less than 1500 ppm.
  • the present embodiment provides a preparation method of submicron-micron Fe powder, and the preparation method comprises the following steps:
  • the alloy with the atomic ratio formula of La 40 Fe 60 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 La with a thickness of 500 ⁇ m at a solidification rate of about 10 3 K/s. 40 Fe 60 alloy strip.
  • the solidified structure of the alloy strip is composed of a matrix phase with a composition of La and a large amount of dispersed particles with a composition of Fe, wherein the shape of the Fe particles is nearly spherical, and the particle size ranges from 500 nm to 5 ⁇ m.
  • the volume content of Fe particles in the alloy strip is about 32%; impurity elements are enriched in the La matrix during solidification.
  • the La in the La 40 Fe 60 alloy is transformed into lanthanum oxide through the natural oxidation-powdering process of the La matrix in the air, and then the Fe particles are separated from the lanthanum oxide by the magnetic properties of Fe, that is, the sub-micron-micron Fe powder is obtained,
  • the particle size ranges from 500 nm to 5 ⁇ m, and the total content of H, O, N, S, P, F, Cl, I, and Br in the Fe powder is less than 1500 ppm.
  • the present embodiment provides a preparation method of nano Fe powder, and the preparation method comprises the following steps:
  • the alloy with the atomic ratio formula of La 25 Fe 75 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 La with a thickness of 20 ⁇ m at a solidification rate of about 10 6 K/s. 25 Fe 75 alloy strip.
  • the solidified structure of the alloy strip is composed of a matrix phase with a composition of La and a large amount of dispersed particles with a composition of Fe, wherein the shape of the Fe particles is nearly spherical, and the particle size ranges from 3nm to 200nm.
  • the volume content of Fe particles in the alloy strip is about 49%; impurity elements are enriched in the La matrix during solidification.
  • the La in the La 25 Fe 75 alloy is transformed into lanthanum oxide through the natural oxidation-powdering process of the La matrix in the air, and then the magnetic properties of Fe are used to separate the nano Fe particles from the lanthanum oxide, that is, the nano Fe powder is obtained.
  • the diameter range is from 3nm to 200nm, and the total content of H, O, N, S, P, F, Cl, I, and Br in Fe powder is less than 1800ppm.
  • This embodiment provides a preparation method of submicron-micron FeNi powder, and the preparation method includes the following steps:
  • the alloy whose atomic ratio formula is Li 50 (Fe 50 Ni 50 ) 50 weigh the raw material according to the formula, and after the initial alloy raw material is melted uniformly, it is prepared by the copper roller stripping technique with a solidification rate of about 10 3 K/s.
  • the solidification structure of the alloy strip is composed of a matrix phase composed of Li and a large number of dispersed particle phases composed of Fe 50 Ni 50 , wherein the Fe 50 Ni 50 particles are nearly spherical or dendritic in shape, and the particle size ranges from 500 nm to 500 nm. 5 ⁇ m.
  • the volume content of Fe 50 Ni 50 particles in the alloy strip is about 34%; impurity elements are enriched in the Li matrix during solidification.
  • the Li in Li 50 (Fe 50 Ni 50 ) 50 alloy is transformed into oxide powder through the natural oxidation-powdering process of Li matrix in air, and then Fe 50 Ni 50 particles are combined with Li by utilizing the magnetic properties of Fe 50 Ni 50
  • the oxidation product is separated, namely obtains sub-micron-micron Fe 50 Ni 50 powder with a particle size range of 500 nm to 5 ⁇ m, and H, O, N, S, P, F, Cl, I in the Fe 50 Ni 50 powder ,
  • the total Br content is less than 1800ppm.
  • This embodiment provides a preparation method of nano-Ti-Al-V powder, and the preparation method includes the following steps:
  • the solidification structure of the alloy strip is composed of a matrix phase with a composition of Ce 85 Al 15 and a large amount of dispersed particles with a composition of (Ti 96 V 4 ) 90 Al 10 , wherein the shape of the (Ti 96 V 4 ) 90 Al 10 particles is Nearly spherical, the particle size ranges from 3nm to 200nm.
  • the volume content of (Ti 96 V 4 ) 90 Al 10 particles in the alloy strip is about 52%; impurity elements are enriched in the Ce 85 Al 15 matrix during solidification.
  • the Ce 85 Al 15 matrix phase in the Ce 30 Al 12 (Ti 96 V 4 ) 58 alloy strip is removed by the dilute hydrochloric acid solution, so that the (Ti 96 V 4 ) 90 Al 10 particles that are difficult to react with the dilute hydrochloric acid solution are separated out , that is, to obtain nano (Ti 96 V 4 ) 90 Al 10 powder with a particle size range of 3 nm to 200 nm, and the H, O, N, S, P, F in the nano (Ti 96 V 4 ) 90 Al 10 powder , Cl, I, Br total content less than 1400ppm.
  • This embodiment provides a preparation method of submicron-micron Ti-Al-V powder, and the preparation method includes the following steps:
  • the solidification structure of the alloy strip is composed of a matrix phase with a composition of Ce 85 Al 15 and a large amount of dispersed particles with a composition of (Ti 96 V 4 ) 90 Al 10 , wherein the shape of the (Ti 96 V 4 ) 90 Al 10 particles is Nearly spherical or dendritic, with a particle size ranging from 500nm to 5 ⁇ m.
  • the volume content of (Ti 96 V 4 ) 90 Al 10 particles in the alloy strip is about 52%; impurity elements are enriched in the Ce 85 Al 15 matrix during solidification.
  • the Ce 85 Al 15 matrix phase in the Ce 30 Al 12 (Ti 96 V 4 ) 58 alloy strip is removed by the dilute hydrochloric acid solution, so that the (Ti 96 V 4 ) 90 Al 10 particles that are difficult to react with the dilute hydrochloric acid solution are separated out , that is, to obtain submicron-micron (Ti 96 V 4 ) 90 Al 10 powder, the particle size of which ranges from 500 nm to 5 ⁇ m, and the H, O, N, S, The total content of P, F, Cl, I and Br is less than 1400ppm.
  • the present embodiment provides a preparation method of nano-Ti powder, and the preparation method comprises the following steps:
  • the raw materials of sponge Ti and rare earth Ce with the atomic percentage content of T (including O, H, N, P, S, F, Cl, Br, and I) impurity elements are respectively 3 at.% and 2.5 at.% are selected. According to the molar ratio of Ce to Ti about 1:1, the sponge Ti and the rare earth Ce are fully melted to obtain a uniform initial alloy melt whose atomic percentage is mainly Ce 47.25 Ti 47.25 T 2.5 .
  • the initial alloy melt was prepared into Ce 47.25 Ti 47.25 T 2.5 alloy strips with a thickness of 15 ⁇ 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 mainly composed of Ce 95.2 T 4.8 and a large number of dispersed particles mainly composed of Ti 99.8 T 0.2 .
  • the shape of the Ti 99.8 T 0.2 dispersed particles is nearly spherical, and the particle size ranges It is 3nm ⁇ 150nm.
  • the volume content of Ti 99.8 T 0.2 dispersed particles in the alloy strip is about 34%;
  • the obtained Ce 47.25 Ti 47.25 T 2.5 alloy strip is an alloy strip composed of endogenous powder and cladding.
  • the Ce 95.2 T 4.8 matrix in the alloy strip is removed by the dilute acid solution, so that the Ti 99.8 T 0.2 particles in the alloy strip that are difficult to react with the dilute acid solution are detached, that is, the Ti 99.8 T 0.2 nano-powder is obtained.
  • the range is 3 nm to 150 nm, and the total content of O, H, N, P, S, F, Cl, Br, and I contained in it is 0.2 at.%.
  • the nanometer powder whose main component is Ti 99.8 T 0.2 is mixed with epoxy resin and other coating components under a protective atmosphere, thereby preparing a nanometer Ti modified polymer anti-corrosion coating.
  • This embodiment provides a preparation method of micron dendritic Ti-Nb powder, and the preparation method includes the following steps:
  • the atomic percentage content of T (including O, H, N, P, S, F, Cl, Br, I) impurity elements is selected as sponge Ti, Nb sheet, rare earth with 3 at.%, 1 at.%, 2.5 at.% respectively Gd raw material. According to the molar ratio of Gd:Ti:Nb about 2:1:1, each alloy raw material was melted to obtain a uniform initial alloy melt whose atomic percentage composition was mainly Gd 48.75 Ti 24.5 Nb 24.5 T 2.25 .
  • the initial alloy melt was prepared into Gd 48.75 Ti 24.5 Nb 24.5 T 2.25 alloy strips with a thickness of -300 ⁇ m by copper roll stripping technique at a solidification rate of about -10 3 K/s.
  • the solidification structure of the alloy strip is composed of a matrix phase whose atomic percentage is mainly Gd 95.9 T 4.1 and a large amount of dispersed particles whose composition is mainly Ti 49.85 Nb 49.85 T 0.3 .
  • the shape of the Ti 49.85 Nb 49.85 T 0.3 dispersed particles is dendritic, and the particle size ranges from 1 ⁇ m to 50 ⁇ m.
  • the volume percentage of Ti 49.85 Nb 49.85 T 0.3 dispersed particles in the alloy strip is about 35%;
  • the Gd 95.9 T 4.1 matrix phase in the alloy strip is removed by the dilute acid solution, so that the Ti 49.85 Nb 49.85 T 0.3 dispersed particles in the alloy strip that are difficult to react with the dilute acid solution are separated out, that is, the main component is Ti 49.85 Nb 49.85
  • the micron powder with T 0.3 has a particle size range of 1 ⁇ m to 50 ⁇ m, and the total content of O, H, N, P, S, F, Cl, Br, and I contained in it is 0.3 at.%.
  • the above-mentioned Ti 49.85 Nb 49.85 T 0.3 alloy powder is sieved through a 1000-mesh and 2000-mesh sieve to obtain a graded Ti 49.85 Nb 49.85 T 0.3 alloy powder with particle sizes ranging from 53 ⁇ m to 13 ⁇ m and 13 ⁇ m to 6.5 ⁇ m, respectively.
  • Plasma spheroidization was performed on them respectively to further obtain Ti-Nb-T alloy powders with particle sizes ranging from 53 ⁇ m to 13 ⁇ m and 13 ⁇ m to 6.5 ⁇ m, and shapes close to spherical.
  • the obtained spherical Ti-Nb-T alloy powder can be used in the fields of 3D metal printing, metal injection molding and powder metallurgy.
  • the present embodiment provides a preparation method of nano-TiNi powder, and the preparation method comprises the following steps:
  • the initial alloy melt was prepared into Gd 48.8 Ti 25.25 Ni 25.25 T 1.7 alloy strips with a thickness of ⁇ 15 ⁇ 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 mainly composed of Gd 96.8 T 3.2 and a large amount of dispersed particle phase mainly composed of Ti 49.9 Ni 49.9 T 0.2 (which is a TiNi intermetallic compound), wherein Ti 49.9 Ni 49.9 T 0.2
  • the shape of the dispersed particles is nearly spherical, and the particle size ranges from 3 nm to 150 nm.
  • the volume content of Ti 49.9 Ni 49.9 T 0.2 dispersed particles in the alloy strip is about 32%;
  • the Gd 96.8 T 3.2 matrix in the alloy strip is removed by the dilute acid solution, so that the Ti 99.8 T 0.2 particles in the alloy strip that are difficult to react with the dilute acid solution are detached, that is, the Ti 49.9 Ni 49.9 T 0.2 nano-powder is obtained.
  • the diameter ranges from 3 nm to 150 nm, and the total content of O, H, N, P, S, F, Cl, Br, and I contained in it is 0.2 at.%.
  • the present embodiment provides a preparation method of submicron-micron Fe powder, and the preparation method comprises the following steps:
  • La raw materials with atomic percentage contents of T including O, H, N, P, S, F, Cl, Br, and I
  • impurity elements are selected respectively as 1 at.% and 2.5 at.%.
  • each alloy raw material is melted to obtain a uniform initial alloy melt whose atomic percentage composition is mainly La 32.8 Fe 65.7 T 1.5 .
  • the initial alloy melt was prepared into La 32.8 Fe 65.7 T 1.5 alloy strips with a thickness of ⁇ 100 ⁇ m by the copper roll stripping technique at a solidification rate of about ⁇ 10 4 K/s.
  • the solidification structure of the alloy strip is composed of a matrix phase whose atomic percentage is mainly La 95.9 T 4.1 and a large amount of which is a dispersed particle phase whose composition is mainly Fe 99.85 T 0.15 .
  • the shape of Fe 99.85 T 0.15 dispersed particles is nearly spherical or dendritic, and their particle size ranges from 500 nm to 3 ⁇ m.
  • the volume percentage of Fe 99.85 T 0.15 dispersed particles in the alloy strip is about 36%;
  • the La 95.9 T 4.1 matrix phase in the alloy strips is removed by the dilute acid solution, and the Fe 99.85 T 0.15 disperse particles are rapidly separated from the acid solution by the magnetic properties of Fe, that is, the main component of Fe 99.85 T 0.15 is obtained.
  • the micron-micron powder has a particle size range of 500 nm to 3 ⁇ m, and the total content of O, H, N, P, S, F, Cl, Br, and I contained in it is 0.15 at.%.
  • This embodiment provides a preparation method of nano-Ti-V-Al alloy powder, and the preparation method includes the following steps:
  • the atomic percentages of T (including O, H, N, P, S, F, Cl) impurity elements are selected as sponge Ti, V block, 1at.%, 2.5at.%, 0.2at. Rare earth Ce, and Al raw materials.
  • the initial alloy raw materials are fully melted according to a certain proportion to obtain an initial alloy melt whose atomic percentage composition is mainly Ce 40.2 (Ti 96 V 4 ) 37.9 Al 20.5 T 1.4 .
  • the initial alloy melt was prepared into Ce 40.2 (Ti 96 V 4 ) 37.9 Al 20.5 T 1.4 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 with an average composition of Ce 73.2 Al 24.3 T 2.5 and a large number of dispersed particles with a main composition of (Ti 96 V 4 ) 84 Al 15.8 T 0.2 , of which (Ti 96 V 4 )
  • the shape of the 84 Al 15.8 T 0.2 dispersed particles is nearly spherical, and the particle size ranges from 5 nm to 200 nm.
  • the volume content of (Ti 96 V 4 ) 84 Al 15.8 T 0.2 dispersed particles in the alloy strip is about 33%;
  • the nanometer powder whose main component is (Ti 96 V 4 ) 84 Al 15.8 T 0.2 is mixed with epoxy resin and other coating components under a protective atmosphere to prepare a nano-Ti alloy modified polymer anti-corrosion coating.
  • This embodiment provides a preparation method of nano-Ti-Al alloy powder, and the preparation method includes the following steps:
  • the atomic percentage content of T (including at least one of O, H, N, P, S, F, and Cl) impurity elements is selected as sponge Ti and rare earth Ce, which are 3 at.%, 2.5 at.%, and 0.2 at.% respectively. , and Al raw materials.
  • sponge Ti also contains 0.5at.% Mn; rare earth Ce also contains 0.7at.% Mg.
  • the initial alloy raw materials are fully melted according to a certain proportion to obtain an initial alloy melt whose atomic percentage composition is mainly (Ce 99.3 Mg 0.7 ) 40 (Ti 99.5 Mn 0.5 ) 38 Al 20.6 T 1.4 .
  • the initial alloy melt was prepared as ⁇ 20 ⁇ m thick (Ce 99.3 Mg 0.7 ) 40 (Ti 99.5 Mn 0.5 ) 38 Al 20.6 T 1.4 alloy strips 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 with an average composition of (Ce 99.3 Mg 0.7 )Al 24.3 T 2.5 and a large amount of dispersed particles with a major composition of (Ti 99.5 Mn 0.5 ) 84 Al 15.8 T 0.2 , of which (Ti 99.5 Mn 0.5 ) 84 Al 15.8 T 0.2
  • the shape of the 99.5 Mn 0.5 ) 84 Al 15.8 T 0.2 dispersed particles is nearly spherical, and the particle size ranges from 5 nm to 200 nm.
  • the volume content of (Ti 99.5 Mn 0.5 ) 84 Al 15.8 T 0.2 dispersed particles in the alloy strip is about 33%; and the introduction of Mn and Mg in the alloy melt did not lead to the formation of Ce, It is an intermetallic compound composed of Mg, Ti and Mn; 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.
  • the (Ce 99.3 Mg 0.7 )Al 24.3 T 2.5 matrix in the alloy strip is removed by the dilute acid solution, so that the (Ti 99.5 Mn 0.5 ) 84 Al 15.8 T 0.2 particles in the alloy strip that are difficult to react with the dilute acid solution are separated out, That is to obtain nano-powder whose main component is (Ti 99.5 Mn 0.5 ) 84 Al 15.8 T 0.2 , its particle size range is 5nm-200nm, and it contains O, H, N, P, S, F, Cl, Br, The total content of I was 0.2 at.%.
  • the nanometer powder whose main component is (Ti 99.5 Mn 0.5 ) 84 Al 15.8 T 0.2 is mixed with epoxy resin and other coating components under protective atmosphere to prepare nano-Ti alloy modified polymer anti-corrosion coating.

Abstract

A preparation method for a high-purity powder material, comprising: first preparing, by means of melt solidification, an alloy ribbon having a solidified structure consisting of a matrix phase and a disperse particle phase, wherein during the solidification process of the alloy ribbon, impurity elements are enriched to the matrix phase, so that the disperse particle phase is purified; and removing the matrix phase in the alloy ribbon to obtain a high-purity target powder material constituted by the disperse particle phase. The preparation method features a simple technology, easy operations, and low costs, can prepare nano-scale, submicron-scale, micron-scale, and millimeter-scale high-purity powder materials, and has good application prospects in the fields of catalytic materials, powder metallurgy, composite materials, wave-absorbing materials, sterilization materials, magnetic materials, metal injection molding, 3D printing, and coatings.

Description

一种高纯粉体材料的制备方法及其应用及一种合金条带Preparation method and application of high-purity powder material and alloy strip 技术领域technical field
本发明涉及金属材料技术领域，特别涉及一种高纯粉体材料的制备方法及其应用及一种合金条带。The invention relates to the technical field of metal materials, in particular to a preparation method and application of a high-purity powder material and an alloy strip.
背景技术Background technique
微纳米粒径的粉体，由于具有特殊的表面效应、量子尺寸效应，量子隧道效应以及库仑阻塞效应等，在光学、电学、磁学、催化等方面表现出诸多与传统材料不同的奇特性能，因此被广泛地应用于光电子器件、吸波材料、高效催化剂等多个领域。Due to the special surface effect, quantum size effect, quantum tunneling effect and Coulomb blocking effect, powders with micro-nano particle size show many strange properties different from traditional materials in optics, electricity, magnetism, catalysis, etc. Therefore, it is widely used in optoelectronic devices, absorbing materials, high-efficiency catalysts and other fields.
目前，超细粉体的制备方法从物质的状态分有固相法、液相法和气相法。固相法主要有机械粉碎法、超声波粉碎法、热分解法、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。虽然超细粉末的制备方法有很多种，但每种方法都有一定的局限性。例如，液相法的缺点是产量低、成本高和工艺复杂等。机械法的缺点是在制取粉末后存在分级困难的问题，且产品的纯度、细度和形貌均难以保证。旋转电极法和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，超细粉末的收得率不高，能耗相对较大；气流磨法、氢化脱氢法适合大批量工业化生产，但对原料金属和合金的选择性较强。At present, the preparation methods of ultrafine powder are divided into solid phase method, liquid phase method and gas phase method according to the state of matter. The solid-phase methods mainly include mechanical pulverization, ultrasonic pulverization, thermal decomposition, and explosion methods. Liquid phase methods mainly include precipitation method, alkoxide method, carbonyl method, spray thermal drying method, freeze drying method, electrolysis method, chemical coagulation method, etc. The gas phase method mainly includes gas phase reaction method, plasma method, high temperature plasma method, evaporation method, chemical vapor deposition method, etc. Although there are many ways to prepare ultrafine powders, 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 is prepared, and the purity, fineness and morphology of the product are difficult to guarantee. Rotating electrode method and atomization method are the main methods for preparing high-performance metal and alloy powder at present, but the production efficiency is low, the yield of ultrafine powder is not high, and the energy consumption is relatively large; jet milling method and hydrogenation dehydrogenation method are suitable for Large-scale industrial production, but strong selectivity to raw metals and alloys.
此外，粉体的杂质含量，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, 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，有必要针对上述技术问题，提供一种工艺简单、易于操作的高纯粉体材料的制备方法及其应用。Based on this, it is necessary to provide a preparation method of high-purity powder material with simple process and easy operation and its application in view of the above technical problems.
一种高纯粉体材料的制备方法，其特征在于，包括以下步骤：A preparation method of high-purity powder material, 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T的均匀初始合金熔体，其中，T包含O、H、N、P、S、F、Cl、I、Br中的至少一种，且所述初始合金熔体的平均成分包括如下组合(1)-(4)中的任意一种：Step S1, select an 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 an impurity element T, wherein T includes O, H, N, P, S, F, Cl, At least one of I, Br, and the average composition of the initial alloy melt includes any one of the following combinations (1)-(4):
组合(1)：所述初始合金熔体的平均成分主要为A a(M xD y) bT d，其中，A包含Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的至少一种，M包含W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti中的至少一种，D包含Fe、Co、Ni中的至少一种，其中，x、y；a、b、d均代表对应组成元素的原子百分比含量，且24.9％≤a≤99.4％，0.5％≤b≤75％，0<d≤10％；作为优选，24.9％≤a≤59.9％，40％<b≤75％，0<d≤10％； Combination (1): the average composition of the initial alloy melt is mainly A a (M x D y ) b T d , wherein A includes Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, At least one of Tb, Dy, Ho, Er, Tm, Yb, Lu, M includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti, D includes Fe, Co, At least one of Ni, wherein x, y; a, b, and d all represent the atomic percentage content of the corresponding constituent elements, and 24.9%≤a≤99.4%, 0.5%≤b≤75%, 0<d≤10 %; preferably, 24.9%≤a≤59.9%, 40%<b≤75%, 0<d≤10%;
进一步地，10％≤x≤55％，45％≤y≤90％；Further, 10%≤x≤55%, 45%≤y≤90%;
进一步地，摩尔比x:y＝0.9～1.1；Further, the molar ratio x:y=0.9～1.1;
作为优选，x＝y＝50％，即摩尔比x:y＝1:1；Preferably, x=y=50%, that is, the molar ratio x:y=1:1;
组合(2)：所述初始合金熔体的平均成分主要为A aM bT d，其中，A包含Mg、Ca、Li、Na、K、Cu、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的至少一种，M包含W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti中的至少一种；其中a、b、d代表对应组成元素的原子百分比含量，且24.9％≤a≤99.4％，0.5％≤b≤75％，0<d≤10％； Combination (2): the average composition of the initial alloy melt is mainly A a M b T d , wherein A includes Mg, Ca, Li, Na, K, Cu, Y, La, Ce, Pr, Nd, Pm , at least one of Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, M includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti ; where a, b, d represent the atomic percentage content of the corresponding constituent elements, and 24.9%≤a≤99.4%, 0.5%≤b≤75%, 0<d≤10%;
作为优选，当M包含W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti中的至少一种时，A包含Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的一种；Preferably, when M includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, and Ti, A includes Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, One of Tb, Dy, Ho, Er, Tm, Yb, Lu;
作为优选，当M包含W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti中的至少一种时，A包含Cu；Preferably, when M includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, and Ti, A includes Cu;
作为优选，24.9％≤a≤54.9％，45％<b≤75％，0<d≤10％；Preferably, 24.9%≤a≤54.9%, 45%<b≤75%, 0<d≤10%;
组合(3)：所述初始合金熔体的平均成分主要为A aM bT d，其中，A包含Zn、Mg、Sn、Pb、Ga、In、Al、La、Ge、Cu、K、Na、Li中的至少一种，M包含B、Bi、Fe、Ni、Cu、Ag、Si、Ge、Cr、V中的至少一种，其中a、b、d代表对应组成元素的原子百分比含量，且24.9％≤a≤59.9％，40％<b≤75％，0<d≤10％； Combination (3): the average composition of the initial alloy melt is mainly A a M b T d , wherein A includes Zn, Mg, Sn, Pb, Ga, In, Al, La, Ge, Cu, K, Na , at least one of Li, M includes at least one of B, Bi, Fe, Ni, Cu, Ag, Si, Ge, Cr, V, wherein a, b, d represent the atomic percentage content of the corresponding constituent elements, And 24.9%≤a≤59.9%, 40%<b≤75%, 0<d≤10%;
作为优选，当M包含B时，A包含Sn、Ge、Cu、Zn中的至少一种；当M包含Bi时，A包含Sn、Ga、Al中的至少一种；Preferably, when M contains B, A contains at least one of Sn, Ge, Cu, and Zn; when M contains Bi, A contains at least one of Sn, Ga, and Al;
作为优选，当M包含Fe、Ni、Cu、Ag中的至少一种时，A包含La、In、Na、K、Li、Pb、Mg中的至少一种；作为优选，当M包含Fe、Ni中的至少一种时，A包含La、In、Na、K、Li、Mg中的至少一种；当M包含Cu、Ag中的至少一种时，A包含Pb、Na、K、Li中的至少一种；Preferably, when M contains at least one of Fe, Ni, Cu, and Ag, A contains at least one of La, In, Na, K, Li, Pb, and Mg; preferably, when M contains Fe, Ni When at least one of La, In, Na, K, Li, and Mg is contained in A; when M contains at least one of Cu and Ag, A contains at least one of Pb, Na, K, and Li. at least one;
作为优选，当M包含Si、Ge中的至少一种时，A包含Zn、Sn、Pb、Ga、In、Al中的至少一种；Preferably, when M contains at least one of Si and Ge, A contains at least one of Zn, Sn, Pb, Ga, In, and Al;
作为优选，当M包含Cr、V中的至少一种时，A包含Zn；Preferably, when M contains at least one of Cr and V, A contains Zn;
组合(4):当所述初始合金熔体的平均成分主要为A aM bAl cT d时，A包含Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的至少一种；M包含W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti中的至少一种；Al为铝；其中a、b、c、d分别代表对应组成元素的原子百分比含量，且29.8％≤a≤64.8％，35％<b≤70％，0.1％≤c≤25％，0<d≤10％； Combination (4): When the average composition of the initial alloy melt is mainly A a M b Al c T d , A contains Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy , at least one of Ho, Er, Tm, Yb, Lu; M includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti; Al is aluminum; wherein a, b, c and d respectively represent the atomic percentage content of the corresponding constituent elements, and 29.8%≤a≤64.8%, 35%<b≤70%, 0.1%≤c≤25%, 0<d≤10%;
进一步地，所述初始合金熔体的平均成分为如上组合(1)-(4)中的任意一种；Further, the average composition of the initial alloy melt is any one of the above combinations (1)-(4);
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T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 T 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;
当初始合金熔体的平均成分为步骤S1组合(1)所述时，所述初始合金条带中弥散颗粒相的成分主要为(M xD y) x1T z1，基体相的平均成分主要为A x2T z2；且98.5％≤x1<100％,0<z1≤1.5％；80％≤x2<100％,0<z2≤20％；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； When the average composition of the initial alloy melt is as described in step S1 combination (1), the composition of the dispersed particle phase in the initial alloy strip is mainly (M x D y ) x1 T z1 , and the average composition of the matrix phase is mainly A x2 T z2 ; and 98.5%≤x1<100%, 0<z1≤1.5%;80%≤x2<100%,0<z2≤20%;z1<d<z2,2z1<z2; x1, z1, x2 and z2 respectively represent the atomic percentage content of the corresponding constituent elements;
作为优选，当初始合金熔体的平均成分为步骤S1组合(1)所述时，成分主要为(M xD y) x1T z1的弥散颗粒相中不含有A元素。 Preferably, when the average composition of the initial alloy melt is as described in step S1 combination (1), the dispersed particle phase whose composition is mainly (M x D y ) x1 T z1 does not contain A element.
作为优选，当初始合金熔体的平均成分为步骤S1组合(1)所述时，所述初始合金条带中弥散颗粒相的成分为(M xD y) x1T z1，基体相的平均成分为A x2T z2； Preferably, when the average composition of the initial alloy melt is as described in step S1 combination (1), the composition of the dispersed particle phase in the initial alloy strip is (M x D y ) x1 T z1 , and the average composition of the matrix phase is is A x2 T z2 ;
当初始合金熔体的平均成分为步骤S1组合(2)或组合(3)所述时，所述初始合金条带中弥散颗粒相的成分主要为M x1T z1，基体相的平均成分主要为A x2T z2；且98.5％≤x1<100％,0<z1≤1.5％；80％≤x2<100％,0<z2≤20％；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； When the average composition of the initial alloy melt is described in combination (2) or (3) of step S1, the composition of the dispersed particle phase in the initial alloy strip is mainly M x1 T z1 , and the average composition of the matrix phase is mainly A x2 T z2 ; and 98.5%≤x1<100%, 0<z1≤1.5%;80%≤x2<100%,0<z2≤20%;z1<d<z2,2z1<z2; x1, z1, x2 and z2 respectively represent the atomic percentage content of the corresponding constituent elements;
作为优选，当初始合金熔体的平均成分为步骤S1组合(2)或组合(3)所述时，成分主要为M x1T z1的弥散颗粒相中不含有A元素。 Preferably, when the average composition of the initial alloy melt is as described in combination (2) or combination (3) in step S1, the dispersed particle phase with the main composition M x1 T z1 does not contain A element.
作为优选，当初始合金熔体的平均成分为步骤S1组合(2)或组合(3)所述时，所述初始合金条带中的弥散颗粒相的成分为M x1T z1，基体相的平均成分为A x2T z2； Preferably, when the average composition of the initial alloy melt is described in combination (2) or combination (3) in step S1, the composition of the dispersed particle phase in the initial alloy strip is M x1 T z1 , and the average composition of the matrix phase is M x1 T z1 . The composition is A x2 T z2 ;
当初始合金熔体的平均成分为步骤S1组合(4)所述时，所述初始合金条带中弥散颗粒相的成分主要为M x1Al y1T z1，基体相的平均成分主要为A x2Al y2T z2；且77.8％≤x1≤99.8％，0.1％≤y1≤22％，0<z1≤1.5％；69.8％≤x2≤99.7％，0.2％≤y2≤30％，0<z2≤20％，z1<d<z2，2z1<z2，y1<y2，x1、y1、z1、x2、y2、z2分别代表对应组成元素的原子百分比含量； When the average composition of the initial alloy melt is as described in step S1 combination (4), the composition of the dispersed particle phase in the initial alloy strip is mainly M x1 Al y1 T z1 , and the average composition of the matrix phase is mainly A x2 Al y2 T z2 ; and 77.8%≤x1≤99.8%, 0.1%≤y1≤22%, 0<z1≤1.5%; 69.8%≤x2≤99.7%, 0.2%≤y2≤30%, 0<z2≤20% , z1<d<z2, 2z1<z2, y1<y2, x1, y1, z1, x2, y2, z2 respectively represent the atomic percentage content of the corresponding constituent elements;
作为优选，当初始合金熔体的平均成分为步骤S1组合(4)所述时，成分主要为M x1Al y1T z1的弥散颗粒相中不含有A元素。 Preferably, when the average composition of the initial alloy melt is as described in step S1 combination (4), the dispersed particle phase whose composition is mainly M x1 Aly1 T z1 does not contain A element.
作为优选，当初始合金熔体的平均成分为步骤S1组合(4)所述时，所述初始合金条带中弥散颗粒相的成分为M x1Al y1T z1，基体相的平均成分为A x2Al y2T z2； Preferably, when the average composition of the initial alloy melt is as described in step S1 combination (4), the composition of the dispersed particle phase in the initial alloy strip is M x1 Al y1 T z1 , and the average composition of the matrix phase is A x2 Al y2 T z2 ;
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, and the shedding dispersed particle phase is collected, that is, a high-purity particle composed of the original dispersed particles is obtained. Target powder material.
所述步骤S1中，In the step S1,
进一步地，所述初始合金熔体中的T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 T 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，T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T杂质元素的含量；Further, T is an impurity element and contains 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 T 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.
进一步地，所述初始合金原料包括含有杂质元素T的M-T原料。例如，当M为Ti，且T包含O时，M-T原料即包括含有O杂质的Ti-O原料。Further, the initial alloy raw material includes an M-T raw material containing an impurity element T. For example, when M is Ti and T contains O, the M-T raw material includes Ti-O raw material containing O impurities.
进一步的，所述步骤S1中初始合金熔体平均成分中A与M的组合极为重要，其选择原则是确保合金熔体凝固过程中A与M之间不形成金属间化合物；或者即使M与其它元素(D)可以形成高熔点金属间化合物，但A与M之间仍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A主的基体相和与M为的颗粒相的两相分离，有利于后续制备以M为主的粉体材料。Further, the combination of A and M in the average composition of the initial alloy melt in the step S1 is extremely important, and the selection principle is to ensure that no intermetallic compound is formed between A and M during the solidification of the alloy melt; or even if M and other Element (D) can form a high melting point intermetallic compound, but still no intermetallic compound is formed between A and M. In this way, the two-phase separation of the matrix phase dominated by A and the particle phase dominated by M can be realized during the solidification of the initial alloy melt, which is beneficial to the subsequent preparation of powder materials dominated by M.
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A与M构成的金属间化合物；Further, the initial alloy strip does not contain intermetallic compounds comprising A and M;
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～50mm；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 50 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。Further, the width of the cross-section of the initial alloy strip is more than twice the thickness.
进一步地，所述初始合金条带的长度是其厚度的10倍以上。Further, the length of the initial alloy strip is more than 10 times its thickness.
作为优选，所述初始合金条带的长度是其厚度的50倍以上。Preferably, the length of the initial alloy strip is more than 50 times its thickness.
作为优选，所述初始合金条带的长度是其厚度的100倍以上。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 1 K/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.
当基体相主元素为大原子元素时，基体相可以通过较小的原子比百分含量获得较高的体积百分比含量。如原子百分比组成为La 25Fe 75的初始合金条带(为了计算方便，不考虑杂质存在情况)，La与Fe的重量百分含量分别为45.33wt％与54.67wt％，结合两者密度分别为6.2g/cm 3与7.8g/cm 3，可以计算得到La、Fe在原子百分比组成为La 25Fe 75的初始合金条带中的体积百分含量分别为51vol.％与49vol.％。这表明：即使La-Fe合金中Fe的原子百分比含量高达75at.％，其体积百分比含量仍然低于50vol.％，从而有利于初始合金条带中Fe颗粒的弥散分布。 When the main element of the matrix phase is a large atomic element, the matrix phase can obtain a higher volume percentage content through a smaller atomic percentage content. For example, the atomic percentage composition of the initial alloy strip of La 25 Fe 75 (for the convenience of calculation, the existence of impurities is not considered), the weight percentages of La and Fe are 45.33wt% and 54.67wt%, respectively, and the combined densities of the two are 6.2 g/cm 3 and 7.8 g/cm 3 , the volume percentages of La and Fe in the initial alloy strip with the atomic percentage composition La 25 Fe 75 can be calculated to be 51 vol.% and 49 vol.%, respectively. This shows that even though the atomic percent content of Fe in the La-Fe alloy is as high as 75 at.%, its volume percent content is still lower than 50 vol.%, which is favorable for the dispersion distribution of Fe particles in the initial alloy strips.
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％vol.％。Further, the volume percentage content of the dispersed particle phase in its corresponding initial alloy strip is not higher than 50% vol.%.
进一步地，所述弥散颗粒中的T杂质元素原子百分比含量z1小于M-T原料中的T杂质元素原子百分比含量。Further, the atomic percentage content z1 of the T impurity element in the dispersed particles is less than the atomic percentage content of the T impurity element in the M-T raw material.
进一步地，z1<d<z2，且2z1<z2，Further, z1<d<z2, and 2z1<z2,
作为优选，z1<d<z2，且3z1<z2，Preferably, z1<d<z2, and 3z1<z2,
作为优选，0<z1<d<z2，3z1<z2，且0<z1≤1.5％；即所述弥散颗粒相中T杂质含量低于所述初始合金熔体中的T杂质含量，且所述弥散颗粒相中T杂质含量的3倍仍然低于所述基体相中的T杂质含量；Preferably, 0<z1<d<z2, 3z1<z2, and 0<z1≤1.5%; that is, the T impurity content in the dispersed particle phase is lower than the T impurity content in the initial alloy melt, and the 3 times the T impurity content in the dispersed particle phase is still lower than the T impurity content in the matrix phase;
作为优选，0<z1<d<z2，3z1<z2，且0<z1≤0.75％。Preferably, 0<z1<d<z2, 3z1<z2, and 0<z1≤0.75%.
本发明采用原子百分比含量来表达T杂质含量。通过元素的原子百分比含量来表征各元素的组成，可以通过物质的量的概念准确地表达元素含量的增减变化，比如杂质元素的增减与 变化。如果采用元素的质量百分比含量(或ppm概念)来表征各个元素的含量，由于各元素原子量的不同，则容易产生错误的结论。举例来说，如原子百分比含量为Ti 45Gd 45O 10的合金，包含100个原子，O的原子百分比含量为10at％。将这100个原子分成Ti 45O 4(原子百分比组成为Ti 91.8O 8.2)与Gd 45O 6(原子百分比组成为Gd 88.2O 11.8)两部分，Gd 45O 6中氧的原子百分比含量增为11.8at％，Ti 45O 4中氧的原子百分比含量减为8.2at％，可以很准确地表达Gd中富集了O。但若采用O的质量百分比含量来衡量，Ti 45Gd 45O 10中O的质量百分比含量为1.70wt％，Ti 45O 4与Gd 45O 6中O的质量百分比含量分别为2.9wt.％与1.34wt.％，将会得出Ti 45O 4中O含量相比Gd 45O 6中O含量明显增加的错误结论。 The present invention adopts the atomic percentage content to express the T impurity content. The composition of each element is characterized by the atomic percentage content of the element, and the increase or decrease of element content, such as the increase or decrease of impurity elements, can be accurately expressed through the concept of material quantity. If the mass percentage content (or ppm concept) of elements is used to characterize the content of each element, it is easy to produce wrong conclusions due to the difference in atomic weight of each element. For example, an alloy whose atomic percent content is Ti 45 Gd 45 O 10 contains 100 atoms, and the atomic percent content of O is 10 at %. The 100 atoms are divided into two parts: Ti 45 O 4 (the atomic percentage composition is Ti 91.8 O 8.2 ) and Gd 45 O 6 (the atomic percentage composition is Gd 88.2 O 11.8 ), and the atomic percentage content of oxygen in Gd 45 O 6 is increased to 11.8at%, the atomic percentage of oxygen in Ti 45 O 4 is reduced to 8.2at%, which can accurately express that O is enriched in Gd. However, if the mass percent content of O is used to measure, the mass percent content of O in Ti 45 Gd 45 O 10 is 1.70 wt %, and the mass percent content of O in Ti 45 O 4 and Gd 45 O 6 is 2.9 wt. % and 2.9 wt % respectively. 1.34wt.%, it would lead to the wrong conclusion that the O content in Ti 45 O 4 is significantly increased compared to that in Gd 45 O 6 .
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、碱反应去除、真空挥发去除中的至少一种。Further, the method for removing the matrix phase from the alloy strip includes at least one of acid reaction removal, alkali reaction removal, and vacuum volatilization removal.
所述酸溶液与碱溶液的组成与浓度不做具体限定，只要能够保证去除基体相，同时保留弥散颗粒相即可。The composition and concentration of the acid solution and the alkali solution are not specifically limited, as long as the matrix phase can be removed and the dispersed particle phase can be retained at the same time.
所述真空处理的温度与真空度不做具体限定，只要能够保证去除基体相，同时保留弥散颗粒相即可。The temperature and vacuum degree of the vacuum treatment are not specifically limited, as long as the matrix phase can be removed and the dispersed particle phase can be retained at the same time.
进一步地，所述将初始合金条带中基体相去除方法包括基体相自然氧化-粉化剥落去除。Further, the method for removing the matrix phase in the initial alloy strip includes the natural oxidation of the matrix phase-powdering and exfoliation removal.
当基体相为极易与氧发生自然氧化的元素，如La、Ce等时，通过基体相的自然氧化-粉化过程，就可以将基体相与弥散颗粒相分开，再辅以其它技术手段，如磁选，就可以将诸如具有磁性的弥散颗粒相与基体相的自然氧化物分开。When the matrix phase is an element that is easily oxidized naturally with oxygen, such as La, Ce, etc., the matrix phase can be separated from the dispersed particle phase through the natural oxidation-pulverization process of the matrix phase, and then supplemented by other technical means, Such as magnetic separation, it is possible to separate, for example, the magnetically dispersed particle phase from the natural oxides of the matrix phase.
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，所述目标粉体材料的颗粒粒径范围为2nm～3mm；作为优选，所述目标粉体材料的颗粒粒径范围为2nm～500μm；作为优选，所述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 is 2 nm to 3 mm; preferably, the particle size range of the target powder material is 2 nm to 500 μm; The diameter range is 2nm～99μm; as a further preference, the particle diameter range of the target powder material is 2nm～5μm; as a further preference, the particle diameter range of the target powder material is 2nm～200nm; as a further preference , the particle size of the target powder material ranges from 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，即得到高纯目标粉体材料。Further, after the initial alloy strip is reacted with the acid solution, the dispersed particles are separated from the initial alloy strip, cleaned and dried to obtain a high-purity target powder material.
作为优选，当初始合金熔体的平均成分为步骤S1组合(1)所述时，所述高纯目标粉体材料的成分主要为(M xD y) x1T z1； Preferably, when the average composition of the initial alloy melt is described in step S1 combination (1), the composition of the high-purity target powder material is mainly (M x D y ) x1 T z1 ;
进一步地，当初始合金熔体的平均成分为步骤S1组合(1)所述时，所述成分主要为(M xD y) x1T z1的弥散颗粒中不含有A元素； Further, when the average composition of the initial alloy melt is described in the combination (1) of step S1, the dispersed particles whose composition is mainly (M x D y ) x1 T z1 do not contain A element;
作为优选，当初始合金熔体的平均成分为步骤S1组合(1)所述时，所述高纯目标粉体材料的成分为(M xD y) x1T z1； Preferably, when the average composition of the initial alloy melt is as described in step S1 combination (1), the composition of the high-purity target powder material is (M x D y ) x1 T z1 ;
进一步地，当初始合金熔体的平均成分为步骤S1组合(2)或(3)所述时，所述高纯目标粉体材料的成分主要为M x1T z1； Further, when the average composition of the initial alloy melt is described in combination (2) or (3) in step S1, the composition of the high-purity target powder material is mainly M x1 T z1 ;
作为优选，当初始合金熔体的平均成分为步骤S1组合(2)或(3)所述时，成分主要为M x1T z1的弥散颗粒中不含有A元素； Preferably, when the average composition of the initial alloy melt is described in combination (2) or (3) in step S1, the dispersed particles whose composition is mainly M x1 T z1 do not contain A element;
作为优选，当初始合金熔体的平均成分为步骤S1组合(2)或(3)所述时，所述高纯目标粉体材料的成分为M x1T z1； Preferably, when the average composition of the initial alloy melt is described in combination (2) or (3) in step S1, the composition of the high-purity target powder material is M x1 T z1 ;
进一步地，当初始合金熔体的平均成分为步骤S1组合(4)所述时，所述高纯目标粉体材料的成分主要为M x1Al y1T z1。 Further, when the average composition of the initial alloy melt is as described in step S1 combination (4), the composition of the high-purity target powder material is mainly M x1 Aly1 T z1 .
作为优选，当初始合金熔体的平均成分为步骤S1组合(4)所述时，成分主要为M x1Al y1T z1的弥散颗粒中不含有A元素； Preferably, when the average composition of the initial alloy melt is described in step S1 combination (4), the dispersed particles whose composition is mainly M x1 Aly1 T z1 do not contain A element;
作为优选，当初始合金熔体的平均成分为步骤S1组合(4)所述时，所述高纯目标粉体材料的成分为M x1Al y1T z1。 Preferably, when the average composition of the initial alloy melt is as described in step S1 combination (4), the composition of the high-purity target powder material is M x1 Aly1 T z1 .
进一步地，所述目标金属粉中的T杂质元素的原子百分比含量不超过1.5％；Further, the atomic percentage content of the T impurity element in the target metal powder does not exceed 1.5%;
作为优选，所述目标金属粉中的T杂质元素的原子百分比含量不超过0.75％。Preferably, the atomic percentage content of the T impurity element in the target metal powder does not exceed 0.75%.
进一步地，在所述步骤S3之后还进行以下步骤：将所述高纯粉体材料筛分后，选择粒径范围为5μm～200μm的高纯粉体材料进行等离子球化处理，以得到呈球形的高纯粉体材料；Further, after the step S3, the following steps are also performed: after sieving the high-purity powder material, select a high-purity powder material with a particle size ranging from 5 μm to 200 μm for plasma spheroidization, so as to obtain a spherical shape. of high-purity powder materials;
本发明还涉及上述制备方法得到的高纯粉体材料或球形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、涂料中的应用。The invention also relates to the application of the high-purity powder material or spherical high-purity powder material obtained by the above preparation method in catalytic materials, powder metallurgy, composite materials, wave absorbing materials, sterilization materials, metal injection molding, 3D printing, and coatings.
进一步地，如上述制备方法得到的球形高纯粉体材料在金属粉3D打印领域中的应用，其特征在于，球形高纯粉体材料的粒径范围为10μm～200μm。Further, the application of the spherical high-purity powder material obtained by the above preparation method in the field of metal powder 3D printing is characterized in that the particle size of the spherical high-purity powder material ranges from 10 μm to 200 μm.
进一步地，如上述制备方法得到的高纯粉体材料在金属注射成型、粉末冶金中的应用，其特征在于，高纯粉体材料的粒径范围为0.1μm～200μm。Further, the application of the high-purity powder material obtained by the above preparation method in metal injection molding and powder metallurgy is characterized in that the particle size of the high-purity powder material ranges from 0.1 μm to 200 μm.
进一步地，如上述制备方法得到的高纯粉体材料在涂料中的应用，其特征在于，高纯粉体材料的粒径范围为2nm～5μm。Further, the application of the high-purity powder material obtained by the above preparation method in a coating is characterized in that the particle size of the high-purity 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;
所述合金条带的化学组成与结构包含以下四种组合中的任意一种：The chemical composition and structure of the alloy strip includes any one of the following four combinations:
1)所述合金条带中内生粉的成分主要为(M xD y) x1T z1，包覆体的平均成分主要为A x2T z2；且98.5％≤x1<100％,0<z1≤1.5％；80％≤x2<100％,0<z2≤20％；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，A包含Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的至少一种，M包含W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti中的至少一种，D包含Fe、Co、Ni中的至少一种；T包含O、H、N、P、S、F、Cl、I、Br中的至少一种；x、y代表对应组成元素的原子百分比含量，10％≤x≤55％，45％≤y≤90％；进一步地，摩尔比x:y＝0.9～1.1；作为优选，x＝y＝50％，即摩尔比x:y＝1:1； 1) The composition of the endogenous powder in the alloy strip is mainly (M x D y ) x1 T z1 , and the average composition of the clad is mainly A x2 T z2 ; and 98.5%≤x1<100%, 0<z1 ≤1.5%; 80%≤x2<100%, 0<z2≤20%;z1<d<z2,2z1<z2; x1, z1, x2, z2 respectively represent the atomic percentage content of the corresponding constituent elements; among them, A contains At least one of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, M includes W, Cr, Mo, V, Ta, Nb , at least one of Zr, Hf, Ti, D includes at least one of Fe, Co, Ni; T includes at least one of O, H, N, P, S, F, Cl, I, Br; x and y represent the atomic percentage content of the corresponding constituent elements, 10%≤x≤55%, 45%≤y≤90%; further, the molar ratio x:y=0.9～1.1; preferably, x=y=50% , that is, the molar ratio x:y=1:1;
作为优选，合金条带中成分主要为(M xD y) x1T z1的内生粉中不含有A元素。 Preferably, the endogenous powder whose composition is mainly (M x D y ) x1 T z1 in the alloy strip does not contain A element.
作为优选，所述合金条带中内生粉的成分为(M xD y) x1T z1，包覆体的平均成分为A x2T z2； Preferably, the composition of the endogenous powder in the alloy strip is (M x D y ) x1 T z1 , and the average composition of the cladding body is A x2 T z2 ;
2)所述合金条带中内生粉的成分主要为M x1T z1，包覆体的平均成分主要为A x2T z2；且98.5％≤x1<100％,0<z1≤1.5％；80％≤x2<100％,0<z2≤20％；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，A包含Mg、Ca、Li、Na、K、Cu、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的至少一种，M包含W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti中的至少一种；T包含O、H、N、P、S、F、Cl、I、Br中的至少一种； 2) The composition of the endogenous powder in the alloy strip is mainly M x1 T z1 , and the average composition of the clad is mainly A x2 T z2 ; and 98.5%≤x1<100%, 0<z1≤1.5%; 80 %≤x2<100%, 0<z2≤20%;z1<d<z2,2z1<z2; x1, z1, x2, z2 represent the atomic percentage content of the corresponding constituent elements respectively; among them, A contains Mg, Ca, Li , at least one of Na, K, Cu, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, M includes W, Cr, At least one of Mo, V, Ta, Nb, Zr, Hf, Ti; T includes at least one of O, H, N, P, S, F, Cl, I, Br;
作为优选，当M包含W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti中的至少一种时，A包含Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的一种；Preferably, when M includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, and Ti, A includes Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, One of Tb, Dy, Ho, Er, Tm, Yb, Lu;
作为优选，当M包含W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti中的至少一种时，A包含Cu；Preferably, when M includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, and Ti, A includes Cu;
作为优选，合金条带中成分主要为M x1T z1的内生粉中不含有A元素； Preferably, the inner powder whose composition is mainly M x1 T z1 in the alloy strip does not contain A element;
作为优选，所述合金条带中内生粉的成分为M x1T z1，包覆体的平均成分为A x2T z2； Preferably, the composition of the endogenous powder in the alloy strip is M x1 T z1 , and the average composition of the cladding body is A x2 T z2 ;
3)所述合金条带中内生粉的成分主要为M x1T z1，包覆体的平均成分主要为A x2T z2；且98.5％≤x1<100％,0<z1≤1.5％；80％≤x2<100％,0<z2≤20％；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，A包含Zn、Mg、Sn、Pb、Ga、In、Al、La、Ge、Cu、K、Na、Li中的至少一种，M包含B、Bi、Fe、Ni、Cu、Ag、Si、Ge、Cr、V中的至少一种； 3) The composition of the endogenous powder in the alloy strip is mainly M x1 T z1 , and the average composition of the clad is mainly A x2 T z2 ; and 98.5%≤x1<100%, 0<z1≤1.5%; 80 %≤x2<100%, 0<z2≤20%;z1<d<z2,2z1<z2; x1, z1, x2, and z2 represent the atomic percentage content of the corresponding constituent elements, respectively; A contains Zn, Mg, Sn , at least one of Pb, Ga, In, Al, La, Ge, Cu, K, Na, Li, M includes at least one of B, Bi, Fe, Ni, Cu, Ag, Si, Ge, Cr, V A sort of;
作为优选，当M包含B时，A包含Sn、Ge、Cu、Zn中的至少一种；当M包含Bi时，A包含Sn、Ga、Al中的至少一种；Preferably, when M contains B, A contains at least one of Sn, Ge, Cu, and Zn; when M contains Bi, A contains at least one of Sn, Ga, and Al;
作为优选，当M包含Fe、Ni、Cu、Ag中的至少一种时，A包含La、In、Na、K、Li、 Pb、Mg中的至少一种；作为优选，当M包含Fe、Ni中的至少一种时，A包含La、In、Na、K、Li、Mg中的至少一种；当M包含Cu、Ag中的至少一种时，A包含Pb、Na、K、Li中的至少一种；Preferably, when M contains at least one of Fe, Ni, Cu, and Ag, A contains at least one of La, In, Na, K, Li, Pb, and Mg; preferably, when M contains Fe, Ni When at least one of La, In, Na, K, Li, and Mg is contained in A; when M contains at least one of Cu and Ag, A contains at least one of Pb, Na, K, and Li. at least one;
作为优选，当M包含Si、Ge中的至少一种时，A包含Zn、Sn、Pb、Ga、In、Al中的至少一种；Preferably, when M contains at least one of Si and Ge, A contains at least one of Zn, Sn, Pb, Ga, In, and Al;
作为优选，当M包含Cr、V中的至少一种时，A包含Zn；Preferably, when M contains at least one of Cr and V, A contains Zn;
作为优选，合金条带中成分主要为M x1T z1的内生粉中不含有A元素。 Preferably, the endogenous powder whose composition is mainly M x1 T z1 in the alloy strip does not contain A element.
作为优选，所述合金条带中的内生粉的成分为M x1T z1，包覆体的平均成分为A x2T z2； Preferably, the composition of the endogenous powder in the alloy strip is M x1 T z1 , and the average composition of the cladding body is A x2 T z2 ;
4)所述合金条带中内生粉的成分主要为M x1Al y1T z1，包覆体的平均成分主要为A x2Al y2T z2；且77.8％≤x1≤99.8％，0.1％≤y1≤22％，0<z1≤1.5％；69.8％≤x2≤99.7％，0.2％≤y2≤30％，0<z2≤20％，z1<d<z2，2z1<z2，y1<y2，x1、y1、z1、x2、y2、z2分别代表对应组成元素的原子百分比含量；其中，A包含Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的至少一种；M包含W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti中的至少一种；Al为铝； 4) The composition of the endogenous powder in the alloy strip is mainly M x1 A y1 T z1 , and the average composition of the clad is mainly A x2 A y2 T z2 ; and 77.8%≤x1≤99.8%, 0.1%≤y1 ≤22%, 0<z1≤1.5%; 69.8%≤x2≤99.7%, 0.2%≤y2≤30%, 0<z2≤20%, z1<d<z2, 2z1<z2, y1<y2, x1, y1, z1, x2, y2, and z2 respectively represent the atomic percentage content of the corresponding constituent elements; among them, A includes Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm , at least one of Yb, Lu; M includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti; Al is aluminum;
作为优选，合金条带中成分主要为M x1Al y1T z1的内生粉中不含有A元素； Preferably, the inner powder whose composition is mainly M x1 Al y1 T z1 in the alloy strip does not contain A element;
作为优选，所述合金条带中内生粉的成分为M x1Al y1T z1，包覆体的平均成分为A x2Al y2T z2； Preferably, the composition of the endogenous powder in the alloy strip is M x1 Aly1 T z1 , and the average composition of the clad is A x2 A y2 T z2 ;
作为优选，所述合金条带的化学组成与结构为以上1)－4)所述四种组合中的任意一种；Preferably, the chemical composition and structure of the alloy strip is any one of the above four combinations in 1)-4);
进一步地，所述合金条带的厚度范围为5μm～50mm；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 strips ranges from 5 μm to 50 mm; preferably, the thickness of the alloy strips ranges from 5 μm to 5 mm; preferably, the thickness of the alloy strips ranges from 5 μm to 1 mm; 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，2z2≤z1，且0≤z2≤1.5％；Further, 2z2≤z1, and 0≤z2≤1.5%;
作为优选，3z2<z1，且0<z2≤1.5％；Preferably, 3z2<z1, and 0<z2≤1.5%;
作为进一步优选，3z2<z1，且0<z2≤0.75％。As a further preference, 3z2<z1, and 0<z2≤0.75%.
需要说明的是，本发明所述方案中所述A、M、D或者T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 A, M, D or T 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A、M、D或者T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 A, M, D or T contains other elements or impurity elements other than those listed above, the following 1 )-3) The factual processes and laws listed still exist:
1)所述初始合金条带中不含有主要由A与M，或A与D构成的金属间化合物；1) The initial alloy strip does not contain intermetallic compounds mainly composed of A and M, or A and D;
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T杂质含量不为0时，所述弥散颗粒相中T杂质含量低于所述初始合金熔体中的T杂质含量，且所述弥散颗粒相中T杂质含量的2倍仍然低于所述基体相中的T杂质含量。3) When the T impurity content in the initial alloy melt is not 0, the T impurity content in the dispersed particle phase is lower than the T impurity content in the initial alloy melt, and the T impurity content in the dispersed particle phase is less than 2 times is still lower than the T 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)高活性的基体主元素(如RE稀土元素)对初始合金熔体杂质元素的“吸收”作用。 由于基体元素一般为高活性，低熔点的元素，在合金熔体熔化及凝固过程中其与杂质元素T之间具有极强的亲和力，这可以使得初始合金熔体中的杂质元素T要么更多地进入主要由基体相主元素组成的基体相中，要么在熔体状态时与基体主元素形成熔渣，并与合金熔体分离去除；2)内生析出的弥散颗粒相形核长大过程中，杂质元素T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)由于第二相基体的存在，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第二相基体中，这就进一步降低了目标粉体材料中的杂质含量，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 material can be obtained from the low-purity raw material, and a new way is pointed out for the preparation of the high-purity powder material from the low-purity raw material, which is 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 highly active matrix main elements (such as RE rare earth elements) on impurity elements in the initial alloy melt. Since the matrix element is generally a highly active, low melting point element, it has a strong affinity with the impurity element T during the melting and solidification of the alloy melt, which can make the impurity element T in the initial alloy melt more It enters into the matrix phase mainly composed of the main elements of the matrix phase, or forms slag with the main elements of the matrix in the melt state, and separates and removes it from the alloy melt; 2) During the nucleation and growth of the endogenously precipitated dispersed particle , the impurity element T 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 second phase matrix, 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 second phase matrix, which further reduces the target powder material. The impurity content of the smelting process further reduces the requirements for the crucible, 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 dendritic 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, and it 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 the (111) plane arrangement, which will endow the target metal powder with special mechanical, physical and chemical properties, thereby producing beneficial effects.
第四，当初始合金熔体的平均成分为步骤S1组合(4)所述时，实现了包含有W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti等元素的金属或合金材料中Al元素的固溶。在上述合金材料中，Al元素的添加具有非常重要的作用。例如，目前使用最广泛的钛合金即Ti6Al4V合金。对于Ti6Al4V合金粉末来说，一般通过熔炼Ti6Al4V合金熔体，然后通过雾化制粉技术获得Ti6Al4V合金粉末。受雾化制粉技术的限制，其很难获得超细的Ti6Al4V合金粉末，甚至不能通过雾化制粉技术获得纳米级的Ti6Al4V合金粉末。因此，通过本发明所涉及的“去相法”实现Al元素在Ti-V合金中的添加，并制备各种粒径的Ti6Al4V合金粉末，具有非常重要的意义。本发明发现，当在A(A＝稀土元素RE中的至少一种)与M(M＝W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti等元素中的至少一种)组成的合金中添加可观含量Al元素时(可以超过10at.％甚至更高)，合金凝固组织中Al元素可以通过一定的含量分配关系同时存在于主要由RE组成的基体相与主要由M组成的弥散颗粒相中。由于RE-Al基体相可以很容易被酸 反应去除，而以M为主的含Al的弥散颗粒中的Al受惰性M元素的保护，不会轻易被酸反应去除(如Ti6Al4V合金具有很好的耐酸腐蚀能力)，这就使得通过酸反应去除基体相制备含Al钛合金粉末成为了可能。Fourth, when the average composition of the initial alloy melt is as described in step S1 combination (4), a metal or alloy material containing W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti and other elements is realized solid solution of Al element. In the above alloy materials, the addition of Al element plays a very important role. For example, the most widely used titanium alloy is Ti6Al4V alloy. For the Ti6Al4V alloy powder, the Ti6Al4V alloy powder is generally obtained by smelting the Ti6Al4V alloy melt, and then using the atomization powder technology. Due to the limitation of atomization powder technology, it is difficult to obtain ultra-fine Ti6Al4V alloy powder, and even nano-scale Ti6Al4V alloy powder cannot be obtained by atomization powder technology. Therefore, it is very important to realize the addition of Al element in the Ti-V alloy by the "dephase method" involved in the present invention, and to prepare Ti6Al4V alloy powders of various particle sizes. The present invention finds that when A (A = at least one of rare earth elements RE) and M (M = at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti and other elements) composition When a considerable content of Al is added to the alloy (which can exceed 10 at.% or even higher), the Al element in the solidified structure of the alloy can exist in the matrix phase mainly composed of RE and the dispersion mainly composed of M through a certain content distribution relationship. in the particle phase. Since the RE-Al matrix phase can be easily removed by acid reaction, the Al in M-based Al-containing dispersed particles is protected by inert M element and will not be easily removed by acid reaction (eg Ti6Al4V alloy has good Acid corrosion resistance), which makes it possible to prepare Al-containing titanium alloy powder by removing the matrix phase by acid reaction.
第五，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，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。Fifth, the alloy strip composed of the endogenous powder and the coating body (matrix phase) creatively uses the in-situ generated matrix phase to wrap the endogenous powder, and maintains 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 view of this problem, the technical solution of the present invention does not rush to remove the cladding body after preparing the alloy strip composed of the endogenous metal powder and the cladding body (matrix phase), but directly uses the cladding body Protect 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 nanopowder, the endogenous metal powder can be compounded with the resin at the same time as the endogenous metal powder is released from the cladding body or immediately afterward, so as to prepare the resin-based composite material with the addition of endogenous metal powder with high activity.
第六，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。Sixth, 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、磁性材料、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 including nano-scale, sub-micron-scale and micro-scale, and can be used in catalytic materials, powder metallurgy, composite materials , absorbing materials, sterilization materials, magnetic materials, metal injection molding, 3D printing, coatings and other fields have good application prospects.
作为备选方案，本发明还提供一种高纯金属粉的制备方法，其包括以下步骤：As an alternative, the present invention also provides a method for preparing high-purity metal powder, which comprises the following steps:
步骤一：选择初始合金，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，然后将合金熔体通过快速凝固技术制备成合金条带；Step 1: select the initial alloy, melt the initial alloy raw material according to the initial alloy composition ratio to obtain a uniform alloy melt, and then prepare the alloy melt into alloy strips by rapid solidification technology;
当所述初始合金的成分配比为A aM b时，A选自Mg、Ca、Li、Na、K、Zn、Pb、Sn、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的至少一种，M选自W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti、Fe、Co、Ni、Cu、Ag、Si、Ge中的至少一种，且M中不单独只含Fe；其中a、b代表对应组成元素的原子百分比含量，45％<b≤75％，a+b＝100％；且A aM b合金条带的凝固组织中不含有由A与M构成的金属间化合物，其凝固组织由成分为A的基体相以及成分为M的弥散颗粒相组成； When the composition ratio of the initial alloy is A a M b , A is selected from Mg, Ca, Li, Na, K, Zn, Pb, Sn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu , at least one of Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, M is selected from W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti, Fe, Co, Ni, Cu , at least one of Ag, Si, and Ge, and M does not contain only Fe alone; where a, b represent the atomic percentage content of the corresponding constituent elements, 45%<b≤75%, a+b=100%; and The solidified structure of the A a M b alloy strip does not contain intermetallic compounds composed of A and M, and its solidified structure is composed of the matrix phase with the composition A and the dispersed particle phase with the composition M;
当所述初始合金的成分配比为La aFe b时，40％<b≤75％，a+b＝100％，a、b代表对应组成元素的原子百分比含量；且La aFe b合金条带的凝固组织中不含有由La与Fe构成的金属间化合物，其凝固组织由成分为La的基体相以及成分为Fe的弥散颗粒相组成； When the composition ratio of the initial alloy is La a Fe b , 40%<b≤75%, a+b=100%, a and b represent the atomic percentage contents of the corresponding constituent elements; and La a Fe b alloy strips The solidified structure of the belt does not contain intermetallic compounds composed of La and Fe, and its solidified structure is composed of a matrix phase composed of La and a dispersed particle phase composed of Fe;
当所述初始合金的成分配比为A aM bAl c时，A选自Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的至少一种，Al为铝，M选自W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti、Fe、Co、Ni中的至少一种；其中a、b、c分别代表对应组成元素的原子百分比含量，35％<b≤75％，0.1％≤c≤30％，a+b+c＝100％；且A aM bAl c合金条带的凝固组织中不含有由A与M构成的金属间化合物，其凝固组织由成分为M x1Al y1的弥散颗粒相以及成分为A x2Al y2的基体相组成；其中x1、y1、x2、y2分别代表对应组成元素的原子百分比含量，且0.1％≤y1≤25％，0.1％≤y2≤35％，x1+y1＝100％，x2+y2＝100％； When the composition ratio of the initial alloy is A a M b Al c , A is selected from Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb , at least one of Lu, Al is aluminum, M is selected from at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti, Fe, Co, Ni; wherein a, b, c Respectively represent the atomic percentage content of the corresponding constituent elements, 35%<b≤75%, 0.1%≤c≤30%, a+b+c=100%; and the solidification structure of the A a M b Al c alloy strip is not Contains an intermetallic compound composed of A and M, and its solidification structure is composed of a dispersed particle phase with a composition of M x1 Al y1 and a matrix phase with a composition of A x2 Al y2 ; where x1, y1, x2, y2 represent the corresponding constituent elements respectively , and 0.1%≤y1≤25%, 0.1%≤y2≤35%, x1+y1=100%, x2+y2=100%;
所述初始合金熔体凝固过程中，合金熔体中的杂质元素与凝固过程中引入的杂质元素富集于所述基体相中，从而使所述弥散颗粒相得到纯化；During the solidification process of the initial alloy melt, the impurity elements in the alloy melt and the impurity elements introduced during the solidification process are enriched in the matrix phase, so that the dispersed particle phase is purified;
步骤二：将所述合金条带中的基体相去除并保留弥散颗粒相，富集于基体相中的杂质元素随之被去除，即得到由弥散颗粒组成的高纯目标金属粉。Step 2: The matrix phase in the alloy strip is removed and the dispersed particle phase is retained, and the impurity elements enriched in the matrix phase are removed accordingly, that is, a high-purity target metal powder composed of dispersed particles is obtained.
通过上述技术方案，可以实现超细且低杂质含量金属粉的制备。在细粉获得方面，合金熔体凝固速率越高，所获得的合金条带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。在杂质控制方面，由于所述基体相一般由低熔点、高活性元素组成，这就使得合金熔炼与快速凝固过程中杂质元素富集于基体相中，从而使得弥散颗粒相得到纯化与保护，实现高纯目标金属粉的制备。Through the above technical solutions, ultrafine and low impurity content metal powder can be prepared. In terms of obtaining fine powder, the higher the solidification rate of the alloy melt, the smaller the dispersed particle phase in the solidified structure of the obtained alloy strip. 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 matrix phase, which greatly reduces the ultra-fine metal powder. cost of powder preparation. In terms of impurity control, since the matrix phase is generally composed of elements with low melting point and high activity, the impurity elements are enriched in the matrix phase during the alloy smelting and rapid solidification process, so that the dispersed particle phase can be purified and protected. Preparation of high-purity target metal powder.
此外，在合金成分配比的选择上，虽然所述A aM b、La aFe b以及A aM bAl c合金中b(原子百分比含量)的最大值为75％，但这并不会影响弥散颗粒在基体相中的分散析出。因为本发明 的基体相主要由大原子元素组成，即使基体相的原子百分比含量不到50％，但其在合金条带中的体积百分比含量却可以远远高于其原子百分比含量。如La 25Fe 75(原子比成分)合金的凝固组织中，La基体的体积百分比含量仍然可达51％。在合金熔体凝固速率足够快，且Fe颗粒为纳米级时，La 25Fe 75合金凝固组织中的Fe颗粒来不及合并长大，仍然可以弥散析出。 In addition, in the selection of alloy composition ratio, although the maximum value of b (atomic percentage content) in the A a M b , La a Fe b and A a M b Al c alloys is 75%, this does not It affects the dispersion and precipitation of dispersed particles in the matrix phase. Because the matrix phase of the present invention is mainly composed of large atomic elements, even if the matrix phase contains less than 50 atomic percent, its volume percent content in the alloy strip can be much higher than its atomic percent content. For example, in the solidified structure of La 25 Fe 75 (atomic ratio composition) alloy, the volume percentage content of La matrix can still reach 51%. When the solidification rate of the alloy melt is fast enough and the Fe particles are nanoscale, the Fe particles in the solidified structure of La 25 Fe 75 alloy can still disperse and precipitate before they can merge and grow.
进一步地，为了保证弥散颗粒的分散析出，所述合金条带中基体相的体积百分比含量不低于44％。Further, in order to ensure the dispersion and precipitation of the dispersed particles, the volume percentage content of the matrix phase in the alloy strip is not less than 44%.
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50K/s～10 7K/s。当凝固速率高于10 5K/s时，可以获得纳米级的弥散颗粒相；当凝固速率为10 3K/s～10 5K/s时，可以获得亚微米级的弥散颗粒相；当凝固速率低于10 3K/s时，可以获得微米级的弥散颗粒相。 Further, the rapid solidification technology includes an alloy melt metal roll stripping method, and the solidification rate of the alloy melt is 50K/s˜10 7 K/s. When the solidification rate is higher than 10 5 K/s, nano-scale dispersed particles can be obtained; when the solidification rate is 10 3 K/s～10 5 K/s, sub-micron dispersed particles can be obtained; when solidified When the rate is lower than 10 3 K/s, the micron-scale dispersed particle phase can be obtained.
进一步地，所述合金条带的厚度为5μm～5mm。Further, the thickness of the alloy strip is 5 μm˜5 mm.
进一步地，所述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，颗粒大小范围为2nm～200μm。Further, the shape of the dispersed particle phase includes at least one of dendritic shape, spherical shape, nearly spherical shape, square shape, cake shape, and rod shape, and the particle size ranges from 2 nm to 200 μm.
进一步地，所述合金熔体中的杂质元素与凝固过程中引入的杂质元素包含H、O、N、S、P、F、Cl、I、Br中的至少一种。Further, the impurity elements in the alloy melt and the impurity elements introduced in the solidification process include at least one of H, O, N, S, P, F, Cl, I, and Br.
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、碱反应去除、真空挥发去除中的至少一种。酸溶液与碱溶液的组成与浓度不做具体限定，只要能够保证去除基体相，同时保留弥散颗粒相即可。Further, the method for removing the matrix phase from the alloy strip includes at least one of acid reaction removal, alkali reaction removal, and vacuum volatilization removal. The composition and concentration of the acid solution and the alkali solution are not specifically limited, as long as the matrix phase can be removed and the dispersed particle phase can be retained at the same time.
进一步地，所述将合金条带中基体相去除方法包括基体相自然氧化-粉化剥落去除。Further, the method for removing the matrix phase in the alloy strip includes the natural oxidation of the matrix phase-powdering and exfoliation removal.
进一步地，所述由弥散颗粒相组成的高纯目标金属粉的粒径范围为2nm～200μm。Further, the particle size range of the high-purity target metal powder composed of the dispersed particle phase is 2 nm˜200 μm.
进一步地，所述高纯目标金属粉的形状包括球形、近球形、枝晶形、棒条形、板条形。Further, the shape of the high-purity target metal powder includes spherical, nearly spherical, dendritic, rod-shaped, and lath-shaped.
进一步地，所述高纯目标金属粉中H、O、N、S、P、F、Cl、I、Br的总含量低于2000ppm。Further, the total content of H, O, N, S, P, F, Cl, I, and Br in the high-purity target metal powder is less than 2000 ppm.
以下进一步详细说明上述备选技术特点的有益方面：Beneficial aspects of the aforementioned alternative technical features are further detailed 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，由于熔体凝固过程中，熔体中的杂质元素易于与基体相结合从而富集与基体相。因此，即使采用非高纯的原料与普通的坩埚，或者熔炼过程有其它气体杂质元素进入熔体，都可以获得低杂质含量的弥散颗粒相与目标金属粉，这就极大地降低了高纯粉体材料的生产成本。Secondly, due to the solidification process of the melt, the impurity elements in the melt are easy to combine with the matrix so as to be enriched with the matrix phase. Therefore, even if non-high-purity raw materials and ordinary crucibles are used, or other gas impurity elements enter the melt during the smelting process, the dispersed particle phase and target metal powder with low impurity content can be obtained, which greatly reduces the high-purity powder. production cost of bulk material.
第三，当所述初始合金A aM b或A aM bAl c中M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变得更为简便可行，极大地扩展了目标合金粉的成分范围与应用领域。 Third, when M in the initial alloy A a M b or A a M b Al c is a combination of multiple elements, the resulting disperse grain phase is also composed of multiple elements, which makes the preparation of a disperse grain phase composed of The target alloy powder becomes more convenient and feasible, which greatly expands the composition range and application field of the target alloy powder.
最后，本发明的步骤二中，根据合金条带中基体相为低熔点、高活性组分的特点，可以通过以下三种方式中的至少一种将基体相去除，并保留弥散颗粒相：1)通过酸溶液或者碱溶液腐蚀的方法将基体相去除，同时保留弥散颗粒相；2)对于极易挥发的基体相，通过真空挥发的方法将基体相去除，同时保留弥散颗粒相；3)对于极易自然氧化的基体相，如主要组分为稀土元素的基体相，还可以通过基体相元素的自然氧化-粉化的方式，使基体相变成粉化后的氧化物粉末，然后进一步将弥散颗粒相与基体粉化后的产物进行分离，得到目标金属粉。Finally, in the second step of the present invention, according to the characteristics that the matrix phase in the alloy strip is a low melting point and high activity component, the matrix phase can be removed by at least one of the following three methods, and the dispersed particle phase can be retained: 1. ) The matrix phase is removed by etching with an acid solution or an alkaline solution, while the dispersed particle phase is retained; 2) For the highly volatile matrix phase, the matrix phase is removed by vacuum evaporation, while the dispersed particle phase is retained; 3) For the highly volatile matrix phase, the matrix phase is removed by vacuum evaporation. The matrix phase that is easy to be naturally oxidized, such as the matrix phase whose main component is rare earth elements, can also be converted into pulverized oxide powder by the natural oxidation-pulverization of the matrix phase elements, and then further The dispersed particle phase is separated from the pulverized product of the matrix to obtain the target metal powder.
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高纯粉体材料，在催化、粉末冶金、复合材料、杀菌、金属注射成成型、3D打印、以及其它增材制造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 including nano-, sub-micro and micro-scale, and is used in catalysis, powder metallurgy, composite materials, sterilization, etc. , metal injection molding, 3D printing, and other fields of additive manufacturing have good application prospects.
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粉体材料的制备方法做进一步的说明。Hereinafter, the preparation method of the high-purity powder material will be further described by the following specific examples.
实施例1Example 1
本实施例提供一种纳米CrV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-CrV powder, and the preparation method comprises the following steps:
选用原子比配方为Zn 54Cr 23V 23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20μm的Zn 54Cr 23V 23合金条带。该合金条带的凝固组织由成分为Zn的基体相与大量成分为Cr 50V 50的弥散颗粒相组成，其中Cr 50V 50颗粒的形状为近球形，粒径大小范围为3nm～200nm。Cr 50V 50颗粒在合金条带中的体积含量约为42％；凝固过程中杂质元素富集于Zn基体中。 The alloy with the atomic ratio formula of Zn 54 Cr 23 V 23 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 20 μm at a solidification rate of 10 6 K/s. Zn 54 Cr 23 V 23 alloy strip. The solidification structure of the alloy strip is composed of a matrix phase with a composition of Zn and a large amount of dispersed particles with a composition of Cr 50 V 50 , wherein the shape of the Cr 50 V 50 particles is nearly spherical, and the particle size ranges from 3nm to 200nm. The volume content of Cr 50 V 50 particles in the alloy strip is about 42%; impurity elements are enriched in the Zn matrix during solidification.
通过真空热处理的方法将合金条带中的Zn挥发去除，使得合金条带中难以挥发的Cr 50V 50颗粒脱离出来，即得到纳米Cr 50V 50粉，其粒径大小范围为3nm～200nm，且纳米Cr 50V 50粉中的H、O、N、S、P、F、Cl、I、Br总含量低于1500ppm。 The Zn in the alloy strip is volatilized and removed by the method of vacuum heat treatment, so that the Cr 50 V 50 particles that are difficult to volatilize in the alloy strip are detached, and the nano-Cr 50 V 50 powder is obtained, and its particle size ranges from 3nm to 200nm. And the total content of H, O, N, S, P, F, Cl, I, and Br in the nano-Cr 50 V 50 powder is less than 1500 ppm.
实施例2Example 2
本实施例提供一种纳米CrV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-CrV powder, and the preparation method comprises the following steps:
选用原子比配方为Zn 54Cr 23V 23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约10 6K/s的凝固速率制备成厚度为20μm的Zn 54Cr 23V 23合金条带。该合金条带的凝固组织由成分为Zn的基体相与大量成分为Cr 50V 50的弥散颗粒相组成，其中 Cr 50V 50颗粒的形状为近球形，粒径大小范围为3nm～200nm。Cr 50V 50颗粒在合金条带中的体积含量约为42％；凝固过程中杂质元素富集于Zn基体中。 The alloy with the atomic ratio formula of Zn 54 Cr 23 V 23 was selected, and the raw materials were weighed according to the formula. After the initial alloy raw material was melted uniformly, it was prepared into a thickness of 20 μm by the copper roller stripping technology at a solidification rate of about 10 6 K/s. Zn 54 Cr 23 V 23 alloy strips. The solidification structure of the alloy strip is composed of a matrix phase with a composition of Zn and a large amount of dispersed particles with a composition of Cr 50 V 50 , wherein the shape of the Cr 50 V 50 particles is nearly spherical, and the particle size ranges from 3nm to 200nm. The volume content of Cr 50 V 50 particles in the alloy strip is about 42%; impurity elements are enriched in the Zn matrix during solidification.
通过氢氧化钠碱溶液将合金条带中的Zn溶解去除，使得合金条带中难以与碱溶液反应的的Cr 50V 50颗粒脱离出来，即得到纳米Cr 50V 50粉，其粒径大小范围为3nm～200nm，且纳米Cr 50V 50粉中的H、O、N、S、P、F、Cl、I、Br总含量低于1500ppm。 The Zn in the alloy strip is dissolved and removed by the sodium hydroxide alkali solution, so that the Cr 50 V 50 particles in the alloy strip that are difficult to react with the alkali solution are detached, that is, the nano Cr 50 V 50 powder is obtained. It is 3nm to 200nm, and the total content of H, O, N, S, P, F, Cl, I, and Br in the nano-Cr 50 V 50 powder is less than 1500 ppm.
实施例3Example 3
本实施例提供了一种纳米Ti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-Ti powder, and the preparation method comprises the following steps:
选用原子比配方为Ce 30Ti 70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约10 7K/s的凝固速率制备成厚度为15μm的Ce 30Ti 70合金条带。该合金条带的凝固组织由成分为Ce的基体相与大量成分为Ti的弥散颗粒相组成，其中Ti颗粒的形状为近球形，粒径大小范围为3nm～150nm。Ti颗粒在合金条带中的体积含量约为55％；凝固过程中杂质元素富集于Ce基体中。 The alloy with the atomic ratio formula of Ce 30 Ti 70 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 Ce with a thickness of 15 μm at a solidification rate of about 10 7 K/s. 30 Ti 70 alloy strip. The solidified structure of the alloy strip is composed of a matrix phase with a composition of Ce and a large amount of dispersed particle phases with a composition of Ti, wherein the shape of the Ti particles is nearly spherical, and the particle size ranges from 3nm to 150nm. The volume content of Ti particles in the alloy strip is about 55%; impurity elements are enriched in the Ce matrix during solidification.
通过盐酸溶液将合金条带中的Ce基体溶解去除，使得合金条带中难以与酸溶液反应的的Ti颗粒脱离出来，即得到纳米Ti粉，其粒径大小范围为3nm～150nm，且纳米Ti粉中的H、O、N、S、P、F、Cl、I、Br总含量低于1500ppm。The Ce matrix in the alloy strip is dissolved and removed by the hydrochloric acid solution, so that the Ti particles in the alloy strip that are difficult to react with the acid solution are separated, and the nano-Ti powder is obtained, and the particle size of the nano-Ti powder ranges from 3 nm to 150 nm. The total content of H, O, N, S, P, F, Cl, I and Br in the powder is less than 1500ppm.
实施例4Example 4
本实施例提供了一种纳米Ti-Zr-Hf-Nb-Ta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-Ti-Zr-Hf-Nb-Ta powder, and the preparation method includes the following steps:
选用原子比配方为Ce 40(Ti 20Zr 20Hf 20Nb 20Ta 20) 60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约10 7K/s的凝固速率制备成厚度为15μm的Ce 40(Ti 20Zr 20Hf 20Nb 20Ta 20) 60合金条带。该合金条带的凝固组织由成分为Ce的基体相与大量成分为Ti 20Zr 20Hf 20Nb 20Ta 20的弥散颗粒相组成，其中Ti 20Zr 20Hf 20Nb 20Ta 20颗粒的形状为近球形，粒径大小范围为3nm～150nm。Ti 20Zr 20Hf 20Nb 20Ta 20颗粒在合金条带中的体积含量约为50％；凝固过程中杂质元素富集于Ce基体中。 Select the alloy whose atomic ratio formula is Ce 40 (Ti 20 Zr 20 Hf 20 Nb 20 Ta 20 ) 60 , weigh the raw materials according to the formula, and after the initial alloy raw material is melted uniformly, the copper roller stripping technology is used to obtain about 10 7 K/ The solidification rate of s was prepared as a Ce 40 (Ti 20 Zr 20 Hf 20 Nb 20 Ta 20 ) 60 alloy ribbon with a thickness of 15 μm. The solidification structure of the alloy strip is composed of a matrix phase with a composition of Ce and a large number of dispersed particles with a composition of Ti 20 Zr 20 Hf 20 Nb 20 Ta 20 , wherein the shape of the Ti 20 Zr 20 Hf 20 Nb 20 Ta 20 particles is approximately Spherical, with particle size ranging from 3nm to 150nm. The volume content of Ti 20 Zr 20 Hf 20 Nb 20 Ta 20 particles in the alloy strip is about 50%; impurity elements are enriched in the Ce matrix during solidification.
通过盐酸溶液将合金条带中的Ce基体溶解去除，使得合金条带中难以与酸溶液反应的的Ti 20Zr 20Hf 20Nb 20Ta 20颗粒脱离出来，即得到纳米Ti 20Zr 20Hf 20Nb 20Ta 20粉，其粒径大小范围为3nm～150nm，且纳米Ti 20Zr 20Hf 20Nb 20Ta 20粉中的H、O、N、S、P、F、Cl、I、Br总含量低于1500ppm。 The Ce matrix in the alloy strip is dissolved and removed by the hydrochloric acid solution, so that the Ti 20 Zr 20 Hf 20 Nb 20 Ta 20 particles in the alloy strip that are difficult to react with the acid solution are separated out, that is, nano-Ti 20 Zr 20 Hf 20 Nb is obtained. 20 Ta 20 powder, its particle size range is 3nm ~ 150nm, and the total content of H, O, N, S, P, F, Cl, I, Br in the nano Ti 20 Zr 20 Hf 20 Nb 20 Ta 20 powder is low at 1500ppm.
实施例5Example 5
本实施例提供了一种纳米-亚微米Ti-Nb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-submicron Ti-Nb powder, and the preparation method includes the following steps:
选用原子比配方为Ce 50(Ti 50Nb 50) 50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约10 4K/s的凝固速率制备成厚度为150μm的Ce 50(Ti 50Nb 50) 50合金条带。该合金条带的凝固组织由成分为Ce的基体相与大量成分为Ti 50Nb 50的弥散颗粒相组成，其中Ti 50Nb 50颗粒的形状为近球形，粒径大小范围为50nm～1μm。Ti 50Nb 50颗粒在合金条带中的体积含量约为34％；凝固过程中杂质元素富集于Ce基体中。 Select the alloy whose atomic ratio formula is Ce 50 (Ti 50 Nb 50 ) 50 , weigh the raw material according to the formula, and after the initial alloy raw material is melted uniformly, it is prepared by copper roller stripping technology with a solidification rate of about 10 4 K/s. Ce 50 (Ti 50 Nb 50 ) 50 alloy ribbons with a thickness of 150 μm. The solidification structure of the alloy strip is composed of a matrix phase with a composition of Ce and a large number of dispersed particle phases with a composition of Ti 50 Nb 50 , wherein the shape of the Ti 50 Nb 50 particles is nearly spherical, and the particle size ranges from 50 nm to 1 μm. The volume content of Ti 50 Nb 50 particles in the alloy strip is about 34%; impurity elements are enriched in the Ce matrix during solidification.
通过盐酸溶液将合金条带中的Ce基体溶解去除，使得合金条带中难以与酸溶液反应的的Ti 50Nb 50颗粒脱离出来，即得到纳米-亚微米级的Ti 50Nb 50粉，其粒径大小范围为50nm～1μm，且Ti 50Nb 50粉中的H、O、N、S、P、F、Cl、I、Br总含量低于1500ppm。 The Ce matrix in the alloy strip is dissolved and removed by the hydrochloric acid solution, so that the Ti 50 Nb 50 particles in the alloy strip that are difficult to react with the acid solution are detached, that is, the nano-submicron Ti 50 Nb 50 powder is obtained. The diameter range is from 50 nm to 1 μm, and the total content of H, O, N, S, P, F, Cl, I, and Br in the Ti 50 Nb 50 powder is less than 1500 ppm.
实施例6Example 6
本实施例提供了一种微米Ti-Co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 Ti-Co powder, and the preparation method comprises the following steps:
选用原子比配方为Gd 50(Ti 50Co 50) 50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约150K/s的凝固速率制备成厚度为3mm的Gd 50(Ti 50Co 50) 50合金条带。该合金条带的凝固组织由成分为Gd的基体相与大量成分为Ti 50Co 50的弥散颗粒相组成，其中Ti 50Co 50颗粒的形状为枝晶形，粒径大小范围为1μm～100μm。Ti 50Co 50颗粒在合金条带中的体积含量约为30％；凝固过程中杂质元素富集于Gd基体中。 The alloy whose atomic ratio formula is Gd 50 (Ti 50 Co 50 ) 50 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 3mm strip of Gd50 ( Ti50Co50 ) 50 alloy. The solidification structure of the alloy strip is composed of a matrix phase with a composition of Gd and a large number of dispersed particle phases with a composition of Ti 50 Co 50 , wherein the shape of the Ti 50 Co 50 particles is dendrite, and the particle size ranges from 1 μm to 100 μm. The volume content of Ti 50 Co 50 particles in the alloy strip is about 30%; impurity elements are enriched in the Gd matrix during solidification.
通过稀盐酸溶液将合金条带中的Gd基体溶解去除，使得合金条带中难以与稀酸溶液反应的的Ti 50Co 50颗粒脱离出来，即得到微米级的Ti 50Co 50粉，其粒径大小范围为1μm～100μm，且Ti 50Co 50粉中的H、O、N、S、P、F、Cl、I、Br总含量低于1500ppm。 The Gd matrix in the alloy strip is dissolved and removed by the dilute hydrochloric acid solution, so that the Ti 50 Co 50 particles in the alloy strip that are difficult to react with the dilute acid solution are detached, that is, the micron-scale Ti 50 Co 50 powder is obtained. The size ranges from 1 μm to 100 μm, and the total content of H, O, N, S, P, F, Cl, I, and Br in the Ti 50 Co 50 powder is less than 1500 ppm.
实施例7Example 7
本实施例提供了一种亚微米-微米Fe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-micron Fe powder, and the preparation method comprises the following steps:
选用原子比配方为La 40Fe 60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约10 3K/s的凝固速率制备成厚度为500μm的La 40Fe 60合金条带。该合金条带的凝固组织由成分为La的基体相与大量成分为Fe的弥散颗粒相组成，其中Fe颗粒的形状为近球形，粒径大小范围为500nm～5μm。Fe颗粒在合金条带中的体积含量约为32％；凝固过程中杂质元素富集于La基体中。 The alloy with the atomic ratio formula of La 40 Fe 60 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 La with a thickness of 500 μm at a solidification rate of about 10 3 K/s. 40 Fe 60 alloy strip. The solidified structure of the alloy strip is composed of a matrix phase with a composition of La and a large amount of dispersed particles with a composition of Fe, wherein the shape of the Fe particles is nearly spherical, and the particle size ranges from 500 nm to 5 μm. The volume content of Fe particles in the alloy strip is about 32%; impurity elements are enriched in the La matrix during solidification.
通过La基体在空气中的自然氧化-粉化过程将La 40Fe 60合金中的La变成氧化镧，然后利用Fe的磁性特性将Fe颗粒与氧化镧分离，即得到亚微米-微米Fe粉，其粒径大小范围为500nm～5μm，且Fe粉中的H、O、N、S、P、F、Cl、I、Br总含量低于1500ppm。 The La in the La 40 Fe 60 alloy is transformed into lanthanum oxide through the natural oxidation-powdering process of the La matrix in the air, and then the Fe particles are separated from the lanthanum oxide by the magnetic properties of Fe, that is, the sub-micron-micron Fe powder is obtained, The particle size ranges from 500 nm to 5 μm, and the total content of H, O, N, S, P, F, Cl, I, and Br in the Fe powder is less than 1500 ppm.
实施例8Example 8
本实施例提供了一种纳米Fe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 Fe powder, and the preparation method comprises the following steps:
选用原子比配方为La 25Fe 75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约10 6K/s的凝固速率制备成厚度为20μm的La 25Fe 75合金条带。该合金条带的凝固组织由成分为La的基体相与大量成分为Fe的弥散颗粒相组成，其中Fe颗粒的形状为近球形，粒径大小范围为3nm～200nm。Fe颗粒在合金条带中的体积含量约为49％；凝固过程中杂质元素富集于La基体中。 The alloy with the atomic ratio formula of La 25 Fe 75 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 La with a thickness of 20 μm at a solidification rate of about 10 6 K/s. 25 Fe 75 alloy strip. The solidified structure of the alloy strip is composed of a matrix phase with a composition of La and a large amount of dispersed particles with a composition of Fe, wherein the shape of the Fe particles is nearly spherical, and the particle size ranges from 3nm to 200nm. The volume content of Fe particles in the alloy strip is about 49%; impurity elements are enriched in the La matrix during solidification.
通过La基体在空气中的自然氧化-粉化过程将La 25Fe 75合金中的La变成氧化镧，然后利用Fe的磁性特性将纳米Fe颗粒与氧化镧分离，即得到纳米Fe粉，其粒径大小范围为3nm～200nm，且Fe粉中的H、O、N、S、P、F、Cl、I、Br总含量低于1800ppm。 The La in the La 25 Fe 75 alloy is transformed into lanthanum oxide through the natural oxidation-powdering process of the La matrix in the air, and then the magnetic properties of Fe are used to separate the nano Fe particles from the lanthanum oxide, that is, the nano Fe powder is obtained. The diameter range is from 3nm to 200nm, and the total content of H, O, N, S, P, F, Cl, I, and Br in Fe powder is less than 1800ppm.
实施例9Example 9
本实施例提供一种亚微米-微米FeNi粉的制备方法，该制备方法包括如下步骤：This embodiment provides a preparation method of submicron-micron FeNi powder, and the preparation method includes the following steps:
选用原子比配方为Li 50(Fe 50Ni 50) 50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约10 3K/s的凝固速率制备成厚度为500μm的Li 50(Fe 50Ni 50) 50合金条带。该合金条带的凝固组织由成分为Li的基体相与大量成分为Fe 50Ni 50的弥散颗粒相组成，其中Fe 50Ni 50颗粒的形状为近球形或枝晶形，粒径大小范围为500nm～5μm。Fe 50Ni 50颗粒在合金条带中的体积含量约为34％；凝固过程中杂质元素富集于Li基体中。 Select the alloy whose atomic ratio formula is Li 50 (Fe 50 Ni 50 ) 50 , weigh the raw material according to the formula, and after the initial alloy raw material is melted uniformly, it is prepared by the copper roller stripping technique with a solidification rate of about 10 3 K/s. Li 50 (Fe 50 Ni 50 ) 50 alloy ribbon with a thickness of 500 μm. The solidification structure of the alloy strip is composed of a matrix phase composed of Li and a large number of dispersed particle phases composed of Fe 50 Ni 50 , wherein the Fe 50 Ni 50 particles are nearly spherical or dendritic in shape, and the particle size ranges from 500 nm to 500 nm. 5μm. The volume content of Fe 50 Ni 50 particles in the alloy strip is about 34%; impurity elements are enriched in the Li matrix during solidification.
通过Li基体在空气中的自然氧化-粉化过程将Li 50(Fe 50Ni 50) 50合金中的Li变成氧化物粉末，然后利用Fe 50Ni 50的磁性特性将Fe 50Ni 50颗粒与Li的氧化产物分离，即得到亚微米-微米Fe 50Ni 50粉，其粒径大小范围为500nm～5μm，且Fe 50Ni 50粉中的H、O、N、S、P、F、Cl、I、Br总含量低于1800ppm。 The Li in Li 50 (Fe 50 Ni 50 ) 50 alloy is transformed into oxide powder through the natural oxidation-powdering process of Li matrix in air, and then Fe 50 Ni 50 particles are combined with Li by utilizing the magnetic properties of Fe 50 Ni 50 The oxidation product is separated, namely obtains sub-micron-micron Fe 50 Ni 50 powder with a particle size range of 500 nm to 5 μm, and H, O, N, S, P, F, Cl, I in the Fe 50 Ni 50 powder , The total Br content is less than 1800ppm.
实施例10Example 10
本实施例提供了一种纳米Ti-Al-V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-Ti-Al-V powder, and the preparation method includes the following steps:
选用原子比配方为Ce 30Al 12(Ti 96V 4) 58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约10 6K/s的凝固速率制备成厚度为20μm的Ce 30Al 12(Ti 96V 4) 58合金条带。该合金条带的凝固组织由成分为Ce 85Al 15的基体相与大量成分为(Ti 96V 4) 90Al 10的弥散颗粒相组成，其中(Ti 96V 4) 90Al 10颗粒的形状为近球形，粒径大小范围为3nm～200nm。(Ti 96V 4) 90Al 10颗粒在合金条带中的体积含量约为52％；凝固过程中杂质元素富集于Ce 85Al 15基体中。 Select the alloy whose atomic ratio formula is Ce 30 Al 12 (Ti 96 V 4 ) 58 , weigh the raw materials according to the formula, after the initial alloy raw material is melted uniformly, the solidification rate of about 10 6 K/s is carried out by the copper roller stripping technique. A Ce 30 Al 12 (Ti 96 V 4 ) 58 alloy ribbon with a thickness of 20 μm was prepared. The solidification structure of the alloy strip is composed of a matrix phase with a composition of Ce 85 Al 15 and a large amount of dispersed particles with a composition of (Ti 96 V 4 ) 90 Al 10 , wherein the shape of the (Ti 96 V 4 ) 90 Al 10 particles is Nearly spherical, the particle size ranges from 3nm to 200nm. The volume content of (Ti 96 V 4 ) 90 Al 10 particles in the alloy strip is about 52%; impurity elements are enriched in the Ce 85 Al 15 matrix during solidification.
通过稀盐酸溶液将Ce 30Al 12(Ti 96V 4) 58合金条带中的Ce 85Al 15基体相反应去除，使得难与稀盐酸溶液反应的(Ti 96V 4) 90Al 10颗粒脱离出来，即得到纳米(Ti 96V 4) 90Al 10粉，其粒径大小范围为3nm～200nm，且纳米(Ti 96V 4) 90Al 10粉中的H、O、N、S、P、F、Cl、I、Br总含量低于1400ppm。 The Ce 85 Al 15 matrix phase in the Ce 30 Al 12 (Ti 96 V 4 ) 58 alloy strip is removed by the dilute hydrochloric acid solution, so that the (Ti 96 V 4 ) 90 Al 10 particles that are difficult to react with the dilute hydrochloric acid solution are separated out , that is, to obtain nano (Ti 96 V 4 ) 90 Al 10 powder with a particle size range of 3 nm to 200 nm, and the H, O, N, S, P, F in the nano (Ti 96 V 4 ) 90 Al 10 powder , Cl, I, Br total content less than 1400ppm.
实施例11Example 11
本实施例提供了一种亚微米-微米Ti-Al-V粉的制备方法，该制备方法包括如下步骤：This embodiment provides a preparation method of submicron-micron Ti-Al-V powder, and the preparation method includes the following steps:
选用原子比配方为Ce 30Al 12(Ti 96V 4) 58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约10 3K/s的凝固速率制备成厚度为约500μm的Ce 30Al 12(Ti 96V 4) 58合金条带。该合金条带的凝固组织由成分为Ce 85Al 15的基体相与大量成分为(Ti 96V 4) 90Al 10的弥散颗粒相组成，其中(Ti 96V 4) 90Al 10颗粒的形状为近球形或枝晶形，粒径大小范围为500nm～5μm。(Ti 96V 4) 90Al 10颗粒在合金条带中的体积含量约为52％；凝固过程中杂质元素富集于Ce 85Al 15基体中。 Select the alloy whose atomic ratio formula is Ce 30 Al 12 (Ti 96 V 4 ) 58 , weigh the raw material according to the formula, after the initial alloy raw material is melted uniformly, the solidification rate of about 10 3 K/s is carried out by the copper roller stripping technique. Ce 30 Al 12 (Ti 96 V 4 ) 58 alloy ribbons were prepared with a thickness of about 500 μm. The solidification structure of the alloy strip is composed of a matrix phase with a composition of Ce 85 Al 15 and a large amount of dispersed particles with a composition of (Ti 96 V 4 ) 90 Al 10 , wherein the shape of the (Ti 96 V 4 ) 90 Al 10 particles is Nearly spherical or dendritic, with a particle size ranging from 500nm to 5μm. The volume content of (Ti 96 V 4 ) 90 Al 10 particles in the alloy strip is about 52%; impurity elements are enriched in the Ce 85 Al 15 matrix during solidification.
通过稀盐酸溶液将Ce 30Al 12(Ti 96V 4) 58合金条带中的Ce 85Al 15基体相反应去除，使得难与稀盐酸溶液反应的(Ti 96V 4) 90Al 10颗粒脱离出来，即得到亚微米-微米(Ti 96V 4) 90Al 10粉，其粒径大小范围为500nm～5μm，且纳米(Ti 96V 4) 90Al 10粉中的H、O、N、S、P、F、Cl、I、Br总含量低于1400ppm。 The Ce 85 Al 15 matrix phase in the Ce 30 Al 12 (Ti 96 V 4 ) 58 alloy strip is removed by the dilute hydrochloric acid solution, so that the (Ti 96 V 4 ) 90 Al 10 particles that are difficult to react with the dilute hydrochloric acid solution are separated out , that is, to obtain submicron-micron (Ti 96 V 4 ) 90 Al 10 powder, the particle size of which ranges from 500 nm to 5 μm, and the H, O, N, S, The total content of P, F, Cl, I and Br is less than 1400ppm.
实施例12Example 12
本实施例提供了一种纳米Ti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-Ti powder, and the preparation method comprises the following steps:
选用T(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3at.％与2.5at.％的海绵Ti与稀土Ce原料。按照Ce与Ti的摩尔比约为1:1将海绵Ti与稀土Ce充分熔化，得到原子百分比成分主要为Ce 47.25Ti 47.25T 2.5的均匀初始合金熔体。 The raw materials of sponge Ti and rare earth Ce with the atomic percentage content of T (including O, H, N, P, S, F, Cl, Br, and I) impurity elements are respectively 3 at.% and 2.5 at.% are selected. According to the molar ratio of Ce to Ti about 1:1, the sponge Ti and the rare earth Ce are fully melted to obtain a uniform initial alloy melt whose atomic percentage is mainly Ce 47.25 Ti 47.25 T 2.5 .
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15μm的Ce 47.25Ti 47.25T 2.5合金条带。该合金条带的凝固组织由成分主要为Ce 95.2T 4.8的基体相与大量成分主要为Ti 99.8T 0.2的弥散颗粒相组成，其中Ti 99.8T 0.2弥散颗粒的形状为近球形，粒径大小范围为3nm～150nm。Ti 99.8T 0.2弥散颗粒在合金条带中的体积含量约为34％； The initial alloy melt was prepared into Ce 47.25 Ti 47.25 T 2.5 alloy strips with a thickness of 15 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 mainly composed of Ce 95.2 T 4.8 and a large number of dispersed particles mainly composed of Ti 99.8 T 0.2 . The shape of the Ti 99.8 T 0.2 dispersed particles is nearly spherical, and the particle size ranges It is 3nm～150nm. The volume content of Ti 99.8 T 0.2 dispersed particles in the alloy strip is about 34%;
所得Ce 47.25Ti 47.25T 2.5合金条带即为由内生粉与包覆体构成的合金条带。 The obtained Ce 47.25 Ti 47.25 T 2.5 alloy strip is an alloy strip composed of endogenous powder and cladding.
通过稀酸溶液将合金条带中的Ce 95.2T 4.8基体去除，使得合金条带中难与稀酸溶液反应的Ti 99.8T 0.2颗粒脱离出来，即得到Ti 99.8T 0.2纳米粉，其粒径大小范围为3nm～150nm，且其含有的O、H、N、P、S、F、Cl、Br、I的总含量为0.2at.％。 The Ce 95.2 T 4.8 matrix in the alloy strip is removed by the dilute acid solution, so that the Ti 99.8 T 0.2 particles in the alloy strip that are difficult to react with the dilute acid solution are detached, that is, the Ti 99.8 T 0.2 nano-powder is obtained. The range is 3 nm to 150 nm, and the total content of O, H, N, P, S, F, Cl, Br, and I contained in it is 0.2 at.%.
在保护气氛下将主要成分为Ti 99.8T 0.2的纳米粉与环氧树脂及其它涂料组分混合，从而制备得到纳米Ti改性聚合物防腐涂料。 The nanometer powder whose main component is Ti 99.8 T 0.2 is mixed with epoxy resin and other coating components under a protective atmosphere, thereby preparing a nanometer Ti modified polymer anti-corrosion coating.
实施例13Example 13
本实施例提供了一种微米枝晶Ti-Nb粉的制备方法，该制备方法包括如下步骤：This embodiment provides a preparation method of micron dendritic Ti-Nb powder, and the preparation method includes the following steps:
选用T(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3at.％、 1at.％、2.5at.％的海绵Ti、Nb片、稀土Gd原料。按照Gd:Ti:Nb的摩尔比约为2:1:1将各合金原料熔化，得到得到原子百分比成分主要为Gd 48.75Ti 24.5Nb 24.5T 2.25的均匀初始合金熔体。 The atomic percentage content of T (including O, H, N, P, S, F, Cl, Br, I) impurity elements is selected as sponge Ti, Nb sheet, rare earth with 3 at.%, 1 at.%, 2.5 at.% respectively Gd raw material. According to the molar ratio of Gd:Ti:Nb about 2:1:1, each alloy raw material was melted to obtain a uniform initial alloy melt whose atomic percentage composition was mainly Gd 48.75 Ti 24.5 Nb 24.5 T 2.25 .
通过铜辊甩带技术以约～10 3K/s的凝固速率将初始合金熔体制备成厚度为～300μm的Gd 48.75Ti 24.5Nb 24.5T 2.25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Gd 95.9T 4.1的基体相与大量成分主要为Ti 49.85Nb 49.85T 0.3的弥散颗粒相组成。其中Ti 49.85Nb 49.85T 0.3弥散颗粒的形状为枝晶形，其粒径大小范围为1μm～50μm。Ti 49.85Nb 49.85T 0.3弥散颗粒在合金条带中的体积百分含量约为35％； The initial alloy melt was prepared into Gd 48.75 Ti 24.5 Nb 24.5 T 2.25 alloy strips with a thickness of -300 μm by copper roll stripping technique at a solidification rate of about -10 3 K/s. The solidification structure of the alloy strip is composed of a matrix phase whose atomic percentage is mainly Gd 95.9 T 4.1 and a large amount of dispersed particles whose composition is mainly Ti 49.85 Nb 49.85 T 0.3 . The shape of the Ti 49.85 Nb 49.85 T 0.3 dispersed particles is dendritic, and the particle size ranges from 1 μm to 50 μm. The volume percentage of Ti 49.85 Nb 49.85 T 0.3 dispersed particles in the alloy strip is about 35%;
通过稀酸溶液将合金条带中的Gd 95.9T 4.1基体相去除，使得合金条带中难与稀酸溶液反应的Ti 49.85Nb 49.85T 0.3弥散颗粒脱离出来，即得到主要成分为Ti 49.85Nb 49.85T 0.3的微米粉，其粒径大小范围为1μm～50μm，且其含有的O、H、N、P、S、F、Cl、Br、I的总含量为0.3at.％。 The Gd 95.9 T 4.1 matrix phase in the alloy strip is removed by the dilute acid solution, so that the Ti 49.85 Nb 49.85 T 0.3 dispersed particles in the alloy strip that are difficult to react with the dilute acid solution are separated out, that is, the main component is Ti 49.85 Nb 49.85 The micron powder with T 0.3 has a particle size range of 1 μm to 50 μm, and the total content of O, H, N, P, S, F, Cl, Br, and I contained in it is 0.3 at.%.
将上述Ti 49.85Nb 49.85T 0.3合金粉体通过1000目、2000目的筛网进行筛分，得到粒径范围分别为53μm～13μm和13μm～6.5μm的分级Ti 49.85Nb 49.85T 0.3合金粉体。分别对其进行等离子球化处理，进一步制得粒径范围分别为53μm～13μm与13μm～6.5μm，且形状接近球形的Ti-Nb-T合金粉体。所得球形Ti-Nb-T合金粉体可用于3D金属打印、金属注射成型、粉末冶金领域。 The above-mentioned Ti 49.85 Nb 49.85 T 0.3 alloy powder is sieved through a 1000-mesh and 2000-mesh sieve to obtain a graded Ti 49.85 Nb 49.85 T 0.3 alloy powder with particle sizes ranging from 53 μm to 13 μm and 13 μm to 6.5 μm, respectively. Plasma spheroidization was performed on them respectively to further obtain Ti-Nb-T alloy powders with particle sizes ranging from 53 μm to 13 μm and 13 μm to 6.5 μm, and shapes close to spherical. The obtained spherical Ti-Nb-T alloy powder can be used in the fields of 3D metal printing, metal injection molding and powder metallurgy.
实施例14Example 14
本实施例提供一种纳米TiNi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-TiNi powder, and the preparation method comprises the following steps:
选用T(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1at.％、0.5at.％、2.5at.％的Ti原料、Ni片、稀土Gd原料。按照Gd:Ti:Ni的摩尔比约为2:1:1将初始原料熔化，得到原子百分比成分主要为Gd 48.8Ti 25.25Ni 25.25T 1.7的均匀初始合金熔体。 Select Ti raw materials, Ni sheets, Rare earth Gd raw material. According to the molar ratio of Gd:Ti:Ni about 2:1:1, the initial raw material was melted to obtain a uniform initial alloy melt whose atomic percentage composition was mainly Gd 48.8 Ti 25.25 Ni 25.25 T 1.7 .
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～15μm的Gd 48.8Ti 25.25Ni 25.25T 1.7合金条带。该合金条带的凝固组织由成分主要为Gd 96.8T 3.2的基体相与大量成分主要为Ti 49.9Ni 49.9T 0.2的弥散颗粒相组成(其为TiNi金属间化合物)，其中Ti 49.9Ni 49.9T 0.2弥散颗粒的形状为近球形，粒径大小范围为3nm～150nm。Ti 49.9Ni 49.9T 0.2弥散颗粒在合金条带中的体积含量约为32％； The initial alloy melt was prepared into Gd 48.8 Ti 25.25 Ni 25.25 T 1.7 alloy strips with a thickness of ~15 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 mainly composed of Gd 96.8 T 3.2 and a large amount of dispersed particle phase mainly composed of Ti 49.9 Ni 49.9 T 0.2 (which is a TiNi intermetallic compound), wherein Ti 49.9 Ni 49.9 T 0.2 The shape of the dispersed particles is nearly spherical, and the particle size ranges from 3 nm to 150 nm. The volume content of Ti 49.9 Ni 49.9 T 0.2 dispersed particles in the alloy strip is about 32%;
通过稀酸溶液将合金条带中的Gd 96.8T 3.2基体去除，使得合金条带中难与稀酸溶液反应的Ti 99.8T 0.2颗粒脱离出来，即得到Ti 49.9Ni 49.9T 0.2纳米粉，其粒径大小范围为3nm～150nm，且其含有的O、H、N、P、S、F、Cl、Br、I的总含量为0.2at.％。 The Gd 96.8 T 3.2 matrix in the alloy strip is removed by the dilute acid solution, so that the Ti 99.8 T 0.2 particles in the alloy strip that are difficult to react with the dilute acid solution are detached, that is, the Ti 49.9 Ni 49.9 T 0.2 nano-powder is obtained. The diameter ranges from 3 nm to 150 nm, and the total content of O, H, N, P, S, F, Cl, Br, and I contained in it is 0.2 at.%.
实施例15Example 15
本实施例提供一种亚微米-微米Fe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-micron Fe powder, and the preparation method comprises the following steps:
选用T(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1at.％ 与2.5at.％的Fe片与稀土La原料。按照La:Fe的摩尔比约为1:2将各合金原料熔化，得到得到原子百分比成分主要为La 32.8Fe 65.7T 1.5的均匀初始合金熔体。 Fe flakes and rare earth La raw materials with atomic percentage contents of T (including O, H, N, P, S, F, Cl, Br, and I) impurity elements are selected respectively as 1 at.% and 2.5 at.%. According to the molar ratio of La:Fe of about 1:2, each alloy raw material is melted to obtain a uniform initial alloy melt whose atomic percentage composition is mainly La 32.8 Fe 65.7 T 1.5 .
通过铜辊甩带技术以约～10 4K/s的凝固速率将初始合金熔体制备成厚度为～100μm的La 32.8Fe 65.7T 1.5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La 95.9T 4.1的基体相与大量成分主要为Fe 99.85T 0.15的弥散颗粒相组成。其中Fe 99.85T 0.15弥散颗粒的形状为近球形或枝晶形，其粒径大小范围为500nm～3μm。Fe 99.85T 0.15弥散颗粒在合金条带中的体积百分含量约为36％； The initial alloy melt was prepared into La 32.8 Fe 65.7 T 1.5 alloy strips with a thickness of ˜100 μm by the copper roll stripping technique at a solidification rate of about ˜10 4 K/s. The solidification structure of the alloy strip is composed of a matrix phase whose atomic percentage is mainly La 95.9 T 4.1 and a large amount of which is a dispersed particle phase whose composition is mainly Fe 99.85 T 0.15 . Among them, the shape of Fe 99.85 T 0.15 dispersed particles is nearly spherical or dendritic, and their particle size ranges from 500 nm to 3 μm. The volume percentage of Fe 99.85 T 0.15 dispersed particles in the alloy strip is about 36%;
通过稀酸溶液将合金条带中的La 95.9T 4.1基体相去除，同时利用Fe的磁性将脱离出来的Fe 99.85T 0.15弥散颗粒与酸溶液迅速分离，即得到主要成分为Fe 99.85T 0.15的亚微米-微米粉，其粒径大小范围为500nm～3μm，且其含有的O、H、N、P、S、F、Cl、Br、I的总含量为0.15at.％。 The La 95.9 T 4.1 matrix phase in the alloy strips is removed by the dilute acid solution, and the Fe 99.85 T 0.15 disperse particles are rapidly separated from the acid solution by the magnetic properties of Fe, that is, the main component of Fe 99.85 T 0.15 is obtained. The micron-micron powder has a particle size range of 500 nm to 3 μm, and the total content of O, H, N, P, S, F, Cl, Br, and I contained in it is 0.15 at.%.
实施例16Example 16
本实施例提供一种纳米Ti-V-Al合金粉体的制备方法，该制备方法包括如下步骤：This embodiment provides a preparation method of nano-Ti-V-Al alloy powder, and the preparation method includes the following steps:
选用T(包含O、H、N、P、S、F、Cl)杂质元素的原子百分比含量分别为1at.％，1at.％，2.5at.％，0.2at.％的海绵Ti、V块、稀土Ce，以及Al原料。将初始合金原料按照一定配比充分熔化，得到原子百分比成分主要为Ce 40.2(Ti 96V 4) 37.9Al 20.5T 1.4的初始合金熔体。 The atomic percentages of T (including O, H, N, P, S, F, Cl) impurity elements are selected as sponge Ti, V block, 1at.%, 2.5at.%, 0.2at. Rare earth Ce, and Al raw materials. The initial alloy raw materials are fully melted according to a certain proportion to obtain an initial alloy melt whose atomic percentage composition is mainly Ce 40.2 (Ti 96 V 4 ) 37.9 Al 20.5 T 1.4 .
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Ce 40.2(Ti 96V 4) 37.9Al 20.5T 1.4合金条带。该合金条带的凝固组织由平均成分主要为Ce 73.2Al 24.3T 2.5的基体相与大量成分主要为(Ti 96V 4) 84Al 15.8T 0.2的弥散颗粒相组成，其中(Ti 96V 4) 84Al 15.8T 0.2弥散颗粒的形状为近球形，粒径大小范围为5nm～200nm。(Ti 96V 4) 84Al 15.8T 0.2弥散颗粒在合金条带中的体积含量约为33％； The initial alloy melt was prepared into Ce 40.2 (Ti 96 V 4 ) 37.9 Al 20.5 T 1.4 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 with an average composition of Ce 73.2 Al 24.3 T 2.5 and a large number of dispersed particles with a main composition of (Ti 96 V 4 ) 84 Al 15.8 T 0.2 , of which (Ti 96 V 4 ) The shape of the 84 Al 15.8 T 0.2 dispersed particles is nearly spherical, and the particle size ranges from 5 nm to 200 nm. The volume content of (Ti 96 V 4 ) 84 Al 15.8 T 0.2 dispersed particles in the alloy strip is about 33%;
通过稀酸溶液将合金条带中的Ce 73.2Al 24.3T 2.5基体去除，使得合金条带中难与稀酸溶液反应的(Ti 96V 4) 84Al 15.8T 0.2颗粒脱离出来，即得到(Ti 96V 4) 84Al 15.8T 0.2纳米粉，其粒径大小范围为5nm～200nm，且其含有的O、H、N、P、S、F、Cl、Br、I的总含量为0.2at.％。 The Ce 73.2 Al 24.3 T 2.5 matrix in the alloy strip is removed by the dilute acid solution, so that the (Ti 96 V 4 ) 84 Al 15.8 T 0.2 particles in the alloy strip that are difficult to react with the dilute acid solution are separated out, that is, (Ti 96 V 4 ) 84 Al 15.8 T 0.2 particles are obtained. 96 V 4 ) 84 Al 15.8 T 0.2 nano-powder, its particle size range is 5nm-200nm, and the total content of O, H, N, P, S, F, Cl, Br, and I contained in it is 0.2at. %.
在保护气氛下将主要成分为(Ti 96V 4) 84Al 15.8T 0.2的纳米粉与环氧树脂及其它涂料组分混合，从而制备得到纳米Ti合金改性聚合物防腐涂料。 The nanometer powder whose main component is (Ti 96 V 4 ) 84 Al 15.8 T 0.2 is mixed with epoxy resin and other coating components under a protective atmosphere to prepare a nano-Ti alloy modified polymer anti-corrosion coating.
实施例17Example 17
本实施例提供一种纳米Ti-Al合金粉体的制备方法，该制备方法包括如下步骤：This embodiment provides a preparation method of nano-Ti-Al alloy powder, and the preparation method includes the following steps:
选用T(包含O、H、N、P、S、F、Cl中的至少一种)杂质元素的原子百分比含量分别为3at.％，2.5at.％，0.2at.％的海绵Ti、稀土Ce，以及Al原料。其中，海绵Ti中还含有0.5at.％的Mn；稀土Ce中还含有0.7at.％的Mg。The atomic percentage content of T (including at least one of O, H, N, P, S, F, and Cl) impurity elements is selected as sponge Ti and rare earth Ce, which are 3 at.%, 2.5 at.%, and 0.2 at.% respectively. , and Al raw materials. Among them, sponge Ti also contains 0.5at.% Mn; rare earth Ce also contains 0.7at.% Mg.
将初始合金原料按照一定配比充分熔化，得到原子百分比成分主要为(Ce 99.3Mg 0.7) 40(Ti 99.5Mn 0.5) 38Al 20.6T 1.4的初始合金熔体。 The initial alloy raw materials are fully melted according to a certain proportion to obtain an initial alloy melt whose atomic percentage composition is mainly (Ce 99.3 Mg 0.7 ) 40 (Ti 99.5 Mn 0.5 ) 38 Al 20.6 T 1.4 .
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(Ce 99.3Mg 0.7) 40(Ti 99.5Mn 0.5) 38Al 20.6T 1.4合金条带。该合金条带的凝固组织由平均成分主要为(Ce 99.3Mg 0.7)Al 24.3T 2.5的基体相与大量成分主要为(Ti 99.5Mn 0.5) 84Al 15.8T 0.2的弥散颗粒相组成，其中(Ti 99.5Mn 0.5) 84Al 15.8T 0.2弥散颗粒的形状为近球形，粒径大小范围为5nm～200nm。(Ti 99.5Mn 0.5) 84Al 15.8T 0.2弥散颗粒在合金条带中的体积含量约为33％；而且，合金熔体中Mn与Mg的引入，并没有导致初始合金条带中生成由Ce、Mg与Ti、Mn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 as ~20 μm thick (Ce 99.3 Mg 0.7 ) 40 (Ti 99.5 Mn 0.5 ) 38 Al 20.6 T 1.4 alloy strips 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 with an average composition of (Ce 99.3 Mg 0.7 )Al 24.3 T 2.5 and a large amount of dispersed particles with a major composition of (Ti 99.5 Mn 0.5 ) 84 Al 15.8 T 0.2 , of which (Ti 99.5 Mn 0.5 ) 84 Al 15.8 T 0.2 The shape of the 99.5 Mn 0.5 ) 84 Al 15.8 T 0.2 dispersed particles is nearly spherical, and the particle size ranges from 5 nm to 200 nm. The volume content of (Ti 99.5 Mn 0.5 ) 84 Al 15.8 T 0.2 dispersed particles in the alloy strip is about 33%; and the introduction of Mn and Mg in the alloy melt did not lead to the formation of Ce, It is an intermetallic compound composed of Mg, Ti and Mn; 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.
通过稀酸溶液将合金条带中的(Ce 99.3Mg 0.7)Al 24.3T 2.5基体去除，使得合金条带中难与稀酸溶液反应的(Ti 99.5Mn 0.5) 84Al 15.8T 0.2颗粒脱离出来，即得到主要成分为(Ti 99.5Mn 0.5) 84Al 15.8T 0.2的纳米粉，其粒径大小范围为5nm～200nm，且其含有的O、H、N、P、S、F、Cl、Br、I的总含量为0.2at.％。 The (Ce 99.3 Mg 0.7 )Al 24.3 T 2.5 matrix in the alloy strip is removed by the dilute acid solution, so that the (Ti 99.5 Mn 0.5 ) 84 Al 15.8 T 0.2 particles in the alloy strip that are difficult to react with the dilute acid solution are separated out, That is to obtain nano-powder whose main component is (Ti 99.5 Mn 0.5 ) 84 Al 15.8 T 0.2 , its particle size range is 5nm-200nm, and it contains O, H, N, P, S, F, Cl, Br, The total content of I was 0.2 at.%.
在保护气氛下将主要成分为(Ti 99.5Mn 0.5) 84Al 15.8T 0.2的纳米粉与环氧树脂及其它涂料组分混合，从而制备得到纳米Ti合金改性聚合物防腐涂料。 The nanometer powder whose main component is (Ti 99.5 Mn 0.5 ) 84 Al 15.8 T 0.2 is mixed with epoxy resin and other coating components under protective atmosphere to prepare nano-Ti alloy modified polymer anti-corrosion coating.
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 more 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 (19)

  1. 一种高纯粉体材料的制备方法，其特征在于，包括以下步骤：A preparation method of high-purity powder material, 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T的均匀初始合金熔体，其中，T包含O、H、N、P、S、F、Cl、I、Br中的至少一种，且所述初始合金熔体的平均成分包括以下组合中的任意一种：Step S1, select an 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 an impurity element T, wherein T includes O, H, N, P, S, F, Cl, At least one of I, Br, and the average composition of the initial alloy melt includes any one of the following combinations:
    组合(1)：所述初始合金熔体的平均成分主要为A a(M xD y) bT d，其中，A包含Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的至少一种，M包含W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti中的至少一种，D包含Fe、Co、Ni中的至少一种，其中，x、y；a、b、d代表对应组成元素的原子百分比含量，且24.9％≤a≤99.4％，0.5％≤b≤75％，0<d≤10％；10％≤x≤55％，45％≤y≤90％； Combination (1): the average composition of the initial alloy melt is mainly A a (M x D y ) b T d , wherein A includes Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, At least one of Tb, Dy, Ho, Er, Tm, Yb, Lu, M includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti, D includes Fe, Co, At least one of Ni, wherein x, y; a, b, d represent the atomic percentage content of the corresponding constituent elements, and 24.9%≤a≤99.4%, 0.5%≤b≤75%, 0<d≤10% ;10%≤x≤55%, 45%≤y≤90%;
    组合(2)：所述初始合金熔体的平均成分主要为A aM bT d，其中，A包含Mg、Ca、Li、Na、K、Cu、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的至少一种，M包含W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti中的至少一种；其中a、b、d代表对应组成元素的原子百分比含量，且24.9％≤a≤99.4％，0.5％≤b≤75％，0<d≤10％； Combination (2): the average composition of the initial alloy melt is mainly A a M b T d , wherein A includes Mg, Ca, Li, Na, K, Cu, Y, La, Ce, Pr, Nd, Pm , at least one of Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, M includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti ; where a, b, d represent the atomic percentage content of the corresponding constituent elements, and 24.9%≤a≤99.4%, 0.5%≤b≤75%, 0<d≤10%;
    组合(3)：所述初始合金熔体的平均成分主要为A aM bT d，其中，A包含Zn、Mg、Sn、Pb、Ga、In、Al、La、Ge、Cu、K、Na、Li中的至少一种，M包含B、Bi、Fe、Ni、Cu、Ag、Si、Ge、Cr、V中的至少一种，其中a、b、d代表对应组成元素的原子百分比含量，且24.9％≤a≤59.9％，40％<b≤75％，0<d≤10％； Combination (3): the average composition of the initial alloy melt is mainly A a M b T d , wherein A includes Zn, Mg, Sn, Pb, Ga, In, Al, La, Ge, Cu, K, Na , at least one of Li, M includes at least one of B, Bi, Fe, Ni, Cu, Ag, Si, Ge, Cr, V, wherein a, b, d represent the atomic percentage content of the corresponding constituent elements, And 24.9%≤a≤59.9%, 40%<b≤75%, 0<d≤10%;
    组合(4):当所述初始合金熔体的平均成分主要为A aM bAl cT d时，A包含Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的至少一种；M包含W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti中的至少一种；Al为铝；其中a、b、c、d分别代表对应组成元素的原子百分比含量，且29.8％≤a≤64.8％，35％<b≤70％，0.1％≤c≤25％，0<d≤10％； Combination (4): When the average composition of the initial alloy melt is mainly A a M b Al c T d , A contains Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy , at least one of Ho, Er, Tm, Yb, Lu; M includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti; Al is aluminum; wherein a, b, c and d respectively represent the atomic percentage content of the corresponding constituent elements, and 29.8%≤a≤64.8%, 35%<b≤70%, 0.1%≤c≤25%, 0<d≤10%;
    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T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；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 T 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;
    当初始合金熔体的平均成分为步骤S1组合(1)时，所述初始合金条带中弥散颗粒相的成分主要为(M xD y) x1T z1，基体相的平均成分主要为A x2T z2；且98.5％≤x1<100％,0<z1≤1.5％；80％≤x2<100％,0<z2≤20％；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； When the average composition of the initial alloy melt is the combination (1) of step S1, the composition of the dispersed particle phase in the initial alloy strip is mainly (M x D y ) x1 T z1 , and the average composition of the matrix phase is mainly A x2 T z2 ; and 98.5%≤x1<100%, 0<z1≤1.5%;80%≤x2<100%,0<z2≤20%;z1<d<z2,2z1<z2; x1, z1, x2, z2 respectively represent the atomic percentage content of the corresponding constituent elements;
    当初始合金熔体的平均成分为步骤S1组合(2)或组合(3)时，所述初始合金条带中弥散颗粒相的成分主要为M x1T z1，基体相的平均成分主要为A x2T z2；且98.5％≤x1<100％,0<z1≤1.5％； 80％≤x2<100％,0<z2≤20％；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； When the average composition of the initial alloy melt is the combination (2) or the combination (3) in step S1, the composition of the dispersed particle phase in the initial alloy strip is mainly M x1 T z1 , and the average composition of the matrix phase is mainly A x2 T z2 ; and 98.5%≤x1<100%, 0<z1≤1.5%;80%≤x2<100%,0<z2≤20%;z1<d<z2,2z1<z2; x1, z1, x2, z2 respectively represent the atomic percentage content of the corresponding constituent elements;
    当初始合金熔体的平均成分为步骤S1组合(4)时，所述初始合金条带中弥散颗粒相的成分主要为M x1Al y1T z1，基体相的平均成分主要为A x2Al y2T z2；且77.8％≤x1≤99.8％，0.1％≤y1≤22％，0<z1≤1.5％；69.8％≤x2≤99.7％，0.2％≤y2≤30％，0<z2≤20％，z1<d<z2，2z1<z2，y1<y2，x1、y1、z1、x2、y2、z2分别代表对应组成元素的原子百分比含量； When the average composition of the initial alloy melt is the combination (4) of step S1, the composition of the dispersed particle phase in the initial alloy strip is mainly M x1 A y1 T z1 , and the average composition of the matrix phase is mainly A x2 A y2 T z2 ; and 77.8%≤x1≤99.8%, 0.1%≤y1≤22%, 0<z1≤1.5%; 69.8%≤x2≤99.7%, 0.2%≤y2≤30%, 0<z2≤20%, z1 <d<z2, 2z1<z2, y1<y2, x1, y1, z1, x2, y2, z2 respectively 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, and the shedding dispersed particle phase is collected, that is, a high-purity particle composed of the original dispersed particles is obtained. Target powder material.
  2. 根据权利要求1所述的高纯粉体材料的制备方法，其特征在于，所述初始合金熔体中的T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 high-purity powder material according to claim 1, wherein the source of the T 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.
  3. 根据权利要求1所述的高纯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A与M构成的金属间化合物。The method for preparing a high-purity powder material according to claim 1, wherein the initial alloy strip does not contain an intermetallic compound composed of A and M.
  4. 根据权利要求1所述的高纯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 high-purity powder material according to claim 1, wherein the number of single crystal particles of the dispersed particles in the initial alloy strip accounts for no less than 60% of the total number of dispersed particles.
  5. 根据权利要求1所述的高纯粉体材料的制备方法，其特征在于，z1<d<z2，且2z1<z2。The method for preparing a high-purity powder material according to claim 1, wherein z1<d<z2, and 2z1<z2.
  6. 根据权利要求1所述的高纯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、碱反应去除、真空挥发去除、基体相自然氧化-粉化剥落去除中的至少一种。The method for preparing a high-purity powder material according to claim 1, wherein the method for removing the matrix phase in the alloy strip comprises: acid reaction removal, alkali reaction removal, vacuum volatilization removal, and natural oxidation of the matrix phase- At least one of chalking and exfoliation removal.
  7. 根据权利要求1所述的高纯粉体材料的制备方法，其特征在于，所述高纯粉体材料的颗粒粒径范围为2nm～3mm。The method for preparing a high-purity powder material according to claim 1, wherein the particle size of the high-purity powder material ranges from 2 nm to 3 mm.
  8. 根据权利要求1所述的高纯粉体材料的制备方法，其特征在于，在所述步骤S3之后还进行以下步骤：将所述高纯粉体材料筛分后，选择粒径范围为5μm～200μm的高纯粉体材料进行等离子球化处理，得到呈球形的高纯粉体材料。The method for preparing a high-purity powder material according to claim 1, wherein the following step is performed after the step S3: after the high-purity powder material is sieved, a particle size range of 5 μm～ 200μm high-purity powder material is subjected to plasma spheroidization to obtain spherical high-purity powder material.
  9. 根据权利要求1-8任一项所述的高纯粉体材料或球形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、磁性材料、金属注射成型、3D打印、涂料中的应用。The high-purity powder material or spherical high-purity powder material according to any one of claims 1-8 is used in catalytic materials, powder metallurgy, composite materials, wave absorbing materials, sterilization materials, magnetic materials, metal injection molding, 3D printing , Application in coatings.
  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；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;
    所述合金条带的化学组成与结构包含以下四种组合中的任意一种：The chemical composition and structure of the alloy strip includes any one of the following four combinations:
    1)所述合金条带中内生粉的成分主要为(M xD y) x1T z1，包覆体的平均成分主要为A x2T z2；且98.5％≤x1<100％,0<z1≤1.5％；80％≤x2<100％,0<z2≤20％；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，A包含Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的至少一种，M包含W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti中的至少一种，D包含Fe、Co、Ni中的至少一种；T包含O、H、N、P、S、F、Cl、I、Br中的至少一种；x、y代表对应组成元素的原子百分比含量，10％≤x≤55％，45％≤y≤90％； 1) The composition of the endogenous powder in the alloy strip is mainly (M x D y ) x1 T z1 , and the average composition of the clad is mainly A x2 T z2 ; and 98.5%≤x1<100%, 0<z1 ≤1.5%; 80%≤x2<100%, 0<z2≤20%;z1<d<z2,2z1<z2; x1, z1, x2, z2 respectively represent the atomic percentage content of the corresponding constituent elements; among them, A contains At least one of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, M includes W, Cr, Mo, V, Ta, Nb , at least one of Zr, Hf, Ti, D includes at least one of Fe, Co, Ni; T includes at least one of O, H, N, P, S, F, Cl, I, Br; x and y represent the atomic percentage content of the corresponding constituent elements, 10%≤x≤55%, 45%≤y≤90%;
    2)所述合金条带中内生粉的成分主要为M x1T z1，包覆体的平均成分主要为A x2T z2；且98.5％≤x1<100％,0<z1≤1.5％；80％≤x2<100％,0<z2≤20％；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，A包含Mg、Ca、Li、Na、K、Cu、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的至少一种，M包含W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti中的至少一种；T包含O、H、N、P、S、F、Cl、I、Br中的至少一种； 2) The composition of the endogenous powder in the alloy strip is mainly M x1 T z1 , and the average composition of the clad is mainly A x2 T z2 ; and 98.5%≤x1<100%, 0<z1≤1.5%; 80 %≤x2<100%, 0<z2≤20%;z1<d<z2,2z1<z2; x1, z1, x2, z2 represent the atomic percentage content of the corresponding constituent elements respectively; among them, A contains Mg, Ca, Li , at least one of Na, K, Cu, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, M includes W, Cr, At least one of Mo, V, Ta, Nb, Zr, Hf, Ti; T includes at least one of O, H, N, P, S, F, Cl, I, Br;
    3)所述合金条带中内生粉的成分主要为M x1T z1，包覆体的平均成分主要为A x2T z2；且98.5％≤x1<100％,0<z1≤1.5％；80％≤x2<100％,0<z2≤20％；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，A包含Zn、Mg、Sn、Pb、Ga、In、Al、La、Ge、Cu、K、Na、Li中的至少一种，M包含B、Bi、Fe、Ni、Cu、Ag、Si、Ge、Cr、V中的至少一种；T包含O、H、N、P、S、F、Cl、I、Br中的至少一种； 3) The composition of the endogenous powder in the alloy strip is mainly M x1 T z1 , and the average composition of the clad is mainly A x2 T z2 ; and 98.5%≤x1<100%, 0<z1≤1.5%; 80 %≤x2<100%, 0<z2≤20%;z1<d<z2,2z1<z2; x1, z1, x2, and z2 represent the atomic percentage content of the corresponding constituent elements, respectively; A contains Zn, Mg, Sn , at least one of Pb, Ga, In, Al, La, Ge, Cu, K, Na, Li, M includes at least one of B, Bi, Fe, Ni, Cu, Ag, Si, Ge, Cr, V One; T includes at least one of O, H, N, P, S, F, Cl, I, and Br;
    4)所述合金条带中内生粉的成分主要为M x1Al y1T z1，包覆体的平均成分主要为A x2Al y2T z2；且77.8％≤x1≤99.8％，0.1％≤y1≤22％，0<z1≤1.5％；69.8％≤x2≤99.7％，0.2％≤y2≤30％，0<z2≤20％，z1<d<z2，2z1<z2，y1<y2，x1、y1、z1、x2、y2、z2分别代表对应组成元素的原子百分比含量；其中，A包含Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的至少一种；M包含W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti中的至少一种；Al为铝；T包含O、H、N、P、S、F、Cl、I、Br中的至少一种。 4) The composition of the endogenous powder in the alloy strip is mainly M x1 A y1 T z1 , and the average composition of the clad is mainly A x2 A y2 T z2 ; and 77.8%≤x1≤99.8%, 0.1%≤y1 ≤22%, 0<z1≤1.5%; 69.8%≤x2≤99.7%, 0.2%≤y2≤30%, 0<z2≤20%, z1<d<z2, 2z1<z2, y1<y2, x1, y1, z1, x2, y2, and z2 respectively represent the atomic percentage content of the corresponding constituent elements; among them, A includes Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm , at least one of Yb, Lu; M includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti; Al is aluminum; T includes O, H, N, P, S , at least one of F, Cl, I, and Br.
  11. 一种高纯金属粉的制备方法，其特征在于，其包括以下步骤：A preparation method of high-purity metal powder is characterized in that, it comprises the following steps:
    步骤一：选择初始合金，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，然后将合金熔体通过快速凝固技术制备成合金条带；Step 1: select an initial alloy, melt the initial alloy raw material according to the initial alloy composition ratio to obtain a uniform alloy melt, and then prepare the alloy melt into an alloy strip by a rapid solidification technique;
    当所述初始合金的成分配比为A aM b时，A选自Mg、Ca、Li、Na、K、Zn、Pb、Sn、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的至少一种，M选自W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti、Fe、Co、Ni、Cu、Ag、Si、Ge中的至少一种，且M中不单独只含Fe；其中a、b代表对应组成元素的原子百分比含量，45％<b≤75％，a+b＝100％；且A aM b合金条带的凝固组织中不含有由A与M构成的金属间化合物，其凝固组织由成分为A 的基体相以及成分为M的弥散颗粒相组成； When the composition ratio of the initial alloy is A a M b , A is selected from Mg, Ca, Li, Na, K, Zn, Pb, Sn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu , at least one of Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, M is selected from W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti, Fe, Co, Ni, Cu , at least one of Ag, Si, and Ge, and M does not contain only Fe alone; where a, b represent the atomic percentage content of the corresponding constituent elements, 45%<b≤75%, a+b=100%; and The solidified structure of the A a M b alloy strip does not contain intermetallic compounds composed of A and M, and its solidified structure is composed of the matrix phase with the composition A and the dispersed particle phase with the composition M;
    当所述初始合金的成分配比为La aFe b时，40％<b≤75％，a+b＝100％，a、b代表对应组成元素的原子百分比含量；且La aFe b合金条带的凝固组织中不含有由La与Fe构成的金属间化合物，其凝固组织由成分为La的基体相以及成分为Fe的弥散颗粒相组成； When the composition ratio of the initial alloy is La a Fe b , 40%<b≤75%, a+b=100%, a and b represent the atomic percentage contents of the corresponding constituent elements; and La a Fe b alloy strips The solidified structure of the belt does not contain intermetallic compounds composed of La and Fe, and its solidified structure is composed of a matrix phase composed of La and a dispersed particle phase composed of Fe;
    当所述初始合金的成分配比为A aM bAl c时，A选自Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的至少一种，Al为铝，M选自W、Cr、Mo、V、Ta、Nb、Zr、Hf、Ti、Fe、Co、Ni中的至少一种；其中a、b、c分别代表对应组成元素的原子百分比含量，35％<b≤75％，0.1％≤c≤30％，a+b+c＝100％；且A aM bAl c合金条带的凝固组织中不含有由A与M构成的金属间化合物，其凝固组织由成分为M x1Al y1的弥散颗粒相以及成分为A x2Al y2的基体相组成；其中x1、y1、x2、y2分别代表对应组成元素的原子百分比含量，且0.1％≤y1≤25％，0.1％≤y2≤35％，x1+y1＝100％，x2+y2＝100％。 When the composition ratio of the initial alloy is A a M b Al c , A is selected from Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb , at least one of Lu, Al is aluminum, M is selected from at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti, Fe, Co, Ni; wherein a, b, c Respectively represent the atomic percentage content of the corresponding constituent elements, 35%<b≤75%, 0.1%≤c≤30%, a+b+c=100%; and the solidification structure of the A a M b Al c alloy strip is not Contains an intermetallic compound composed of A and M, and its solidification structure is composed of a dispersed particle phase with a composition of M x1 Al y1 and a matrix phase with a composition of A x2 Al y2 ; where x1, y1, x2, y2 represent the corresponding constituent elements respectively , and 0.1%≤y1≤25%, 0.1%≤y2≤35%, x1+y1=100%, x2+y2=100%.
    所述初始合金熔体凝固过程中，合金熔体中的杂质元素与凝固过程中引入的杂质元素富集于所述基体相中，从而使所述弥散颗粒相得到纯化；During the solidification process of the initial alloy melt, the impurity elements in the alloy melt and the impurity elements introduced during the solidification process are enriched in the matrix phase, so that the dispersed particle phase is purified;
    步骤二：将所述合金条带中的基体相去除并保留弥散颗粒相，富集于基体相中的杂质元素随之被去除，即得到由弥散颗粒组成的高纯目标金属粉。Step 2: The matrix phase in the alloy strip is removed and the dispersed particle phase is retained, and the impurity elements enriched in the matrix phase are removed accordingly, that is, a high-purity target metal powder composed of dispersed particles is obtained.
  12. 根据权利要求11所述的高纯金属粉的制备方法，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50K/s～10 7K/s。 The method for preparing high-purity metal powder according to claim 11, wherein the rapid solidification technology comprises an alloy melt metal roll strip method, and the solidification rate of the alloy melt is 50K/s～10 7 K/s.
  13. 根据权利要求11所述的高纯金属粉的制备方法，其特征在于，所述合金条带的厚度为5μm～5mm。The method for preparing high-purity metal powder according to claim 11, wherein the alloy strip has a thickness of 5 μm˜5 mm.
  14. 根据权利要求11所述的高纯金属粉的制备方法，其特征在于，所述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，颗粒大小范围为2nm～200μm。The method for preparing high-purity metal powder according to claim 11, wherein the shape of the dispersed particle phase comprises at least one of dendritic, spherical, near-spherical, square, pie, and rod shape, and the particle The size range is from 2nm to 200μm.
  15. 根据权利要求11所述的高纯金属粉的制备方法，其特征在于，所述合金熔体中的杂质元素与凝固过程中引入的杂质元素包含H、O、N、S、P、F、Cl、I、Br中的至少一种。The method for preparing high-purity metal powder according to claim 11, wherein the impurity elements in the alloy melt and the impurity elements introduced in the solidification process comprise H, O, N, S, P, F, Cl At least one of , I, and Br.
  16. 根据权利要求11所述的高纯金属粉的制备方法，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、碱反应去除、真空挥发去除中的至少一种。The method for preparing high-purity metal powder according to claim 11, wherein the method for removing the matrix phase from the alloy strip comprises at least one of acid reaction removal, alkali reaction removal, and vacuum volatilization removal.
  17. 根据权利要求11所述的高纯金属粉的制备方法，其特征在于，所述将合金条带中基体相去除方法包括基体相自然氧化-粉化剥落去除。The method for preparing high-purity metal powder according to claim 11, wherein the method for removing the matrix phase in the alloy strip comprises the natural oxidation of the matrix phase-powdering and exfoliation removal.
  18. 根据权利要求11所述的高纯金属粉的制备方法，其特征在于，所述由弥散颗粒相组成的高纯目标金属粉的粒径范围为2nm～200μm；所述高纯目标金属粉的形状包括球形、近球形、枝晶形、棒条形、板条形。The method for preparing high-purity metal powder according to claim 11, wherein the particle size range of the high-purity target metal powder composed of the dispersed particle phase is 2 nm to 200 μm; the shape of the high-purity target metal powder Including spherical, nearly spherical, dendritic, rod-shaped, lath-shaped.
  19. 根据权利要求11所述的高纯金属粉的制备方法，其特征在于，所述高纯目标金属粉中H、 O、N、S、P、F、Cl、I、Br的总含量低于2000ppm。The method for preparing high-purity metal powder according to claim 11, wherein the total content of H, O, N, S, P, F, Cl, I, and Br in the high-purity target metal powder is less than 2000 ppm .
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