CN111940750B - Preparation method of alloy powder material - Google Patents
Preparation method of alloy powder material Download PDFInfo
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- CN111940750B CN111940750B CN201910400790.5A CN201910400790A CN111940750B CN 111940750 B CN111940750 B CN 111940750B CN 201910400790 A CN201910400790 A CN 201910400790A CN 111940750 B CN111940750 B CN 111940750B
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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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C3/00—Removing material from alloys to produce alloys of different constitution separation of the constituents of alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C3/00—Removing material from alloys to produce alloys of different constitution separation of the constituents of alloys
- C22C3/005—Separation of the constituents of alloys
Abstract
The invention relates to a preparation method of an alloy powder material. By utilizing the characteristic that the alloy solidification structure contains a matrix phase and an inert dispersion particle phase, the matrix phase is reacted and removed through an acid solution, so that the dispersion particle phase is separated out, and the alloy powder material is obtained. The method has simple process, can prepare various alloy powder materials with different morphologies including nano-scale, submicron-scale, micron-scale and millimeter-scale, and has good application prospects in the fields of catalysis, powder metallurgy, 3D printing and the like.
Description
Technical Field
The invention relates to the technical field of metal materials, in particular to a preparation method of an alloy powder material.
Background
The alloy powder with the micro-nano particle size has special surface effect, quantum size effect, quantum tunneling effect, coulomb blocking effect and the like, and shows a plurality of peculiar properties different from the traditional materials in the aspects of optics, electrics, magnetics, catalysis and the like, so the alloy powder is widely applied to a plurality of fields of photoelectronic devices, wave-absorbing materials, high-efficiency catalysts and the like.
At present, methods for producing ultrafine alloy powder are classified into a solid phase method, a liquid phase method, and a gas phase method from the state of matter. The solid phase method mainly includes mechanical pulverization, ultrasonic pulverization, thermal decomposition, explosion, and the like. The liquid phase method mainly includes precipitation, alkoxide method, carbonyl method, spray heat drying method, freeze drying method, electrolytic method, chemical coagulation method, and the like. The vapor phase method mainly includes a vapor phase reaction method, a plasma method, a high temperature plasma method, an evaporation method, a chemical vapor deposition method, and the like. Although there are many methods for preparing ultra-fine alloy powders, each method has certain limitations. For example, the liquid phase method has disadvantages of low yield, high cost, complicated process, and the like. The mechanical method has the disadvantages that the classification is difficult after the powder is prepared, and the purity, the fineness and the appearance of the product are difficult to ensure. The rotary electrode method and the gas atomization method are the main methods for preparing high-performance alloy powder at present, but the production efficiency is low, the yield of the ultrafine powder is not high, and the energy consumption is relatively large; the jet milling method and the hydrogenation dehydrogenation method are suitable for large-scale industrial production, but have strong selectivity on raw material metals and alloys. Therefore, the development of a new preparation method of the superfine alloy powder material has important significance.
Disclosure of Invention
In view of the above, it is necessary to provide a method for preparing an alloy powder material, which is simple in process and easy to operate.
A preparation method of an alloy powder material comprises the following steps:
providing (M)xTy)aREbThe alloy is characterized in that M is selected from at least one of Fe, Co and Ni, T is selected from at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf and Ti, RE is selected from at least one of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, x and Y and a and b respectively represent the atom percentage content of the corresponding components, x is more than or equal to 33% and less than or equal to 75%, and x + Y is more than or equal to 100%; a is more than or equal to 0.1 percent and less than or equal to 40 percent, a + b is 100 percent, and the (MxTy)aREbThe solidification structure of the alloy is formed by the composition MxTyThe dispersed particle phase consists of a matrix phase with the main component of RE;
will be (M)xTy)aREbMixing the alloy with an acid solution to enable the matrix phase to react with the acid solution to become ions which enter the solution, and separating out the dispersed particle phase to obtain the M-type metal oxidexTyThe alloy powder material.
Further, the (M)xTy)aREbThe alloy is obtained by the following method:
weighing alloy raw materials according to a ratio;
fully melting the alloy raw materials to obtain an alloy melt;
preparing the (M) by a solidification method from an alloy meltxTy)aREbAn alloy, wherein the solidification rate of the alloy melt is 0.001K/s to 107K/s。
Further, the vacuum degree in the alloy melt smelting process is 1 multiplied by 10-4Pa～1.01325×105Pa。
Further, the particle shape of the dispersed particle phase comprises at least one of a dendritic form, a spherical form, a nearly spherical form, a square form, a cake form and a rod form, and the particle size of the dispersed particle phase is 2 nm-100 mm.
Further, the acid in the acid solution is at least one of sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, phosphoric acid, acetic acid, oxalic acid, formic acid, carbonic acid, gluconic acid, oleic acid and polyacrylic acid, and the solvent in the acid solution is water, ethanol, methanol or a mixture of the three in any proportion.
Further, the molar concentration of the acid in the acid solution is 0.001 mol/L-5 mol/L.
Further, the (M)xTy)aREbIn the step of reacting the alloy with the acid solution, the reaction time is 0.1 min-48 h, and the reaction temperature is 0-100 ℃.
Further, said MxTyThe grain diameter of the alloy powder material is 2 nm-100 mm.
Further, in the (M)xTy)aREbThe step of reacting the alloy with the acid solution is further followed by the steps of: screening the obtained alloy powder material with the particle size range of 1 mu m-1 mm, and respectively carrying out plasma spheroidization treatment to finally obtain the spherical alloy powder material with different particle sizes.
Further, the particle size of the spherical alloy powder material with different particle diameters is 1 mu m-1 mm.
In the preparation method of the alloy powder material, the alloy powder material is prepared by selecting metal M, metal T and rare earth RE with specific category and contentxTy)aREbAnd (3) alloying. The alloy solidification structure consists of MxTyThe dispersed particle phase consists of a matrix phase with the main component of RE, and the structure is favorable for subsequent separation. Specifically, the (M)xTy)aREbWhen the alloy is subsequently reacted with dilute acid solution, the matrix phase reacts with H ions in the acid solution to become ions which enter the solution, and the component of the ions is MxTyThe dispersed particle phase of (A) is difficult to react with dilute acid solution, so that (M) can be obtainedxTy)aREbDispersing and separating out the alloy to finally obtain MxTyAn alloy powder material.
In addition, the rare earth elements not only have good absorption effect on oxygen, but also have good absorption effect on other various impurity elements in the alloy raw materials M and T. Thus, (M)xTy)aREbDispersed particle phase in alloy and obtained MxTyThe alloy powder material tends to have a higher purity than the raw materials M and T.
The method has low cost and simple operation, and can prepare various alloy powder materials with different morphologies including nano-scale, submicron-scale, micron-scale and millimeter-scale. The alloy powder material has good application prospects in the fields of hydrogen storage, catalysis, powder metallurgy, 3D printing and the like.
Drawings
FIG. 1 is a SEM of CoTi dendrites prepared in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of CoTi dendrites prepared according to example 1 of the present invention;
FIG. 3 is an energy spectrum of CoTi dendrites prepared according to example 1 of the present invention.
Detailed Description
The invention will be described in further detail below with reference to the accompanying drawings and examples, which are intended to facilitate the understanding of the invention and are not intended to limit the invention in any way.
The preparation method of the alloy powder material provided by the invention comprises the following steps:
s1, providing (M)xTy)aREbThe alloy is characterized in that M is selected from at least one of Fe, Co and Ni, T is selected from at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf and Ti, RE is selected from at least one of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, x and Y and a and b respectively represent the atom percentage content of the corresponding components, x is more than or equal to 33% and less than or equal to 75%, and x + Y is more than or equal to 100%; a is more than or equal to 0.1 percent and less than or equal to 40 percent, a + b is 100 percent, and the (MxTy)aREbThe solidification structure of the alloy is formed by the composition MxTyThe dispersed particle phase consists of a matrix phase with the main component of RE;
s2, mixing the (M)xTy)aREbMixing the alloy with an acid solution to react the matrix phase with the acid solution to become ions which enter the solution, andthe dispersed particle phase is separated to obtain the compound MxTyThe alloy powder material.
In step S1, the step (M)xTy)aREbThe alloy is obtained by the following method:
(1) weighing alloy raw materials according to a ratio;
(2) fully melting the alloy raw materials to obtain an alloy melt;
(3) preparing the (M) by a solidification method from an alloy meltxTy)aREbAn alloy, wherein the solidification rate of the alloy melt is 0.001K/s to 107K/s。
In the step (1), smelting (M) is prepared according to specific composition and contentxTy)aREbThe alloy requires raw materials.
In the step (2), because a large amount of rare earth elements exist in the alloy melt obtained by melting the alloy raw materials, in the melting process, oxygen is completely and rapidly absorbed by the rare earth elements even if entering the alloy melt, and a dense rare earth oxide protective film covering the surface of the alloy melt is formed, so that the oxygen is blocked from further entering a channel of the alloy melt. Therefore, even if the alloy is melted under a low vacuum condition, even under an atmospheric environment, the dispersed particle phase in the alloy solidification structure is not contaminated by oxygen. Therefore, the vacuum degree in the melting process of the alloy melt is 1 multiplied by 10-4Pa～1.01325×105At Pa, the purity of the dispersed particle phase obtained can still be ensured.
In addition, the rare earth elements not only have good absorption effect on oxygen, but also have good absorption effect on other various impurity elements in the alloy raw materials M and T. Thus, (M)xTy)aREbThe dispersed particulate phase in the alloy tends to have a higher purity than the raw materials M and T.
It will be appreciated that if the alloy starting materials are metal M, metal T and rare earth RE, the elements may be melted to produce an alloy melt. If the alloy raw material provided is directly (M)xTy)aREbWhen alloyed, then (M) can bexTy)aREbAnd remelting the alloy to obtain an alloy melt. Of course, the metal M, the metal T and the rare earth RE can be melted and prepared into (M)xTy)aREbAlloy, then (M)xTy)aREbAnd remelting the alloy to obtain an alloy melt.
In the step (3), the solidification structure of the alloy melt is MxTyWith a dispersed particle phase consisting of a matrix phase with a predominant RE component. Wherein the component is MxTyThe dispersed particle phase of the (B) is an inert component under the action of dilute acid and is difficult to react with acid; the matrix phase, the main component of which is RE, is an active component and is very easy to react with acid. Therefore, the (M)xTy)aREbThe solidification structure of the alloy is beneficial to subsequent separation.
Specifically, the solidification method is not limited, and may be casting, melt spinning, melt drawing, or the like. The particle size and shape of the finally formed alloy powder material and (M)xTy)aREbM in the alloyxTyThe dispersed particle phase has substantially uniform particle size and morphology. The M isxTyThe particle size of the dispersed particulate phase is related to the solidification rate of the alloy melt during the manufacturing process. In general, MxTyThe particle size of the dispersed particle phase is inversely related to the cooling rate of the alloy melt, i.e.: the greater the solidification rate of the alloy melt, the smaller the particle size of the dispersed particle phase. Wherein the solidification rate of the alloy melt can be 0.001K/s-107K/s, said MxTyThe particle size of the dispersed particle phase may be from 2nm to 100 mm.
The shape of the dispersed particulate phase is not limited and may include at least one of a dendritic form, a spherical form, a nearly spherical form, a block form, a cake form, and a rod form. When the particles are rod-like in shape, the size of the particles is specified in particular as the diameter dimension of the rod-like cross section.
In step S2, the acid solution contains H+The solution of (1). Due to (M)xTy)aREbThe alloy solidification structure consists of MxTyWith a dispersed particle phase consisting of a matrix phase with a predominant RE component. Therefore, H in the dilute acid solution+M which reacts with rare earth elements in the matrix phase to dissolve the rare earth elements into solution and is difficult to react with dilute acid solutionxTyThe dispersed particle phase is dispersed and separated from the original alloy. Cleaning to obtain MxTyAn alloy powder material. The grain diameter of the alloy powder material can be nano-scale, submicron scale, micron scale or even millimeter scale.
Specifically, the acid in the acid solution may be at least one of sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, phosphoric acid, acetic acid, oxalic acid, formic acid, carbonic acid, gluconic acid, oleic acid, and polyacrylic acid, and is preferably at least one of sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, phosphoric acid, acetic acid, and oxalic acid. The solvent in the acid solution is water, ethanol, methanol or a mixture of the water, the ethanol and the methanol mixed in any proportion.
The concentration of the dilute acid in the acid solution is not particularly limited as long as it can react with the matrix phase and retain the primary crystal phase. The reaction time is not limited, and the reaction temperature is not limited. Preferably, the molar concentration of the acid in the acid solution may be 0.001mol/L to 5 mol/L. The reaction time of the reaction can be 0.1min to 48h, and the reaction temperature can be 0 ℃ to 100 ℃.
Further, after the step S2, if the particle diameter of the obtained alloy powder material is in the range of 1 μm to 1mm, the following steps may be further performed: and screening the obtained alloy powder material, and respectively carrying out plasma spheroidization treatment to finally obtain the spherical alloy powder material with different particle sizes.
The powder material after screening can be spheroidized by plasma spheroidization.
The particle diameter of the spherical alloy powder material with different particle diameters is 1 mu m-1 mm.
Therefore, the method has low cost and simple operation, and can prepare various alloy powder materials with different morphologies including nano-scale, submicron-scale, micron-scale and millimeter-scale. The alloy powder material has good application prospects in the fields of hydrogen storage, catalysis, powder metallurgy, 3D printing and the like.
The following will be further described by way of examples.
Example 1:
the embodiment provides a preparation method of micron-sized CoTi powder, which comprises the following steps:
(1) the formula of the selected formula is (Co)50Ti50)25Gd75The raw materials are weighed according to the formula and are 10-2Fully melting under Pa vacuum condition (Co)50Ti50)25Gd75An alloy melt was poured into a copper mold having a cavity cross-sectional size of 4mm × 6mm, and cast at a cooling rate of about 75K/s to prepare a (Co) alloy having a size of 4mm × 6mm × 30mm50Ti50)25Gd75The alloy thin plate has an alloy solidification structure comprising dispersed dendritic particles composed of CoTi and a matrix phase composed of Gd, wherein the size range of the CoTi dendritic particles is 2-40 mu m.
(2) 0.5 g of (Co) obtained in step (1) was added at room temperature50Ti50)25Gd75The alloy sheet was immersed in 300mL of a 0.2mol/L dilute hydrochloric acid aqueous solution to be reacted. In the reaction process, a matrix phase consisting of Gd reacts with dilute hydrochloric acid to enter a solution, and CoTi dendritic crystal particles which are difficult to react with the dilute hydrochloric acid gradually separate from the matrix and are dispersed. After 20min, separating the obtained CoTi dendritic crystal particles from the solution, and cleaning and drying to obtain micron-sized CoTi dendritic crystal powder, wherein the size range of the dendritic crystal particles is 5-40 mu m.
Scanning electron microscope tests are carried out on the alloy powder material, and as shown in fig. 1 and fig. 2, the alloy powder particles are dendritic.
As shown in FIG. 3, the CoTi powder material has almost no detectable other elements on the energy spectrum, and has a composition of about Co50Ti50。
Example 2:
the embodiment provides a preparation method of spherical micron-sized CoTi powder, which comprises the following steps:
(1) the formula of the selected formula is (Co)50Ti50)25Gd75The raw materials are weighed according to the formula and are 10-2Fully melting under Pa vacuum condition (Co)50Ti50)25Gd75An alloy melt was poured into a copper mold having a cavity cross-sectional size of 4mm × 6mm, and cast at a cooling rate of about 75K/s to prepare a (Co) alloy having a size of 4mm × 6mm × 30mm50Ti50)25Gd75The alloy thin plate has an alloy solidification structure comprising dispersed dendritic particles composed of CoTi and a matrix phase composed of Gd, wherein the size range of the CoTi dendritic particles is 2-40 mu m.
(2) 0.5 g of (Co) obtained in step (1) was added at room temperature50Ti50)25Gd75The alloy sheet was immersed in 300mL of a 0.2mol/L dilute hydrochloric acid aqueous solution to be reacted. In the reaction process, a matrix phase consisting of Gd reacts with dilute hydrochloric acid to enter a solution, and CoTi dendritic crystal particles which are difficult to react with the dilute hydrochloric acid gradually separate from the matrix and are dispersed. After 20min, separating the obtained CoTi dendritic crystal particles from the solution, and cleaning and drying to obtain micron-sized CoTi dendritic crystal powder, wherein the size range of the dendritic crystal particles is 2-40 mu m.
Collecting 0.5 kg of micron-sized CoTi dendritic crystal powder prepared in the step (2), and sieving the micron-sized CoTi dendritic crystal powder through screens of 540 meshes, 1000 meshes and 2000 meshes to obtain dendritic crystal with the grain size ranges of>26 μm, 26 μm to 13 μm, 13 μm to 6.5 μm and less than 6.5 μm. Respectively selecting CoTi dendrite powder with dendrite grain size range of 26-13 μm and 13-6.5 μm, and further preparing the spherical Co dendrite powder with grain size range of 26-13 μm and 13-6.5 μm by using mature plasma spheroidizing technology50Ti50And (3) pulverizing.
Example 3:
the embodiment provides a preparation method of nano-grade CoHf powder, which comprises the following steps:
(1) the formula of the selected formula is (Co)50Hf50)25Y75The raw materials are weighed according to the formula and are 10-2Fully melting under Pa vacuum condition (Co)50Hf50)25Y75Alloy, melt spinning the alloy melt at 105-106Cooling Rate of K/s preparation of (Co) with a thickness of 20-30 μm50Hf50)25Y75Alloy strip. The solidification structure of the alloy strip consists of near-spherical dispersed particles with the composition of CoHf and a matrix phase with the composition of Y, and the size range of the CoHf dispersed particles is 10-200 nm.
(2) 0.5 g of (Co) obtained in step (1) was added at room temperature50Hf50)25Y75The alloy strip was immersed in 300mL of a 0.2mol/L dilute aqueous sulfuric acid solution to carry out the reaction. In the reaction process, a matrix phase consisting of Y reacts with dilute sulfuric acid to enter a solution, and CoHf nano particles which are difficult to react with the dilute sulfuric acid gradually separate from the matrix and disperse. And after 5min, separating the obtained CoHf nano particles from the solution, and cleaning and drying to obtain the nano-scale near-spherical CoHf powder, wherein the size range of the particles is 10-200 nm.
Example 4:
the embodiment provides a preparation method of spherical micron-sized CoCrMo powder, which comprises the following steps:
(1) the formula of the selected formula is (Co)63Cr33Mo4)25Gd75The raw materials are weighed according to the formula and are 10-2Fully melting under Pa vacuum condition (Co)63Cr33Mo4)25Gd75An alloy melt was poured into a copper mold having a cavity cross-sectional size of 4mm × 6mm, and cast at a cooling rate of about 75K/s to prepare a (Co) alloy having a size of 4mm × 6mm × 30mm63Cr33Mo4)25Gd75The alloy sheet has an alloy solidification structure including dispersed dendritic crystal particles composed of Co-Cr-Mo and a matrix phase composed of Gd, and the size range of the Co-Cr-Mo dendritic crystal particles is 3-50 μm.
(2) 0.5 g of (Co) obtained in step (1) was added at room temperature63Cr33Mo4)25Gd75The alloy sheet was immersed in 300mL of a 0.2mol/L dilute hydrochloric acid aqueous solution to be reacted. During the reaction, a group consisting of GdThe bulk phase reacts with the dilute hydrochloric acid into solution, and the Co-Cr-Mo dendritic crystal particles which are difficult to react with the dilute hydrochloric acid gradually separate and disperse from the matrix. After 20min, separating the obtained Co-Cr-Mo dendritic crystal particles from the solution, cleaning and drying to obtain micron-sized Co-Cr-Mo dendritic crystal powder with the components of Co63Cr33Mo4The size range of the dendritic crystal particles is 3-50 mu m.
Collecting 0.5 kg of micron-sized Co-Cr-Mo dendritic crystal powder prepared in the step (2), and sieving the micron-sized Co-Cr-Mo dendritic crystal powder through screens of 540 meshes, 1000 meshes and 2000 meshes to obtain dendritic crystal with grain size ranges respectively>26 microns, 26 microns to 13 microns, 13 microns to 6.5 microns and less than 6.5 microns. Selecting Co-Cr-Mo dendrite powder with dendrite grain size range of 26-13 μm and 13-6.5 μm, and further preparing the spherical Co powder with grain size range of 26-13 μm and 13-6.5 μm by mature plasma spheroidizing technology63Cr33Mo4And (3) pulverizing.
Example 5:
the embodiment provides a preparation method of submicron CoTiHf powder, which comprises the following steps:
(1) the formula of the selected formula is (Co)50Ti25Hf25)20(Gd50Y50)80The raw materials are weighed according to the formula and are 10-2Fully melting under Pa vacuum condition (Co)50Ti25Hf25)20(Gd50Y50)80Alloy, melt spinning the alloy melt to 104Cooling Rate of K/s preparation of (Co) with a thickness of 200-50Ti25Hf25)20(Gd50Y50)80Alloy strip. The alloy strip has a solidification structure composed of Co50Ti25Hf25The near-spherical dispersion particles and the component are Gd50Y50And a matrix phase of Co50Ti25Hf25The size range of the dispersed particles is 100-800 nm.
(2) 0.5 g of (Co) obtained in step (1) was added at room temperature50Ti25Hf25)20(Gd50Y50)80The alloy sheet was immersed in 300mL of a 0.2mol/L dilute sulfuric acid aqueous solution and reacted. During the reaction, the matrix phase formed by GdY reacts with dilute sulfuric acid to form solution, and submicron Co which is difficult to react with dilute sulfuric acid50Ti25Hf25The particles gradually separate and disperse from the matrix. After 10min, the obtained Co50Ti25Hf25Separating the submicron particles from the solution, cleaning and drying to obtain the nearly spherical Co50Ti25Hf25The submicron alloy powder has the particle size range of 100-800 nm.
Example 6:
the embodiment provides a preparation method of micro-nano CoTiZr powder, which comprises the following steps:
(1) the formula of the selected formula is (Co)50Ti25Zr25)30Y70The raw materials are weighed according to the formula and are 10-2Arc melting under Pa vacuum condition to obtain (Co)50Ti25Zr25)30Y70The alloy is remelted by induction heating and then is melt spun by a copper roller to prepare (Co) with the thickness of about 150 mu m50Ti25Zr25)30Y70And (3) alloy thin strips. The alloy structure comprises a matrix consisting of Y and Co50Ti25Zr25) A nearly spherical dispersed particulate phase of composition. The dispersed particles have a diameter in the range of 50-500 nm.
(2) 0.5 g of (Co) obtained in step (1) was added at room temperature50Ti25Zr25)30Y70The alloy ribbon was immersed in 300mL of a 0.2mol/L hydrochloric acid aqueous solution and reacted. In the reaction process, the matrix consisting of the active element Y reacts with hydrochloric acid to enter the solution, but Co which is difficult to react with dilute hydrochloric acid50Ti25Zr25The dispersed particle phase gradually separates and disperses from the matrix phase. After 10min, the obtained Co50Ti25Zr25Separating dispersed particles from the solution, cleaning and drying to obtain the nearly spherical Co50Ti25Zr25Micro-nano alloy powderThe diameter of the particles is 50-500 nm.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The preparation method of the alloy powder material is characterized by comprising the following steps of:
providing (M)xTy)aREbThe alloy is characterized in that M is selected from at least one of Fe, Co and Ni, T is selected from at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf and Ti, RE is selected from at least one of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, x and Y and a and b respectively represent the atom percentage content of the corresponding components, x is more than or equal to 33% and less than or equal to 75%, and x + Y is more than or equal to 100%; a is more than or equal to 0.1 percent and less than or equal to 40 percent, a + b is 100 percent, and the (MxTy)aREbThe solidification structure of the alloy is formed by the composition MxTyThe dispersed particle phase consists of a matrix phase with the main component of RE;
will be (M)xTy)aREbMixing the alloy with an acid solution to enable the matrix phase to react with the acid solution to become ions which enter the solution, and separating out the dispersed particle phase to obtain the M-type metal oxidexTyThe alloy powder material.
2. The alloy powder according to claim 1A process for the preparation of a material, characterized in that (M) isxTy)aREbThe alloy is obtained by the following method:
weighing alloy raw materials according to a ratio;
fully melting the alloy raw materials to obtain an alloy melt;
preparing the (M) by a solidification method from an alloy meltxTy)aREbAn alloy, wherein the solidification rate of the alloy melt is 0.001K/s to 107K/s。
3. The method for preparing the alloy powder material according to claim 1, wherein the degree of vacuum in the alloy melt melting process is 1 x 10-4Pa～1.01325×105Pa。
4. The method according to claim 1, wherein the dispersed particulate phase has a particle shape including at least one of a dendrite shape, a spherical shape, a nearly spherical shape, a cube shape, a cake shape, and a rod shape, and a particle size of 2nm to 100 mm.
5. The method for preparing the alloy powder material according to claim 1, wherein the acid in the acid solution is at least one of sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, phosphoric acid, acetic acid, oxalic acid, formic acid, carbonic acid, gluconic acid, oleic acid and polyacrylic acid, and the solvent in the acid solution is water, ethanol, methanol or a mixture of the three in any proportion.
6. The method for preparing an alloy powder material according to claim 5, wherein the molar concentration of the acid in the acid solution is 0.001mol/L to 5 mol/L.
7. The method according to claim 1, wherein the (M) isxTy)aRbThe alloy is reacted with the acid solutionIn the corresponding steps, the reaction time is 0.1 min-48 h, and the reaction temperature is 0-100 ℃.
8. The method for preparing an alloy powder material according to claim 1, wherein M isxTyThe grain diameter of the alloy powder material is 2 nm-100 mm.
9. The method for preparing an alloy powder material according to any one of claims 1 to 8, wherein the step (M) is performed in the step (A)xTy)aRbThe step of reacting the alloy with the acid solution is further followed by the steps of: screening the obtained alloy powder material with the particle size range of 1 mu m-1 mm, and respectively carrying out plasma spheroidization treatment to finally obtain spherical alloy powder materials with different particle sizes.
10. The method for preparing an alloy powder material according to claim 9, wherein the spherical alloy powder material having different particle diameters has a particle size of 1 μm to 1 mm.
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| CN201910400790.5A CN111940750B (en) | 2019-05-15 | 2019-05-15 | Preparation method of alloy powder material |
| PCT/CN2020/089895 WO2020228709A1 (en) | 2019-05-15 | 2020-05-13 | Method for preparing alloy powder material |
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| WO2022100656A1 (en) * | 2019-11-28 | 2022-05-19 | 赵远云 | Method for preparing aluminum-containing alloy powder, application thereof and alloy strip |
| CN112143926B (en) * | 2019-11-28 | 2021-11-16 | 赵远云 | Preparation method and application of aluminum alloy-containing powder and alloy strip |
| CA3190201A1 (en) * | 2020-08-19 | 2022-02-24 | Li Liu | Method for preparing high-purity powder material, application thereof, and double-phase powder material |
| CN112276106A (en) * | 2020-08-27 | 2021-01-29 | 赵远云 | Preparation method and application of powder material containing precious metal elements |
| WO2023142251A1 (en) * | 2022-01-25 | 2023-08-03 | 赵远云 | Spherical iron alloy powder material, preparation method therefor, and application thereof |
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