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CN-116391051-B - Spherical iron alloy powder material and preparation method and application thereof

CN116391051BCN 116391051 BCN116391051 BCN 116391051BCN-116391051-B

Abstract

The invention relates to a spherical iron alloy powder material, a preparation method and application thereof. By selecting a main alloy system of Fe and La and adding special alloy spheroidizing precipitation and corrosion resistant elements, the dispersion precipitation of a spherical dispersion particle phase which is rich in Fe and is solid-dissolved with spheroidizing precipitation elements in an initial alloy melt in the alloy solidification process in a La-rich matrix phase is realized. By removing the La-rich matrix phase, a spherical iron alloy powder material with a particle diameter ranging from a nanometer scale to tens of micrometers is obtained. The method has simple process, can prepare spherical ferroalloy powder materials with different shapes including nanometer level, submicron level and micron level, and has good application prospect in the fields of powder metallurgy, metal Injection Molding (MIM), 3D printing, magnetic materials, heat-resistant materials, high-temperature alloys, coatings, electric heating materials, wave-absorbing materials, magnetic fluid and the like.

Inventors

  • ZHAO YUANYUN

Assignees

  • 赵远云

Dates

Publication Date
20260505
Application Date
20221031
Priority Date
20220125

Claims (19)

  1. 1. The preparation method of the spherical iron alloy powder material is characterized by comprising the following steps: Firstly, selecting initial alloy raw materials, and melting the initial alloy raw materials according to an initial alloy component proportion to obtain a uniform initial alloy melt, wherein the main component of the initial alloy melt is La x Fe y T z M a D b , T comprises at least one of Cr and V, M comprises at least one of Al, ni, co, si, D comprises at least one of Mo, W and Ti, x, y, z, a, b respectively represents the atomic percentage content of corresponding constituent elements, x is more than or equal to 18% and less than or equal to 95.8%, y is more than or equal to 4% and less than or equal to 81.8%, z is more than or equal to 0.1% and less than or equal to 35%, a is more than or equal to 0 and less than or equal to 40%, and b is more than or equal to 0 and less than or equal to 15%; Solidifying an initial alloy melt into an initial alloy solid through a rapid solidification technology, wherein a solidification structure of the initial alloy solid comprises a matrix phase and a dispersion particle phase, the melting point of the matrix phase is lower than that of the dispersion particle phase, the dispersion particle phase is coated in the matrix phase, the volume percentage of the matrix phase in the solidification structure is not lower than 40%, the average component of the matrix phase is mainly La x1 M a1 , the component of the dispersion particle phase is mainly Fe y2 T z2 M a2 D b2 La x2 , and x1, a1, x2, y2, z2, a2 and b2 respectively represent the atomic percentage content of corresponding constituent elements, and x1 is more than or equal to 45% and less than or equal to 100%, a1 is more than or equal to 55%, y2 is more than or equal to 50% and less than or equal to 98%, z2 is more than or equal to 0.2% and less than or equal to 50%, a2 is more than or equal to 30%, b2 is more than or equal to 0% and less than or equal to 35%, and x2 is more than or equal to 0% and 5%; The shape of the dispersed particle phase is mainly spherical or nearly spherical, the volume percentage of the spherical or nearly spherical dispersed particle phase in all the dispersed particle phases is more than 50 percent, protruding short dendrites grow on the partially spherical or nearly spherical dispersed particle phase, the whole spherical or nearly spherical dispersed particle phase has the shape characteristic similar to a coronavirus, and the particle size of the dispersed particle phase is 5 nm-50 mu m; Removing a matrix phase and mainly retaining a dispersion particle phase in the initial alloy solid to obtain an iron alloy powder material with a main component of Fe y2 T z2 M a2 D b2 La x2 , wherein y2 is more than or equal to 50% and less than or equal to 98%, z2 is more than or equal to 0.2% and less than or equal to 50%, a2 is more than or equal to 0% and less than or equal to 30%, b2 is more than or equal to 0% and less than or equal to 35%, and x2 is more than or equal to 0 and less than or equal to 5%; The shape of the iron alloy powder particles is mainly spherical or nearly spherical, the volume percentage of the spherical or nearly spherical iron alloy powder particles in all the iron alloy powder is more than 50%, protruding short dendrites grow on part of the spherical or nearly spherical iron alloy powder particles, the whole spherical or nearly spherical iron alloy powder particles have shape characteristics similar to a coronavirus, and the particle size of the iron alloy powder particles is 5 nm-50 mu m.
  2. 2. The method for producing a spherical iron alloy powder material according to claim 1, wherein the number of the convex short dendrites is one or more, and the length of the further convex from the spherical surface is less than half the radius of the spherical particle.
  3. 3. The method of producing a spherical iron alloy powder material according to claim 1, wherein the composition of the initial alloy melt in step one further includes a nonmetallic impurity element including at least one of O, N, H, P, S, cl, the nonmetallic impurity element is contained in the initial alloy melt in an atomic percentage of more than 0 and less than 10%, the nonmetallic impurity element is enriched in the La-rich matrix phase in the forming process of the dispersed particle phase in step two, so that the dispersed particle phase is subjected to a purification treatment, that is, the nonmetallic impurity element in the dispersed particle phase is contained in an atomic percentage of less than 1.5% in the initial alloy melt, and the nonmetallic impurity element in the spherical or near-spherical iron alloy powder particle in step three is also contained in an atomic percentage of less than 1.5% in the initial alloy melt.
  4. 4. A spherical iron alloy powder material, characterized by being prepared by the method for preparing a spherical iron alloy powder material according to any one of claims 1 to 3; The spherical iron alloy powder material is characterized by comprising main components of Fe y2 T z2 M a2 D b2 La x2 , wherein y2 is more than or equal to 50% and less than or equal to 98%, z2 is more than or equal to 0.2% and less than or equal to 50%, a2 is more than or equal to 0% and less than or equal to 30%, b2 is more than or equal to 0% and less than or equal to 35%, x2 is more than or equal to 0 and less than or equal to 5%; The shape of the iron alloy powder particles is mainly spherical or nearly spherical, the volume percentage of the spherical or nearly spherical iron alloy powder particles in all iron alloy powder is more than 50 percent, and protruding short dendrites grow on partial spherical or nearly spherical iron alloy powder particles, so that the whole spherical or nearly spherical iron alloy powder particles have shape characteristics similar to a coronavirus; The T comprises at least one of Cr and V, the M comprises at least one of Al, ni, co, si, the D comprises at least one of Mo, W and Ti, and x1, a1, x2, y2, z2, a2 and b2 respectively represent the atomic percentage content of corresponding constituent elements.
  5. 5. A preparation method of a spherical ferrochrome silicon powder material with high silicon content is characterized in that spherical ferroalloy powder material with main constituent elements of Fe-Cr or spherical ferroalloy powder material with main constituent elements of Fe-Cr-Si and low Si content prepared in the steps one to three of claim 1 is subjected to Si infiltration treatment, and then the spherical ferroalloy powder material with high Si content and main constituent elements of Fe-Cr-Si is obtained.
  6. 6. The preparation method of the spherical ferrochrome silicon powder material with high silicon content according to claim 5 is characterized by comprising the steps of preparing an initial alloy solid according to the step I and the step II of claim 1, wherein T comprises Cr, M comprises Si, 0<a-less than or equal to 40%, the average component of matrix phase is mainly La x1 Si a1 , the component of dispersed particle phase is mainly Fe y2 Cr z2 Si a2 D b2 La x2 with low Si content, si in the La x1 Si a1 matrix phase is combined with La in a mode of intermetallic compound, 0< a 2-less than or equal to 8%, la in the matrix phase of the initial alloy solid La x1 Si a1 is removed through dealloying reaction through dilute acid solution, meanwhile Si in the matrix phase of La x1 Si a1 is reserved, composite powder of nano porous Si and Fe y2 Cr z2 Si a2 D b2 La x2 particles with low Si content is obtained, the nano porous Si is used as Si source to carry out the treatment on Fe y2 Cr z2 Si a2 D b2 La x2 particles with low Si content, so as to obtain the spherical Fe-Cr-Si powder material with high Si content, the component composition is mainly Fe y3 Cr z3 Si a3 D b3 La x3 , wherein x3, y3, z3 b represents 0-0 < 2-less than or equal to 0.3-0 atom content of 0< 2-less than or equal to 0.3-0 atom < 2.
  7. 7. A high silicon content spherical ferrochrome silicon powder material, which is characterized by being prepared by the preparation method of the high silicon content spherical ferrochrome silicon powder material in claim 5.
  8. 8. The composite powder of nano porous Si and spherical Fe-Cr-Si particles is characterized in that the composite powder of nano porous Si and Fe y2 Cr z2 Si a2 D b2 La x2 particles with low Si content is prepared by the method of claim 6, and the composite powder of nano porous Si and spherical Fe-Cr-Si particles is obtained.
  9. 9. The preparation method of the iron-chromium-nickel powder metallurgical product with high nickel content is characterized by comprising the following steps of: Step 1, preparing the initial alloy solid according to the step I and the step II of claim 1, wherein T comprises Cr, M comprises Ni,0<a is less than or equal to 40%, the average component of the matrix phase is mainly La x1 Ni a1 , the component of the dispersed particle phase is mainly Fe y2 Cr z2 Ni a2 D b2 La x2 with low Ni content, ni in the La x1 Ni a1 matrix phase is combined with La in a mode of intermetallic compound, and 0< a2 is less than or equal to 12%; Step 2, removing La in the matrix phase of the initial alloy solid La x1 Ni a1 through dealloying reaction by a dilute acid solution, and simultaneously ensuring that most of Ni in the matrix phase of the original La x1 Ni a1 is not removed through reaction, so as to obtain composite powder of nano porous Ni and Fe y2 Cr z2 Ni a2 D b2 La x2 particles with low Ni content; And 3, pressing and forming the composite powder of the nano porous Ni and the Fe y2 Cr z2 Ni a2 D b2 La x2 particles with low Ni content, and performing heat treatment sintering to obtain the Fe-Cr-Ni powder metallurgical product with high Ni content, wherein the main component is Fe y3 Cr z3 Ni a3 D b3 La x3 , x3, y3, z3, a3 and b3 respectively represent the atomic percentage content of corresponding constituent elements, and 0< y3< y2,0< z3< z2,0< a2< a3, 0≤b3 < b2,0< x3< x2.
  10. 10. A high nickel content iron chromium nickel powder metallurgical product prepared by the method of preparing a high nickel content iron chromium nickel powder metallurgical product of claim 9.
  11. 11. A composite powder of nanoporous Ni and low Ni content iron chromium nickel particles, characterized in that it is prepared by step1 and step 2 of the method of claim 9.
  12. 12. The spherical ferroalloy powder material according to claim 4, which is used in any one of the following fields, including common powder metallurgy, metal Injection Molding (MIM), 3D printing, magnetic materials, heat-resistant materials, superalloys, paints, wave-absorbing materials.
  13. 13. The use of the spherical iron alloy powder material according to claim 4 in the field of electric heating materials, wherein the main component of the spherical iron alloy powder material comprises Fe-Cr-Al.
  14. 14. Use of the high silicon content spherical ferrochrome silicon powder material according to claim 7 in magnetic materials.
  15. 15. Use of the high nickel content iron chromium nickel powder metallurgical product according to claim 10 in superalloy.
  16. 16. The alloy solid is characterized by being prepared by the preparation method of the initial alloy solid in the first step and the second step of the claim 1, and is specifically characterized by comprising the following steps: The method comprises the steps of selecting initial alloy raw materials, and melting the initial alloy raw materials according to an initial alloy component proportion to obtain a uniform initial alloy melt, wherein the main component of the initial alloy melt is La x Fe y T z M a D b , T contains at least one of Cr and V, M contains at least one of Al, ni, co, si, D contains at least one of Mo, W and Ti, x, y, z, a, b respectively represents the atomic percentage content of corresponding constituent elements, x is more than or equal to 18% and less than or equal to 95.8%, y is more than or equal to 4% and less than or equal to 81.8%, z is more than or equal to 0.1% and less than or equal to 35%, a is more than or equal to 0 and less than or equal to 40%, and b is more than or equal to 0 and less than or equal to 15%; Solidifying an initial alloy melt into an initial alloy solid through a rapid solidification technology, wherein the solidification structure of the initial alloy solid comprises a matrix phase and a dispersed particle phase, the melting point of the matrix phase is lower than that of the dispersed particle phase, the dispersed particle phase is coated in the matrix phase, the volume percentage of the matrix phase in the solidification structure is not lower than 40%, the average component of the matrix phase is mainly La x1 M a1 , the component of the dispersed particle phase is mainly Fe y2 T z2 M a2 D b2 La x2 , wherein x1, a1, x2, y2, z2, a2 and b2 respectively represent the atomic percentage content of corresponding constituent elements, x1 is more than or equal to 45% and less than or equal to 100%, a1 is more than or equal to 0% and less than or equal to 55%, y2 is more than or equal to 0.2% and less than or equal to 98%, z2 is more than or equal to 0% and less than or equal to 30%, b2 is more than or equal to 0% and less than or equal to 35%, x2 and less than or equal to 5%; The shape of the dispersed particle phase is mainly spherical or nearly spherical, the volume percentage of the spherical or nearly spherical dispersed particle phase in all the dispersed particle phases is more than 50%, protruding short dendrites grow on the partially spherical or nearly spherical dispersed particle phase, the whole spherical or nearly spherical dispersed particle phase has shape characteristics similar to a coronavirus, and the particle size of the dispersed particle phase is 5 nm-50 mu m.
  17. 17. The use of the spherical ferroalloy powder material according to claim 4 in the field of magnetic fluid.
  18. 18. The application of the spherical ferroalloy powder material in the magnetic fluid field according to claim 17, which is characterized by comprising the following steps of uniformly mixing the spherical ferroalloy powder with a carrier liquid and a surfactant to obtain magnetic fluid, wherein the spherical ferroalloy powder material is characterized in that the main component of the spherical ferroalloy powder material is Fe y2 T z2 M a2 D b2 La x2 , wherein y2 is more than or equal to 50% and less than or equal to 98%, z2 is more than or equal to 0.2% and less than or equal to 50%, a2 is more than or equal to 0% and less than or equal to 30%, b2 is more than or equal to 0% and less than or equal to 35%, x2 is more than or equal to 5%, z2+ b2 is more than or equal to 1%, the shape of the ferroalloy powder particles is mainly spherical or approximately spherical, the volume percentage of the spherical or approximately spherical ferroalloy powder particles in all the ferroalloy powder is more than 50%, and convex short dendrites are grown on the spherical or approximately spherical ferroalloy powder particles, so that the whole spherical or approximately spherical ferroalloy powder particles have the characteristic of being similar to a coronal virus; the particle size of the ferroalloy powder particles is 5-100 nm, T comprises at least one of Cr and V, M comprises at least one of Al, ni, co, si, D comprises at least one of Mo, W and Ti, and x1, a1, x2, y2, z2, a2 and b2 respectively represent the atomic percentage content of corresponding constituent elements.
  19. 19. A coronavirus-like spherical iron alloy powder particle is characterized by comprising main components of Fe y2 T z2 M a2 D b2 La x2 , wherein y2 is more than or equal to 50% and less than or equal to 98%, z2 is more than or equal to 0.2% and less than or equal to 50%, a2 is more than or equal to 0% and less than or equal to 30%, b2 is more than or equal to 0% and less than or equal to 35%, x2 is more than or equal to 0%, T comprises at least one of Cr and V, M comprises at least one of Al, ni, co, si, D comprises at least one of Mo, W and Ti, la is rare earth La, la is mainly dissolved in the coronavirus-like spherical iron alloy particle with main components of Fe y2 T z2 M a2 D b2 La x2 , x1, a1, x2, y2, z2 and b2 respectively represent atomic percentage content of corresponding constituent elements, the coronavirus-like spherical iron alloy powder particle comprises a main body part and an attachment body part, wherein the attachment body part is a spherical or nearly spherical sphere, the attachment body part is a plurality of projections growing on the surface of the main body part in situ, the coronavirus-like spherical iron alloy particle has a diameter of more than 20nm, and the coronavirus-like spherical particle is more than or equal to 0.3M, and the diameter of the coronavirus-like spherical particle is more than 20M.

Description

Spherical iron alloy powder material and preparation method and application thereof Technical Field The invention relates to the technical field of metal powder materials, in particular to a spherical iron alloy powder material and a preparation method and application thereof. Background Fe alloys are the most widely used metallic materials. Fe alloy powder with micro-nano particle size is used as a raw material, and a large amount of Fe alloy materials with different performances can be prepared by additive manufacturing technologies such as powder metallurgy, metal Injection Molding (MIM), 3D printing and the like. Such as Fe-Cr ferrite stainless steel, fe-Cr-Ni austenite stainless steel, fe-Cr-Al electrothermal alloy, fe-Cr-Co permanent magnet, fe-Cr-Si soft magnetic material, etc. Spherical or nearly spherical Fe alloy particles are key raw materials in the application fields of powder metallurgy, powder coating, metal Injection Molding (MIM), 3D printing, magnetic materials and the like because of the advantages of excellent flowability, uniformity, powder stacking compactness and the like. In many cases, spherical or near-spherical particles must be used as a raw material to obtain the desired application effect of the final material. At present, spherical Fe alloy powder materials are mainly prepared by an atomization method, namely, liquid metal or alloy is directly crushed by high-speed fluid to obtain metal powder. However, due to the limitation of the atomizing capability limit of an atomization method, the method is generally only suitable for preparing spherical Fe alloy powder with the particle diameter of 10-150 mu m. For spherical Fe alloy powder materials below 10 μm, especially with particle sizes from nanometers to several micrometers (below 10 μm), the atomization process is difficult or impossible to produce. Therefore, the development of the preparation method of the superfine spherical iron alloy powder material with the granularity ranging from nanometer to several micrometers has important application significance. Disclosure of Invention Based on the above, it is necessary to provide a preparation method of spherical iron alloy powder material with simple process, low cost and easy operation, aiming at the technical problems. In order to solve the technical problems, the technical scheme of the invention comprises the following aspects: On the one hand, the preparation method of the spherical iron alloy powder material is characterized by comprising the following steps of: Firstly, selecting initial alloy raw materials, and melting the initial alloy raw materials according to an initial alloy component proportion to obtain a uniform initial alloy melt, wherein the main component of the initial alloy melt is La xFeyTzMaDb, T comprises at least one of Cr and V, M comprises at least one of Al, ni, co, si, D comprises at least one of Mo, W and Ti, x, y, z, a, b respectively represents the atomic percentage content of corresponding constituent elements, x is more than or equal to 18% and less than or equal to 95.8%, y is more than or equal to 4% and less than or equal to 81.8%, z is more than or equal to 0.1% and less than or equal to 35%, a is more than or equal to 0 and less than or equal to 40%, and b is more than or equal to 0 and less than or equal to 15%; The method comprises the steps of solidifying a primary alloy melt into a primary alloy solid through a rapid solidification technology, wherein a solidification structure of the primary alloy solid comprises a matrix phase and a dispersed particle phase, the melting point of the matrix phase is lower than that of the dispersed particle phase, the dispersed particle phase is coated in the matrix phase, the volume percentage of the matrix phase in the solidification structure is not lower than 40%, the average component of the matrix phase is mainly La x1Ma1, the component of the dispersed particle phase is mainly Fe y2Tz2Ma2Db2Lax2, x1, a1, x2, y2, z2, a2 and b2 respectively represent the atomic percentage content of corresponding constituent elements, x1 is not more than 100%, a1 is not more than 55%, y2 is not more than 50% and not more than 98%, z2 is not more than 50%, a2 is not more than 30%, b2 is not more than 35% and not more than 0 and not more than 2, the dispersed particle phase comprises spherical or nearly spherical particle phase with a certain content, and the dispersed particle size of the dispersed particle phase is not more than 5nm and has a certain dendritic particle size of 50-5 nm; Removing a matrix phase in the initial alloy solid and mainly retaining a dispersed particle phase to obtain an iron alloy powder material with a main component of Fe y2Tz2Ma2Db2Lax2, wherein y2 is more than or equal to 50% and less than or equal to 98%, z2 is more than or equal to 0.2% and less than or equal to 50%, a2 is more than or equal to 0% and less than or equal to 30%, b2 is more than or equal to 0% and less than or equal