WO2023142563A1 - 一种球形铁合金粉体材料及其制备方法与用途 - Google Patents

一种球形铁合金粉体材料及其制备方法与用途 Download PDF

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WO2023142563A1
WO2023142563A1 PCT/CN2022/128595 CN2022128595W WO2023142563A1 WO 2023142563 A1 WO2023142563 A1 WO 2023142563A1 CN 2022128595 W CN2022128595 W CN 2022128595W WO 2023142563 A1 WO2023142563 A1 WO 2023142563A1
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spherical
phase
particles
content
powder
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PCT/CN2022/128595
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赵远云
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赵远云
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C3/00—Removing material from alloys to produce alloys of different constitution separation of the constituents of alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C35/00—Master alloys for iron or steel

Definitions

  • the invention relates to the technical field of metal powder materials, in particular to a spherical ferroalloy powder material and its preparation method and application.
  • Fe alloys are the most widely used metal materials. Using Fe alloy powder with micro-nano particle size as raw material, a large number of Fe alloy materials with different properties can be prepared through additive manufacturing technologies such as powder metallurgy, metal injection molding (MIM), or 3D printing. Such as Fe-Cr ferritic stainless steel, Fe-Cr-Ni austenitic stainless steel, Fe-Cr-Al electric heating alloy, Fe-Cr-Co permanent magnet, Fe-Cr-Si soft magnetic material, etc.
  • MIM metal injection molding
  • Spherical or nearly spherical Fe alloy particles are the key to powder metallurgy, powder coating, metal injection molding (MIM), 3D printing, magnetic materials and other application fields because of their excellent fluidity, uniformity, and compactness of powder stacking. raw materials. In many cases, spherical or nearly spherical particles must be used as raw materials to obtain the desired application effect of the final material.
  • the spherical Fe alloy powder material is mainly prepared by the atomization method, that is, the metal powder is obtained by directly smashing the liquid metal or alloy with a high-speed fluid.
  • the technical solution of the present invention includes the following aspects:
  • a method for preparing a spherical iron alloy powder material comprises the following steps:
  • Step 1 selecting the initial alloy raw material, melting the initial alloy raw material according to the distribution ratio of the initial alloy composition to obtain a uniform initial alloy melt;
  • the main component of the initial alloy melt is La x Fe y T z M a D b , wherein T contains at least one of Cr and V, M contains at least one of Al, Ni, Co, and Si, D contains at least one of Mo, W, and Ti, and x, y, z, a, and b represent The atomic percentage content of the corresponding constituent elements, and 18% ⁇ x ⁇ 95.8%, 4% ⁇ y ⁇ 81.8%, 0.1% ⁇ z ⁇ 35%, 0 ⁇ a ⁇ 40%, 0 ⁇ b ⁇ 15%;
  • Step 2 solidifying the initial alloy melt into an initial alloy solid by rapid solidification technology;
  • the solidification structure of the initial alloy solid includes a matrix phase and a dispersed particle phase;
  • the melting point of the matrix phase is lower than the melting point of the dispersed particle phase,
  • the dispersed particle phase is coated in the matrix phase;
  • the volume percentage of the matrix phase in the solidified tissue is not less than 40%;
  • the average composition of the matrix phase is mainly La x1 M a1 ;
  • the composition of the phase is mainly Fe y2 T z2 M a2 D b2 La x2 , where x1, a1, x2, y2, z2, a2, b2 represent the atomic percentage content of the corresponding constituent elements, and 45% ⁇ x1 ⁇ 100%, 0% ⁇ a1 ⁇ 55%, 50% ⁇ y2 ⁇ 98%, 0.2% ⁇ z2 ⁇ 50%, 0% ⁇ a2 ⁇ 30%, 0% ⁇ b2 ⁇ 35%, 0 ⁇
  • Step 3 removing the matrix phase in the initial alloy solid and mainly retaining the dispersed particle phase to obtain an iron alloy powder material whose main component is Fe y2 T z2 M a2 D b2 La x2 ; wherein, 50% ⁇ y2 ⁇ 98% , 0.2% ⁇ z2 ⁇ 50%, 0% ⁇ a2 ⁇ 30%, 0% ⁇ b2 ⁇ 35%, 0 ⁇ x2 ⁇ 5%; the iron alloy powder particles include a considerable amount of spherical or nearly spherical particles, and The partially spherical or nearly spherical iron alloy powder particles contain certain dendrite characteristics; the particle size of the iron alloy powder particles is 5nm-50 ⁇ m.
  • T contains Cr; further, T contains V;
  • M contains Al; further, M contains Ni; further, M contains Co; further, M contains Si;
  • D contains Mo; further, D contains W; further, D contains Ti;
  • the volume percentage content is whether the dispersed particle phase can be dispersed key.
  • the volume percent content of the La matrix can be calculated as 44.35%.
  • y>z that is, the atomic percentage content of Fe in the initial alloy melt is higher than the atomic percentage content of T-type elements
  • the melting points of Fe, Cr, and V are all higher than that of La, and Fe, Cr, and V are all incompatible with La. Intermetallic compounds are formed, and there is no obvious solid solution, and Fe-Cr, Fe-V, and Cr-V are all infinite solid solution alloy systems.
  • the Fe, Cr, and V The dispersed particle phase is first precipitated from the alloy melt, and the matrix phase mainly composed of La is solidified last, and the alloy solidification structure does not contain intermetallic compounds composed of La, Fe, Cr, and V; that is, the initial alloy
  • the solidification structure of the initial alloy solid includes a matrix phase rich in La and a dispersed particle phase rich in Fe, Cr or (and) V, and the melting point of the matrix phase is lower than the required The melting point of the dispersed particle phase, the dispersed particle phase is coated in the matrix phase;
  • the solidification rate of the initial alloy melt is higher than 20K/s; preferably, the solidification rate of the initial alloy melt is higher than 50K/s; preferably, the solidification rate of the initial alloy melt is higher than 100K/s ; Preferably, the solidification rate of the initial alloy melt is higher than 250K/s; as a further preference, the solidification rate of the initial alloy melt is higher than 500K/s;
  • the shape of the initial alloy solid has at least one dimension less than 10 mm in the three-dimensional direction; preferably, the shape of the initial alloy solid has at least one dimension less than 5 mm in the three-dimensional direction; preferably, the initial The shape of the alloy solid has at least one dimension less than 2 mm in the three-dimensional direction; preferably, the shape of the initial alloy solid has at least one dimension less than 1 mm in the three-dimensional direction; preferably, the shape of the initial alloy solid is in the three-dimensional direction At least one dimension in the direction is less than 500 ⁇ m; preferably, the shape of the initial alloy solid has at least one dimension in the three-dimensional direction less than 100 ⁇ m;
  • the shape of the initial alloy solid includes at least one of strip, ribbon, flake, filament, and granular; preferably, the shape of the initial alloy solid includes strip, ribbon, and flake at least one of;
  • the solidification technology for the preparation of the initial alloy solid includes at least one of melt stripping, quick-setting flakes, casting, continuous casting, atomized pulverization, and melt drawing;
  • the initial alloy solid is strip-shaped, and the thickness of the strip is 5 ⁇ m to 5 mm;
  • volume percentage of the matrix phase in the solidified tissue is not lower than 45%; further, the volume percentage of the matrix phase in the solidified tissue is not lower than 50%;
  • the matrix phase is still mainly composed of La. .
  • La element exists in Fe y2 T z2 M a2 D b2 La x2 dispersed particle phase through solid solution;
  • T elements are enriched in Fe y2 T z2 M a2 D b2 La x2 dispersed particle phase;
  • y2>z2 that is, Fe y2 T z2 M a2 D b2 La x2
  • the atomic percentage content of Fe in the dispersed particle phase is higher than the atomic percentage content of T-type elements
  • T elements exist in Fe y2 T z2 M a2 D b2 La x2 dispersed particle phase through solid solution;
  • M elements are enriched in the La x1 M a1 matrix
  • M elements also have a certain content in the Fe y2 T z2 M a2 D b2 La x2 dispersed particle phase.
  • M elements exist in Fe y2 T z2 M a2 D b2 La x2 dispersed particle phase through solid solution;
  • the characteristics of the M-type elements are: during the solidification process of the initial alloy melt, the M-type elements are enriched in the La x1 M a1 matrix phase, and at the same time, the M-type elements are also concentrated in the Fe y2 T z2 M a2 D b2 La x2 dispersed particle phase. Solid solution has a considerable content.
  • the D elements are enriched in Fe y2 T z2 M a2 D b2 La x2 in the dispersed particle phase;
  • D elements exist in Fe y2 T z2 M a2 D b2 La x2 dispersed particle phase through solid solution;
  • phase diagram of Al-Fe and Si-Fe Al and Si have great solid solubility in iron, while Fe-Ni and Fe-Co are completely solid-soluble, so M-type elements can be solid-dissolved in the Fe-rich dispersed particle phase.
  • phase diagrams of Al-La, Ni-La, Co-La, and Si-La, Al, Ni, Co, and Si can all form La-rich intermetallic compounds with La.
  • the melting point of the La-rich intermetallic compound is lower than that of the Fe-rich dispersed particles, during the solidification process of the initial alloy melt, a certain amount of M-type elements are first dissolved in the Fe-rich dispersed particle phase, and the remaining M-type elements are combined with La combines to form a La-rich intermetallic compound matrix; if La is still abundant, the La x1 M a1 matrix phase includes the La-rich intermetallic compound formed by M-type elements and La, as well as the La-rich phase.
  • the selected D-type elements will be enriched in the Fe y2 T z2 M a2 D b2 La x2 dispersed particle phase during the solidification process of the initial alloy melt middle;
  • Nb, Ta, and V belong to the same group of elements, and neither Nb nor Ta forms an intermetallic compound with La, nor does it form a solid solution, but it is different from Mo, W, Ti, and V, because Nb, Ta are in Fe,
  • the solid solubility of Cr and V is extremely low, and they can only form intermetallic compounds with each other; therefore, if Nb and Ta are contained in the initial alloy melt, Nb and Ta will form in Fe y2 T z2 M a2 D b2 La x2
  • the solid solubility in the dispersed particle phase is very low, and only a very small amount can exist or not exist.
  • Nb and Ta may exist in Fe y2 T z2 M a2 D b2 La x2 dispersed particle phase in a very small amount, and it will also form Nb, Ta and Fe, Cr , V dendritic intermetallic compound phase, see Comparative Example 4. None of these intermetallic compounds is the iron alloy phase that is mainly solid solution alloyed in this application.
  • the initial alloy melt contains only La and Fe
  • the solidification rate of the alloy melt is higher than 10 6 K/s
  • a certain amount of nano-scale (below 90nm) dendrite growth insufficient subspherical Fe phase particles can be obtained .
  • the Fe phase particles have a strong dendrite tendency, due to the lack of time to grow, the nearly spherical Fe phase particles with insufficient dendrite growth solidify and precipitate at the nanometer scale.
  • both La and Fe are easily oxidized, they are also very easy to react and dissolve with acid solutions.
  • the dispersed particle phase is a dendritic phase with a large particle size that is sufficient to grow, and after the matrix phase is removed, the obtained dendritic Fe phase Dendrites are intertwined dendritic fibers, see Comparative Example 1.
  • the initial alloy melt contains La and Fe, as well as Cr, V, Mo, W, and Ti elements with high melting points, especially Cr or (and) V, a T-type element that can form a complete solid solution with Fe
  • the initial alloy During the solidification process of the melt, the primary crystal grains that are rich in Fe and solid-dissolved with T elements are first precipitated. Due to the special solid solution of T-type elements, the formation law of the original crystal lattice is destroyed, and the growth of the Fe-rich dendrite phase along the specific crystal plane orientation is hindered, so that the primary grains of Fe-rich and T-type elements are solid-dissolved There is a tendency to spheroidize.
  • the T element is the key to the spheroidization of the Fe-rich primary crystal particles found in the present invention, especially when the Fe-rich dispersed particle size is large.
  • the T-type elements include at least one of the corrosion-resistant Cr and V elements, and the solid solution formed by these elements and Fe is stainless steel (the corrosion resistance of V is even higher than that of Cr). Therefore, the solid solution of T elements greatly improves the corrosion resistance of the Fe-rich dispersed particle phase. Since the matrix phase is mainly composed of highly corrodible La, the matrix phase can be easily corroded by reaction with a certain concentration of acid solution, thereby obtaining dispersed Fe-rich phase dispersed particles. In the case that the corrosion resistance of Fe-rich phase dispersed particles is obviously enhanced, a cooling rate greater than 10 6 K/s can be used to prepare the initial alloy solid of nano-iron-rich spherical particle phase containing T and D elements. , The high corrosion resistance of the nano-iron-rich spherical particle phase of D-type elements is separated from the La-rich matrix by acid reaction to obtain nano-scale iron-rich spherical particles.
  • the M-type elements include at least one of Al, Ni, Co, and Si, all of which are key elements of commercial ferroalloys.
  • Al is one of the key elements of Fe-Cr-Al electrothermal alloy and thermal spray coating
  • Ni is one of the key elements of austenitic stainless steel Fe-Cr-Ni
  • Co is the key element of Fe-Cr-Co permanent magnet
  • Si is one of the key elements of Fe-Cr-Si soft magnetic materials.
  • the atomic percentage solid solution of Ni in the Fe-rich phase dispersed particles is generally no more than 12%; Al and Co all have considerable solid solution in the Fe-rich phase dispersed particles (see Example ), the atomic percentage solid solution can even exceed 20%; and most of the above-mentioned commercial ferroalloys do not have a high requirement for the content of M-type elements, which makes it possible to prepare commercial ferroalloy powders that meet the above-mentioned relevant components.
  • M-type elements When the initial alloy melt contains M-type elements, some M-type elements also exist in Fe-rich phase dispersed particles through solid solution, so M-type elements generally have a positive effect on the spheroidization of Fe-rich phase dispersed particles, see Examples 13 and Example 14. Moreover, M-type elements and La are relatively easy to react with acid solution, so the M-type elements and La in the matrix phase can be removed by acid corrosion reaction to obtain freely dispersed dispersed particles of Fe-rich phase. If the chemical activity difference between La and M elements is poor, and only La in the matrix phase is mainly removed through a suitable acid solution according to the principle of dealloying, a composite powder of freely dispersed Fe-rich phase dispersed particle powder and nanoporous M can be obtained. .
  • D-type elements include Mo, W, and Ti elements with high melting points. Although these elements do not have high solid solubility in Fe in T-type elements (T-type elements are completely solid-soluble in Fe), D-type elements have 10 in Fe. %-20% solid solubility, and completely solid solution in T elements. Therefore, the appropriate addition of Mo, W, and Ti elements with high melting points in the initial alloy melt can not only enhance the sphericity and corrosion resistance of Fe-rich phase dispersed particles, but also significantly improve the melting point and corrosion resistance of Fe-rich phase dispersed particles. heat resistance. Such as the role of Ti in the commercial austenitic stainless steel 1Cr18Ni9Ti, and the role of Mo in the commercial ultra-high temperature resistant Fe-Cr-Al-Mo electrothermal alloy.
  • the types of the T-type elements, M-type elements, and D-type elements are the results of careful design and selection. Through this selection, it is ensured that during the solidification process of the initial alloy melt, Fe, T-type elements, and D-type elements mainly exist in the Fe y2 T z2 M a2 D b2 La x2 dispersed particle phase, and the M-type elements partially exist in the Fe y2 T z2 M a2 D b2 La x2 in the dispersed particle phase; La and M elements mainly exist in the La x1 M a1 matrix phase.
  • M elements also have a considerable amount of solid solubility, and La has a relatively low solid solubility.
  • This ingenious design ensures the spheroidization tendency of the dispersed particles through the T-type elements, and at the same time improves its corrosion resistance, which is conducive to the separation of the dispersed particle phase and the matrix phase through corrosion reactions.
  • the spheroidization of the Fe-rich dispersed particle phase is achieved by inhibiting the formation and growth of the Fe-rich dendrite phase through the solid solution alloying of special elements and the regulation of the melt cooling rate.
  • the volume percentage of spherical or near-spherical dispersed granular phase in all dispersed granular phases can be infinitely close to 100%, but cannot reach 100%.
  • the sphericity (sphericity) of the spherical or nearly spherical dispersed particle phase exceeds 50%;
  • the sphericity of the spherical or nearly spherical dispersed particle phase exceeds 70%
  • the sphericity of the spherical or nearly spherical dispersed particle phase exceeds 85%;
  • the sphericity of the spherical or nearly spherical dispersed particle phase exceeds 95%
  • volume percentage of the spherical or nearly spherical dispersed granular phase in all the dispersed granular phases is greater than 10%;
  • the pure La-Fe alloy can hardly obtain spherical dispersed particle phase by the method; or it needs to pass a very high cooling rate to obtain sub-spherical Fe phase particles below 90nm, and it is also difficult to react with the La matrix to obtain such particles by acid reaction. Nanoparticles (nano-Fe particles will also react with acid and be dissolved). Therefore, through alloy design, after adding corrosion-resistant elements Cr or (and) V, or adding more D-type elements at the same time, if the volume percentage of spherical or nearly spherical dispersed particle phase in all dispersed particle phases is greater than 10%, it can be considered that a considerable amount of spherical or nearly spherical dispersed particle phase has been obtained;
  • volume percentage of the spherical or nearly spherical dispersed granular phase in all the dispersed granular phases is greater than 25%;
  • the shape of the dispersed particle phase is mainly spherical or nearly spherical;
  • volume percentage of the spherical or nearly spherical dispersed granular phase in all the dispersed granular phases is greater than 50%;
  • volume percentage of the spherical or nearly spherical dispersed granular phase in all the dispersed granular phases is greater than 75%
  • volume percentage of the spherical or nearly spherical dispersed granular phase in all the dispersed granular phases is greater than 90%;
  • volume percentage of the spherical or nearly spherical dispersed granular phase in all the dispersed granular phases is greater than 95%
  • the spherical Or the volume percentage of the nearly spherical dispersed granular phase in all the dispersed granular phases is greater than 50%;
  • the spherical Or the volume percentage of the nearly spherical dispersed granular phase in all the dispersed granular phases is greater than 50%;
  • the spherical Or the volume percentage of the nearly spherical dispersed granular phase in all the dispersed granular phases is greater than 50%;
  • the spherical Or the volume percentage of the nearly spherical dispersed granular phase in all the dispersed granular phases is greater than 50%;
  • the spherical Or the volume percentage of the nearly spherical dispersed granular phase in all the dispersed granular phases is greater than 95%;
  • the dispersed particle phase with a sphericity of more than 85% can still be obtained by adjusting the cooling rate and alloy composition;
  • the dispersed particle phase with a sphericity of more than 85% can still be obtained by adjusting the cooling rate and alloy composition;
  • the dispersed particle phase with a sphericity of more than 85% can still be obtained by adjusting the cooling rate and alloy composition;
  • the dispersed particle phase with a sphericity of more than 85% can still be obtained by adjusting the cooling rate and alloy composition;
  • the partially spherical or nearly spherical dispersed particle phase contains certain dendrite characteristics, which means that short convex dendrites grow on the partially spherical or nearly spherical dispersed particle phase, which makes the entire spherical or nearly spherical dispersed particle phase Has a shape characteristic similar to the "coronavirus" virus (the raised short dendrites growing on the spherical or nearly spherical dispersed particle phase correspond to the crown protrusions on the "coronavirus” virus sphere);
  • the number of protruding short dendrites is one or more, and the length of further protruding from the spherical surface is lower than the radius of spherical particles; see the examples for specific shapes;
  • the number of protruding short dendrites is one or more, and the length of further protruding from the spherical surface is less than half of the radius of the spherical particle;
  • the spherical granular phase itself is very high due to the high sphericity of the spherical granular phase that the short
  • the crystals are relatively short, and generally distributed symmetrically and evenly on the surface of the particles. Therefore, even if the partially spherical or nearly spherical dispersed particle phase contains the characteristics of short convex dendrites with insufficient spheroidization, the particles still belong to a spherical shape with a high degree of sphericity. Or nearly spherical particles, which belong to the statistical category of spherical or nearly spherical particles.
  • the shape of the dispersed granular phase is mainly spherical or nearly spherical; in addition, the dispersed granular phase also contains a small amount of typical dendrite granular phase.
  • the dendrite particles have a typical dendrite morphology, do not look spherical, and do not belong to the statistical category of spherical or near-spherical particles.
  • the shape of the dispersed particle phase is mainly spherical or nearly spherical, and the partially spherical or nearly spherical dispersed particle phase contains certain dendrite characteristics; meanwhile, the dispersed particle phase also contains a small amount of typical dendrite particle phase.
  • the presence of these two dendritic features is a unique feature possessed by the iron-rich dispersed granular phase obtained through the present application.
  • the length of the protruding short dendrite from the spherical surface is less than one-third of the radius of the spherical particle
  • the length of the raised short dendrites from the spherical surface is less than one-fifth of the radius of the spherical particle
  • the particle size of the dispersed particle phase is 5 nm to 40 ⁇ m;
  • the particle size of the dispersed particle phase is 5 nm to 30 ⁇ m; further, the particle size of the dispersed particle phase is 5 nm to 20 ⁇ m; further, the particle size of the dispersed particle phase is 5 nm to 10 ⁇ m ;
  • the particle size of the dispersed particle phase is 100nm-50 ⁇ m;
  • the particle size of the dispersed particle phase is 250nm-50 ⁇ m;
  • the particle size of the dispersed particle phase is 500nm-50 ⁇ m;
  • the particle size of the dispersed particle phase is 5 nm to 100 nm;
  • the particle size of the dispersed particle phase is 5 nm to 50 nm;
  • the size of the dispersed particle phase is negatively correlated with the solidification rate of the initial alloy melt, that is, the higher the solidification rate, the smaller the particle size of the dispersed particle phase. Therefore, when the particle size of the dispersed particle phase is smaller, the initial alloy melt. The higher the solidification rate, the higher the spheroidization rate of the corresponding dispersed particle phase, and the higher the volume percentage of the spherical or nearly spherical dispersed particle phase in all the dispersed particle phases;
  • the number of single crystal particles in the dispersed particle phase accounts for no less than 60% of the total number of particles.
  • the iron alloy powder material whose main component is Fe y2 T z2 M a2 D b2 La x2 is obtained by removing the matrix phase in the initial alloy solid and retaining the dispersed particle phase, the iron alloy
  • the characteristics of the powder material are the corresponding characteristics of the dispersed particles described in step 2, and these characteristics are described in step 2 for details.
  • the method for removing the matrix phase and retaining the dispersed particle phase includes at least one of acid solution dissolution reaction removal, matrix oxidation-powdering removal.
  • the selection criterion is to ensure that the matrix whose average composition is mainly La x1 M a1 changes into ions and enters the solution, and the main composition is Fe y2 T z2 M a2 D
  • the dispersed particle phase of b2 La x2 hardly reacts with the corresponding acid, so as to realize the removal of the matrix phase, and obtain the ferroalloy powder material whose main component is Fe y2 T z2 M a2 D b2 La x2 ; or select the appropriate acid type and concentration
  • the selection criterion is to ensure that the matrix phase change nanoporous M with the average composition mainly La x1 M a1 (mainly corrodes La), while the dispersed particle phase with the main composition Fe y2 T z2 M a2 D b2 La x2 is almost incompatible with Corresponding acid reaction to obtain composite powder of nanoporous M and Fe y2 T z2
  • Fe contains Cr and V in solid solution, it is a ferritic stainless steel component, and the dispersed particle phase whose main component is Fe y2 T z2 M a2 D b2 La x2 has good acid corrosion resistance, while La, M Nitrogenous elements are elements that are very easy to react with acid solution, so the La-rich matrix phase can be removed very easily to obtain a ferroalloy powder material whose main component is Fe y2 T z2 M a2 D b2 La x2 .
  • the La-rich matrix phase in the initial alloy solid can also be removed by dry method.
  • the Fe-rich dispersed particle phase will automatically fall out, and the Fe-rich powder particles can be collected by a magnetic field through its magnetic characteristics to realize its separation from the La-rich matrix phase.
  • the oxidation-powdering process of the solid La-rich matrix phase of the initial alloy is accelerated under the condition of heat treatment; the La-rich matrix phase is rapidly oxidized-powdered by heating through heat treatment, thereby improving the separation efficiency. Due to the addition of Cr, V and other elements, the oxidation resistance of the Fe-rich particle phase is enhanced, and the heating temperature is well controlled to avoid oxidation of the Fe-rich particles.
  • the heat treatment temperature is 50°C to 1000°C; preferably, the heat treatment temperature is 50°C to 600°C; preferably, the heat treatment temperature is 50°C to 200°C;
  • the volume percentage of spherical or nearly spherical iron alloy powder particles in all iron alloy powder particles can be infinitely close to 100%, but cannot reach 100%. That is to say, the shape of the iron alloy powder particles is mainly spherical or nearly spherical, and the partially spherical or nearly spherical iron alloy powder particles contain dendrite characteristics of insufficient spheroidization;
  • the sphericity (sphericity) of the spherical or nearly spherical iron alloy powder particles exceeds 50%;
  • the sphericity of the spherical or nearly spherical iron alloy powder particles exceeds 70%
  • the sphericity of the spherical or nearly spherical iron alloy powder particles exceeds 85%;
  • the sphericity of the spherical or nearly spherical iron alloy powder particles exceeds 95%
  • volume percentage of spherical or nearly spherical ferroalloy powder particles in all ferroalloy powders is greater than 10%
  • volume percentage of spherical or nearly spherical ferroalloy powder particles in all ferroalloy powders is greater than 25%;
  • the shape of the iron alloy powder particles is mainly spherical or nearly spherical;
  • volume percentage of spherical or nearly spherical ferroalloy powder particles in all ferroalloy powders is greater than 50%;
  • volume percentage of spherical or nearly spherical ferroalloy powder particles in all ferroalloy powders is greater than 75%
  • volume percentage of spherical or nearly spherical ferroalloy powder particles in all ferroalloy powders is greater than 90%
  • volume percentage of spherical or nearly spherical ferroalloy powder particles in all ferroalloy powders is greater than 95%
  • the content of solid-dissolved T-type elements in the iron alloy powder particles exceeds 4%, or the total content of solid-dissolved elements including T-type elements exceeds 8%, and the cooling rate of the melt exceeds 250K/s, spherical or The volume percentage of nearly spherical iron alloy powder particles in all iron alloy powder particles is greater than 50%;
  • the content of solid-dissolved T-type elements in the iron alloy powder particles exceeds 8%, or the total content of solid-dissolved elements including T-type elements exceeds 12%, and the cooling rate of the melt exceeds 100K/s, spherical or The volume percentage of nearly spherical iron alloy powder particles in all iron alloy powder particles is greater than 50%;
  • the content of solid-dissolved T-type elements in the iron alloy powder particles exceeds 12%, or the total content of solid-dissolved elements including T-type elements exceeds 18%, and the cooling rate of the melt exceeds 50K/s, spherical or The volume percentage of nearly spherical iron alloy powder particles in all iron alloy powder particles is greater than 50%;
  • the content of solid-dissolved T-type elements in the iron alloy powder particles exceeds 16%, or the total content of solid-dissolved elements including T-type elements exceeds 25%, and the cooling rate of the melt exceeds 20K/s, spherical or The volume percentage of nearly spherical iron alloy powder particles in all iron alloy powder particles is greater than 50%;
  • the content of solid-dissolved T-type elements in the iron alloy powder particles exceeds 16%, or the total content of solid-dissolved elements including T-type elements exceeds 25%, and the cooling rate of the melt exceeds 100K/s, spherical or The volume percentage of nearly spherical iron alloy powder particles in all iron alloy powder particles is greater than 95%;
  • the partially spherical or nearly spherical iron alloy powder particles contain certain dendrite characteristics, which means that short convex dendrites grow on the partially spherical or nearly spherical iron alloy powder particles, which makes the entire spherical or nearly spherical iron alloy powder
  • the powder particles have a shape characteristic similar to the "coronavirus" virus (the raised short dendrites growing on the spherical or nearly spherical iron alloy powder particles correspond to the crown protrusions on the "coronavirus" virus ball);
  • the specific shape of the short dendrites is shown in the examples; although the insufficient spheroidized raised short dendrites have a certain influence on the sphericity of the ferroalloy powder particles, but due to the raised short dendrites attached to the grown ferroalloy powder particles The sphericity itself is very high.
  • the shape of the iron alloy powder particles is mainly spherical or nearly spherical; in addition, the iron alloy powder particles also contain a small amount of typical dendritic powder particles.
  • the shape of the ferroalloy powder particles is mainly spherical or nearly spherical, and the partially spherical or nearly spherical ferroalloy powder particles contain certain dendrite characteristics; meanwhile, the ferroalloy powder particles also contain a small amount of typical dendrite particles.
  • the presence of these two dendritic features is a unique feature possessed by the ferroalloy powder particles obtained through the present application.
  • the particle size of the iron alloy powder particles is 5 nm to 40 ⁇ m; further, the particle size of the iron alloy powder particles is 5 nm to 30 ⁇ m; further, the particle size of the iron alloy powder particles is 5nm-20 ⁇ m; further, the particle size of the iron alloy powder particles is 5nm-10 ⁇ m;
  • the particle size of the iron alloy powder particles is 100nm-50 ⁇ m;
  • the particle size of the iron alloy powder particles is 250nm-50 ⁇ m;
  • the particle size of the iron alloy powder particles is 500nm-50 ⁇ m;
  • the particle size of the iron alloy powder particles is 5nm-100nm;
  • the particle size of the iron alloy powder particles is 5nm-50nm;
  • the shape of the powder particles is still mainly spherical;
  • the shape of the powder particles is still mainly spherical;
  • the shape of the powder particles is still mainly spherical;
  • the shape of the powder particles is still mainly spherical;
  • the number of single crystal particles in the iron alloy powder particles accounts for no less than 60% of the total number of particles.
  • La is a special case, and among all iron series elements Fe, Co, and Ni, Fe is also a special case, because among the various combinations of iron series elements and rare earth elements, only La-Fe alloy does not form intermetallic Compounds, the two elements are not obviously solid solution with each other; the utilization of this feature is the basis for the formation of La-rich matrix phase and Fe-rich dispersed particle phase in the solidification structure of the initial alloy solid in the present invention.
  • T-type elements, M-type elements, and D-type elements the original dendritic particle phase changes and grows into a spherical or near-spherical particle phase during the solidification process of the initial alloy melt.
  • the key to the invention of this application is to obtain ultrafine spherical iron alloy powders whose composition is generally similar to that of commercial alloys, but whose particle size can be significantly different (such as smaller particle size, lower oxygen impurities, and solid-dissolved rare earth elements). If there is no selection and content control of T-type elements, M-type elements, and D-type elements, and the spheroidization of T-type elements is discovered and utilized, simply through La-Fe alloys, only dendrite-like corrosion-prone materials can be obtained. Fe dendritic powder has no particle fluidity, and the compactness of powder metallurgy is also low, so the application value is greatly limited.
  • the La raw material may also contain a small amount of other rare earth elements, as long as the atomic percentage content of other rare earth elements does not exceed 25% of the La raw material content, it will have little effect on the law.
  • These other rare earths are solid-dissolved in La, replacing part of the role of La.
  • the meaning of La in the present invention represents La rare earth and other rare earths.
  • the composition of the initial alloy melt in step one also includes non-metallic impurity elements, and the non-metallic impurity elements include at least one of O, N, H, P, S, Cl; the non-metallic impurity elements
  • the atomic percentage content in the initial alloy melt is greater than 0 and less than 10%; during the formation of the Fe-rich dispersed particle phase described in step 2, the non-metallic impurity elements are enriched in the La-rich matrix phase, thereby to the rich
  • the Fe dispersed granular phase has been purified, that is, the atomic percentage content of the non-metallic impurity element in the Fe-rich dispersed granular phase is lower than the atomic percentage content of the non-metallic impurity element in the initial alloy melt; and the Fe-rich dispersed In the particle phase, the atomic percent content of non-metallic impurity elements is lower than 1.5%; and the content of non-metallic impurity elements in the spherical or nearly spherical iron alloy powder particles
  • the present invention also relates to a spherical iron alloy powder material, which is characterized in that it is prepared by the preparation method of the spherical iron alloy powder material described in the first aspect, and its features are detailed in the first aspect;
  • the spherical iron alloy powder material include: the main component of the spherical iron alloy powder material is Fe y2 T z2 M a2 D b2 La x2 ; wherein, 50% ⁇ y2 ⁇ 98%, 0.2% ⁇ z2 ⁇ 50%, 0% ⁇ a2 ⁇ 30%, 0% ⁇ b2 ⁇ 35%, 0 ⁇ x2 ⁇ 5%; the shape of the ferroalloy powder particles is mainly spherical or nearly spherical, and some spherical or nearly spherical ferroalloy powder particles contain certain Dendrite characteristics; the particle size of the ferroalloy powder particles is 5nm-50 ⁇ m.
  • the sphericity of the spherical or nearly spherical iron alloy powder particles exceeds 65%;
  • volume percentage of the spherical or nearly spherical iron alloy powder particles in all iron alloy powders is greater than 25%;
  • the total atomic percent content of O, N, H, P, S, and Cl elements is less than 1.5%.
  • the T includes at least one of Cr and V
  • M includes at least one of Al, Ni, Co, and Si
  • D includes at least one of Mo, W, and Ti
  • x1, a1, x2, y2, z2, a2, and b2 respectively represent the atomic percentage content of the corresponding constituent elements.
  • the present invention also relates to a method for preparing a spherical iron-chromium-silicon powder material with high silicon content, which is characterized in that the spherical iron alloy powder whose main component element is Fe-Cr prepared in steps 1 to 3 on the one hand
  • the material or the spherical iron alloy powder material whose main component element is Fe-Cr-Si with low Si content is subjected to Si infiltration treatment, that is, the spherical powder material with high Si content whose main component is Fe-Cr-Si is obtained.
  • the solid solubility of Si atomic percentage in the Fe-Cr-Si spherical iron alloy powder material obtained directly through steps 1 to 3 on the one hand is difficult to exceed 8%, and it can only be realized when a large amount of Si is contained in the initial alloy melt, However, the atomic percentage of Si in the actual commercial Fe-Cr-Si magnetic ferroalloy powder generally exceeds 8%.
  • the spherical iron alloy powder material whose main constituent element is Fe-Cr or the spherical iron alloy whose main constituent element is Fe-Cr-Si with low Si content can be prepared by step 1 to step 3 on the one hand. The powder material is subjected to Si infiltration treatment to obtain spherical Fe-Cr-Si powder material with high Si content.
  • the Si infiltration treatment includes at least one of solid Si infiltration, liquid Si infiltration and gas infiltration.
  • the silicon source for solid silicon infiltration includes at least one of Si or silicon-rich alloy;
  • the silicon source for liquid silicon infiltration is mainly a liquid containing Si;
  • the silicon source for gas infiltration silicon is mainly a gas containing Si;
  • the treatment temperature of solid siliconizing is 400°C-1200°C.
  • the present invention also provides an improved process for siliconizing:
  • step 1 and step 2 on the one hand prepare the initial alloy solid described in step 2 on the one hand; wherein, T contains Cr, M contains Si, 0 ⁇ a ⁇ 40%; the average composition of the matrix phase Mainly La x1 Si a1 ; the 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 through intermetallic compounds ; 0 ⁇ a2 ⁇ 8%; La in the initial alloy solid La x1 Si a1 matrix phase is removed by a dealloying reaction through a dilute acid solution, while retaining Si in the original La x1 Si a1 matrix phase to obtain nanoporous Composite powder of Si and Fe y2 Cr z2 Si a2 D b2 La x2 particles with low Si content; the nanoporous Si can be used as Si source for Fe y2 Cr z2 Si a2 D b2 La x2 powder for
  • the nanoporous Si is used as a Si source to perform Si infiltration treatment on the Fe y2 Cr z2 Si a2 D b2 La x2 particles with a low Si content, that is, to obtain a spherical Fe-Cr-Si powder material with a high Si content;
  • the method of solid Si infiltration of nanoporous Si and the Fe y2 Cr z2 Si a2 D b2 La x2 particles with low Si content includes: directly performing solid Si infiltration, or first compacting it and then performing solid Si infiltration operation ;
  • treatment temperature of solid Si infiltration is 400°C to 1200°C;
  • the composition of the obtained spherical Fe-Cr-Si powder material with high Si content is mainly Fe y3 Cr z3 Si a3 D b3 La x3 ; where x3, y3, z3, a3, b3 respectively represent the corresponding constituent elements Atomic percentage content, and 0 ⁇ y3 ⁇ y2, 0 ⁇ z3 ⁇ z2, 0 ⁇ a2 ⁇ a3, 0 ⁇ b3 ⁇ b2, 0 ⁇ x3 ⁇ x2.
  • the spherical Fe-Cr-Si powder material with high Si content except that the Si content is increased through siliconizing treatment, and the alloy composition is automatically adjusted accordingly, the shape and size of the powder material still basically remain the same as It is basically the same before siliconizing treatment.
  • the spherical Fe-Cr-Si powder material with high Si content after the siliconizing treatment can be re-pulverized into loose particles by means of dispersion and crushing techniques. Even though the surface of spherical Fe-Cr-Si powders with high Si content may have remaining nanoporous Si not fully infiltrated, it is sometimes beneficial.
  • spherical Fe-Cr-Si powder particles with high Si content for example, separate powders above 10 ⁇ m, powders from 1 ⁇ m to 5 ⁇ m, powders from 5 ⁇ m to 10 ⁇ m, powders below 1 ⁇ m, etc., to obtain different particle sizes
  • the high Si content spherical Fe-Cr-Si powder material can be used in different fields.
  • the present invention also relates to a high-silicon content spherical iron-chromium-silicon powder material, which is characterized in that it is prepared by the preparation method of the high-silicon content spherical iron-chromium-silicon powder material described in the three aspects, and its specific features See its three aspects.
  • the present invention also relates to a composite powder of nanoporous Si and spherical Fe-Cr-Si particles, which is characterized in that nanoporous Si and Fe y2 Cr with low Si content are prepared through its three-sided siliconization improvement process
  • the composite powder of z2 Si a2 D b2 La x2 particles that is, the composite powder of nanoporous Si and spherical Fe-Cr-Si particles; its characteristics can be seen in the description of the improvement process of silicon infiltration in three aspects.
  • the present invention also relates to a method for preparing an iron-chromium-nickel powder metallurgy product with high nickel content, which is characterized in that it includes the following steps:
  • Step 1 prepare the initial alloy solid described in step 2 in one aspect; wherein, T contains Cr, M contains Ni, 0 ⁇ a ⁇ 40%; the average of the matrix phase
  • the composition is mainly La x1 Ni a1 ;
  • the composition of the dispersed particle phase is mainly Fe y2 Cr z2 Ni a2 D b2 La x2 with low Ni content;
  • the Ni in the La x1 Ni a1 matrix phase is intermetallic with La Combination; 0 ⁇ a2 ⁇ 12%;
  • Step 2 using a dilute acid solution to remove La in the initial alloy solid La x1 Ni a1 matrix phase through a dealloying reaction, while ensuring that most of the Ni in the original La x1 Ni a1 matrix phase is not removed by the reaction to obtain nanoporous Composite powder of Ni and Fe y2 Cr z2 Ni a2 D b2 La x2 particles with low Ni content;
  • step 3 the composite powder of nanoporous Ni and the low Ni content Fe y2 Cr z2 Ni a2 D b2 La x2 particles is compacted and heat-treated and sintered to obtain an iron-chromium-nickel powder metallurgy product with a high Ni content.
  • the composition is Fe y3 Cr z3 Ni a3 D b3 La x3 ; among them, x3, y3, z3, a3, b3 represent the atomic percentage content of the corresponding constituent elements, and 0 ⁇ y3 ⁇ y2, 0 ⁇ z3 ⁇ z2, 0 ⁇ a2 ⁇ a3, 0 ⁇ b3 ⁇ b2, 0 ⁇ x3 ⁇ x2.
  • the atomic percent solid solution of Ni in Fe-rich phase dispersed particles generally does not exceed 12%.
  • the Ni content in Fe-Ni-based superalloys needs to reach 30%-40%. Therefore, by increasing the Ni content in Fe y2 Cr z2 Ni a2 D b2 La x2 particles with low Ni content by this method, you can obtain Iron-chromium-nickel powder metallurgy products with high Ni content are suitable for the field of superalloys.
  • the Ni in the La x1 Ni a1 matrix phase is combined with La through an intermetallic compound, including at least one of La 3 Ni intermetallic compound, La 7 Ni 3 intermetallic compound, and LaNi intermetallic compound;
  • La and Ni can react with acid, the rare earth La has higher reactivity, and the La content in intermetallic compounds is generally higher. Therefore, by adjusting the species and concentration of dilute acid, La can be corroded and removed by dealloying reaction. Although a small amount of Ni is inevitably corroded and dissolved, most of Ni can be retained by dealloying into nanoporous Ni.
  • the Fe y2 Cr z2 Ni a2 D b2 La x2 particle phase with low Ni content contains Cr, which is corrosion-resistant and can be completely retained;
  • the size of the nanoporous Ni tie is lower than 200nm;
  • press molding and heat treatment and sintering can be carried out successively, or simultaneously; performing simultaneously is hot pressing sintering;
  • the sintering temperature of the heat treatment is lower than the melting point of the low Ni content Fe y2 Cr z2 Ni a2 D b2 La x2 particles;
  • the sintering temperature of the heat treatment is 400°C to 1400°C;
  • the heat treatment sintering temperature is 400°C to 1100°C;
  • the heat treatment sintering temperature is 400°C to 900°C;
  • nanoporous Ni enters the Fe y2 Cr z2 Ni a2 D b2 La x2 particles with low Ni content, and solid dissolves therein, increasing the nickel content;
  • the present invention also relates to a high-nickel-content iron-chromium-nickel powder metallurgy product, which is characterized in that it is prepared by the method for preparing a high-nickel-content iron-chromium-nickel powder metallurgy product described in its six aspects; aspect mentioned.
  • the present invention also relates to a composite powder of nanoporous Ni and iron-chromium-nickel particles with low Ni content, which is characterized in that it is prepared by step 1 and step 2 of the method described in its six aspects; aspect mentioned.
  • the present invention also relates to the application of the spherical ferroalloy powder material described in the second aspect in any of the following fields, the application fields include general powder metallurgy, metal injection molding (MIM), 3D printing, magnetic materials, Heat-resistant materials, high-temperature alloys, coatings, and microwave-absorbing materials.
  • MIM metal injection molding
  • 3D printing magnetic materials, Heat-resistant materials, high-temperature alloys, coatings, and microwave-absorbing materials.
  • the spherical ferroalloy powder material involved in the first aspect and the second aspect of the present invention can be used in the common powder metallurgy field. That is, the powder is pressed into a blank, and then directly sintered into a bulk powder metallurgy product of the corresponding composition, or the powder is compounded with other powders, then pressed into a blank, and a bulk powder metallurgy product of the corresponding composite composition is sintered. products.
  • the other powders include at least one of metal powder, alloy powder, oxide powder, carbide powder, nitride powder, carbon powder, and ceramic powder of other components;
  • the theoretically optimal particle size of powder materials for MIM is 0.5 ⁇ m to 10 ⁇ m, but currently due to technical limitations, the particle size of powder materials used in MIM is generally greater than 10 ⁇ m, even exceeding 50 ⁇ m; the present invention
  • the method is very suitable for the preparation of 0.5 ⁇ m-10 ⁇ m powder, and the finer the powder, the easier it is to prepare. Therefore, the ferroalloy powder materials involved in the first aspect and the second aspect of the present invention are very suitable for the field of metal injection molding (MIM).
  • MIM technology uses powder and organic binder to make a blank together, and after removing the organic binder, it is sintered to obtain a product. Due to the removal of the binder, the sintered product is relatively small There is a shrinkage of 10% to 20% in volume.
  • the 3D printing of powder coating of fine powder requires spherical powder with a particle size of about 15 ⁇ m to 53 ⁇ m.
  • spherical ferroalloy powder in this particle size range can be obtained, and by further screening, the particles in this particle size range can be The powder is concentrated. Therefore, the spherical ferroalloy powder materials involved in the first aspect and the second aspect of the present invention can also be used in the field of 3D printing in some cases.
  • the spherical ferroalloy powder materials involved in the first aspect and the second aspect of the present invention can also be used for soft magnetic materials or hard magnetic materials (permanent magnets).
  • powder materials whose main element composition is Fe-Cr and Fe-Cr-Si can be used for soft magnetic materials (such as magnetic powder cores), while powder materials whose main element composition is Fe-Cr-Co can be used for hard magnetic materials.
  • the powder material whose main element composition is Fe-Cr and Fe-Cr-Si involved in the present invention includes the application as a magnetic powder core.
  • the magnetic powder core is formed by applying an insulating coating material to the powder material whose main element composition is Fe-Cr and Fe-Cr-Si, and then pressing at a certain temperature; further, the pressing temperature From room temperature to 800°C.
  • the weight percentage of the insulating coating material in the magnetic powder core is more than 0.1% and less than 15%;
  • the insulating covering material includes resin; preferably, the insulating covering material includes at least one of silicone resin, phenolic resin, epoxy resin, polypropylene, and nylon.
  • one aspect of the present invention and the spherical ferroalloy powder materials containing V, W, Mo, Ti and other high-melting elements involved in the two aspects of the present invention or contain Al and can form alumina heat-resistant protection at high temperatures
  • Layered spherical iron alloy powder materials such as powder materials or powder metallurgy products prepared by spherical iron alloy powder materials whose main element composition is Fe-Cr-Al, Fe-Cr-Al-(V/W/Mo/Ti), MIM Products, can greatly improve its heat resistance, can be used for heat-resistant materials.
  • one aspect of the present invention and the spherical iron alloy powder materials involving high melting point elements such as V, W, Mo, Ti, etc., as the main element composition is Fe-Cr-Ni-(V/W /Mo/Ti) spherical iron alloy powder material, which has good high temperature resistance.
  • the composition of the spherical iron alloy powder material containing V, W, Mo, Ti and other high melting point elements involved in one aspect of the present invention and its two aspects is the same as or close to that of the superalloy, it can be used in the field of superalloys.
  • the spherical iron alloy powder materials involved in one aspect of the present invention and its two aspects can be used as key components in the field of coatings, including thermal spray coatings, resin-based coatings, and magnetic shielding coatings;
  • the spherical ferroalloy powder materials involved in the first aspect and the second aspect of the present invention can be used as magnetic metal powder in the field of wave-absorbing materials.
  • the present invention also relates to the application of the spherical iron alloy powder material described in the second aspect in the field of electrothermal materials, and the main component of the spherical iron alloy powder material includes Fe-Cr-Al.
  • the main elements involved in the first aspect and the second aspect of the present invention are Fe-Cr-Al, Fe-Cr-Al-(V/W/Mo/Ti) powder materials, through powder metallurgy technology After being made into a finished product, it is an excellent electric heating material.
  • the service temperature can reach above 1400°C. Due to the high aluminum content in the alloy whose main element composition is Fe-Cr-Al, the alloy has a high resistivity, and the highest value reaches 1.6 ⁇ .m.
  • High resistivity can effectively convert electrical energy into heat energy; meanwhile, the price of Fe-Cr-Al alloy is cheap, only 20% to 25% of that of Ni-Cr alloy, which creates conditions for its mass use. In addition, it has good heat resistance, low specific gravity and excellent high temperature oxidation resistance, and is widely used in various aspects of production and life.
  • the heating elements used by Fe-Cr-Al powder metallurgy alloys include electric furnace wires, electric furnace rods, cooking plates, radiators, toasters, microwave ovens, water heaters, washing machines, boilers, precision resistance elements in automobiles.
  • the present invention also relates to the application of the high-silicon-content spherical iron-chromium-silicon powder material described in its fourth aspect in magnetic materials;
  • the spherical iron-chromium-silicon powder material with high silicon content involved in the four aspects of the present invention includes the application as a magnetic powder core.
  • the magnetic powder core is formed by applying an insulating coating material to the high-silicon-content spherical Fe-Cr-Si powder material, and then pressing at a certain temperature; further, the pressing temperature is from room temperature to 800°C .
  • the weight percentage of the insulating coating material in the magnetic powder core is more than 0.1% and less than 15%;
  • the insulating covering material includes resin; preferably, the insulating covering material includes at least one of silicone resin, phenolic resin, epoxy resin, polypropylene, and nylon.
  • the present invention also relates to the application of the high-nickel-content iron-chromium-nickel powder metallurgy product described in its seventh aspect in high-temperature alloys.
  • Superalloys mainly include nickel-based, iron-based, and nickel-iron-based superalloys.
  • composition of the high-nickel-content iron-chromium-nickel powder metallurgy product described in the seven aspects of the present invention is the same as or close to that of the superalloy, it can be used for field of high temperature alloys.
  • the present invention also relates to an alloy solid, which is characterized in that it is prepared by the method for preparing the initial alloy solid described in step 1 and step 2 of the first aspect, and its features are detailed in the first aspect.
  • Step 1 selecting the initial alloy raw material, melting the initial alloy raw material according to the distribution ratio of the initial alloy composition to obtain a uniform initial alloy melt;
  • the main component of the initial alloy melt is La x Fe y T z M a D b , wherein T contains at least one of Cr and V, M contains at least one of Al, Ni, Co, and Si, D contains at least one of Mo, W, and Ti, and x, y, z, a, and b represent The atomic percentage content of the corresponding constituent elements, and 18% ⁇ x ⁇ 95.8%, 4% ⁇ y ⁇ 81.8%, 0.1% ⁇ z ⁇ 35%, 0 ⁇ a ⁇ 40%, 0 ⁇ b ⁇ 15%;
  • Step 2 solidifying the initial alloy melt into an initial alloy solid by rapid solidification technology;
  • the solidification structure of the initial alloy solid includes a matrix phase and a dispersed particle phase;
  • the melting point of the matrix phase is lower than the melting point of the dispersed particle phase,
  • the dispersed particle phase is coated in the matrix phase;
  • the volume percentage of the matrix phase in the solidified tissue is not less than 40%;
  • the average composition of the matrix phase is mainly La x1 M a1 ;
  • the composition of the phase is mainly Fe y2 T z2 M a2 D b2 La x2 , where x1, a1, x2, y2, z2, a2, b2 represent the atomic percentage content of the corresponding constituent elements, and 45% ⁇ x1 ⁇ 100%, 0% ⁇ a1 ⁇ 55%, 50% ⁇ y2 ⁇ 98%, 0.2% ⁇ z2 ⁇ 50%, 0% ⁇ a2 ⁇ 30%, 0% ⁇ b2 ⁇ 35%, 0 ⁇
  • the composition of the initial alloy melt in step one also includes non-metallic impurity elements, and the non-metallic impurity elements include at least one of O, N, H, P, S, Cl; the non-metallic impurity elements
  • the atomic percent content in the initial alloy melt is greater than 0 and less than 10%; during the formation of the Fe-rich dispersed particle phase described in step 2, the non-metallic impurity elements are enriched in the La-rich matrix phase, thereby contributing to the Fe-rich dispersed particle phase
  • the granular phase has been purified, that is, the atomic percentage content of the non-metallic impurity element in the Fe-rich dispersed granular phase is lower than the atomic percentage content of the non-metallic impurity element in the initial alloy melt; and the Fe-rich dispersed granular phase In, the atomic percent content of non-metallic impurity elements is less than 1.5%.
  • the present invention also relates to the application of the spherical iron alloy powder material described in the second aspect in the field of magnetic fluid.
  • the characteristics of the spherical iron alloy powder material are detailed in the first aspect and the second aspect; some features of the spherical iron alloy powder material include: the main component of the spherical iron alloy powder material is Fe y2 T z2 M a2 D b2 La x2 ; wherein, 50% ⁇ y2 ⁇ 98%, 0.2% ⁇ z2 ⁇ 50%, 0% ⁇ a2 ⁇ 30%, 0% ⁇ b2 ⁇ 35%, 0 ⁇ x2 ⁇ 5%; the iron alloy powder particles
  • the shape of the ferroalloy powder is mainly spherical or nearly spherical, and some spherical or nearly spherical ferroalloy powder particles contain certain dendrite characteristics; the particle size of the ferroalloy powder particles is 5nm to 100nm; T contains at least one of Cr and V M contains at least one of Al, Ni, Co, and Si, and D contains at least one of Mo, W, and Ti; x1, a1, x2, y2,
  • the particle size of the spherical iron alloy powder particles is 5nm-50nm;
  • the particle size of the spherical ferroalloy powder particles is 5nm-25nm;
  • the spherical iron alloy powder material involved in the first aspect and the second aspect of the present invention can be used in the field of magnetic fluid; specifically, it includes: uniformly mixing the spherical iron alloy powder with a carrier liquid and a surfactant to obtain a magnetic fluid;
  • the carrier liquid includes at least one of water, ethanol, carbohydrates, lipids, dilipids, and mercury;
  • the surfactant includes at least one of oleic acid, polyvinylpyrrolidone, polyethylene glycol, ethylene glycol, and sodium dodecylbenzenesulfonate.
  • Magnetic solid particles of magnetic fluid As magnetic solid particles of magnetic fluid, it generally requires its particle size to be nanoscale; Fe is one of the best magnetic materials, but when nano-Fe particles are used as magnetic solid particles of magnetic fluid, due to the extremely easy oxidation of nano-Fe particles, It will lead to unstable performance and it is difficult to be well applied. This application solves this problem very well.
  • the prepared spherical Fe alloy powder particles contain a certain amount of corrosion-resistant Cr, V, Mo, W, and Ti elements in solid solution, it can not only make the spheroidization more obvious, It can also obviously improve the corrosion resistance of nano-Fe alloy powder particles.
  • the present invention also relates to a coronavirus-shaped spherical iron alloy powder particle, which is characterized in that: the main component of the coronavirus-shaped spherical iron alloy powder particle is Fe y2 T z2 M a2 D b2 La x2 ; wherein , 50% ⁇ y2 ⁇ 98%, 0.2% ⁇ z2 ⁇ 50%, 0% ⁇ a2 ⁇ 30%, 0% ⁇ b2 ⁇ 35%, 0 ⁇ x2 ⁇ 5%; T contains at least one of Cr and V , M contains at least one of Al, Ni, Co, and Si, D contains at least one of Mo, W, and Ti, La is a rare earth La, and La mainly exists in solid solution with the main component being Fe y2 T z2 M a2 D In the coronavirus-shaped spherical iron alloy particles of b2 La x2 ; x1, a1, x2, y2, z2, a2, and b2 respectively represent the atomic percentage
  • the number of protrusions on any single coronavirus-shaped spherical iron alloy powder particle exceeds 5;
  • the number of protrusions on any single coronavirus-shaped spherical iron alloy powder particle exceeds 10;
  • the diameter of the sphere of the main part of the coronavirus-shaped spherical iron alloy powder particle is 50 nm to 15 ⁇ m;
  • the diameter of the sphere of the main part of the coronavirus-shaped spherical iron alloy powder particle is 200 nm to 10 ⁇ m;
  • the diameter of the sphere of the main part of the coronavirus-shaped spherical iron alloy powder particle is 200 nm to 5 ⁇ m;
  • any single protrusion of the appendage part is composed of no more than one crystal grain, and the crystal structure and crystal plane orientation of the crystal grain and the crystal structure and crystal plane orientation of the sphere part connected to the junction are the same;
  • the main part and the appendage part of the coronavirus-shaped spherical iron alloy powder particles belong to a large single crystal
  • the height of the protrusion of the appendage is lower than 0.2 times the diameter of the sphere of the main body
  • the protrusions are dendritic protrusions, that is, the protrusions are the preferential growth points for the transition from spherical particles to dendritic particles; or it can be understood as: after the spherical particles grow to a certain stage, some parts of the spherical surface appear preferential growth point, so as to continue to preferentially grow into protrusions according to the original crystal structure and crystal plane orientation of the growth point;
  • the diameter of the protrusion of the appendage part is less than 0.25 times the diameter of the main sphere of the coronavirus-shaped spherical iron alloy powder particle;
  • the morphological characteristics of the coronavirus-shaped spherical iron alloy powder particles can refer to the shapes of the coronavirus-shaped spherical particles shown in Figure 3, Figure 11, Figure 12, and Figure 15 in the embodiments;
  • T-type elements Through the addition design of T-type elements, the precipitation and subsequent separation of corrosion-resistant and oxidation-resistant spherical or nearly spherical Fe-rich dispersed particle phases in La-rich matrix phases are realized. There are many ingenuities in the selection of T-type elements: T-type elements are completely miscible with Fe and can be added in large quantities; T-type elements, like Fe, do not produce any intermetallic compounds with La, and hardly enter the La-rich phase.
  • T-type elements It only enters the Fe-rich dispersed particle phase; the presence of solid solution of T-type elements makes the Fe-rich dispersed particle phase have a tendency to spheroidize, which is the key to preparing spherical or nearly spherical Fe alloy powders; T-type elements and D-type elements are completely miscible, In the case that the solid solubility of D-type elements in Fe is 10%-20%, because of the existence of T-type elements, more D-type elements can be more easily dissolved in the Fe-rich dispersed particle phase; T-type elements Cr V and V are corrosion-resistant elements in Fe alloys.
  • the corrosion resistance and oxidation resistance of the Fe-rich dispersed particle phase are significantly improved, and the Fe-rich dispersed particle phase and the La-rich matrix phase pass through the acid Corrosion reaction separation and oxidation-powdering separation become possible. Otherwise, the pure Fe phase is also easy to react with acid and easy to oxidize, especially when the particle phase is relatively fine.
  • rare earth elements are directly dissolved in spherical or nearly spherical Fe alloy powders.
  • the addition of rare earth elements to iron alloys has a positive effect on the performance of materials.
  • Fe-Cr-Al electrothermal alloy adding a small amount of rare earth elements will improve the performance of the electrothermal alloy.
  • rare earth elements are added to Fe alloys. Since rare earth elements are easy to oxidize, when a small amount of rare earth elements are added, rare earth elements generally combine with impurities such as oxygen in the alloy, and thus exist in the alloy in the form of oxide particles non-uniformly. As a result, the performance of the alloy is limited.
  • the initial alloy melt of the present application contains more La (the La-rich matrix phase volume percentage is higher than 40%). Therefore, the oxygen in the alloy melt mainly exists in the La-rich matrix phase, and the spherical or nearly spherical There is a small amount of La in solid solution in the Fe alloy powder.
  • This La is homogeneously dissolved in the Fe alloy powder in an atomic state, and is an alloyed rare earth element in the strict sense, which has a more positive effect on the properties of the material.
  • the presence of solid solution rare earth element (La) in the Fe alloy powder is one of the key features of the ferroalloy powder material prepared in the present invention.
  • the prepared partially spherical or nearly spherical ferroalloy powder particles contain convex short dendrite features.
  • the strength of rough products is one of the key factors for normal production.
  • the blank product of metal injection molding MIM is obtained by pressing metal powder and organic binder, and then removing the organic binder.
  • MIM blank products are products with high strength after shrinkage through sintering. After removing the organic binder and before sintering, the MIM green product needs to rely on the mechanical combination between the particles to maintain the shape of the green product.
  • the metal powder is all ideal spherical particles, the mechanical-friction bonding force between such ideal spherical particles is extremely poor, which will easily lead to the collapse of the rough product.
  • the partially spherical or nearly spherical iron alloy powder particles contain convex short dendrite features, which have little effect on the sphericity of the particles, but they can greatly enhance the mechanical bonding force or friction between particles , thereby enhancing the strength of the rough product. If all particles have this characteristic of raised short dendrites, this again affects the powder popularity of spherical particles.
  • the raised short dendrite feature only appears on the surface of part of the prepared spherical or nearly spherical ferroalloy powder particles. Therefore, the protruding short dendrites on the partially spherical iron alloy powder particles are another key feature of the Fe alloy powder prepared in the present invention.
  • the Fe-rich dispersed particle phase was purified simultaneously. If the initial alloy is prepared from raw materials containing O, N, H, P, S, Cl and other impurity elements and with low purity, or if the above-mentioned impurities are introduced into the melt during the initial alloy melting process, it will not affect the final ability to obtain the above-mentioned low
  • the Fe-rich dispersed particle phase with impurity content can further obtain spherical iron alloy powder material with low impurity content.
  • the above-mentioned impurity elements in the raw materials, or the above-mentioned impurity elements introduced during the smelting process, during the solidification process of the initial alloy melt most of them will be captured by the La-rich matrix phase and then enter the matrix phase, so that the Fe-rich dispersed particle phase get purified.
  • Ferroalloy powder materials mainly composed of single crystal particles can be obtained. Compared with polycrystalline powder, single crystal powder can obtain many significant and beneficial effects.
  • each endogenous particle nucleates from a certain position in the melt and then grows up according to a specific atomic arrangement.
  • the volume percentage of the matrix phase By controlling the volume percentage of the matrix phase to ensure that each endogenous particle can be dispersedly distributed, it is difficult to bond and entangle among each endogenous dispersed particle. Therefore, the finally obtained dispersed Fe-rich dispersed particle phases are generally single crystal phases.
  • the protruding short dendrites grow further on the spherical particles, they grow according to the fixed crystal direction on the surface of the sphere, that is, the sphere and the protruding short dendrites are one crystal grain.
  • the grain boundaries generally tend to contain impurity elements discharged from the crystal during solidification, so it is difficult to obtain high-purity polycrystalline powder materials.
  • the powder material is mainly composed of single crystal particles, its purity must be guaranteed.
  • the surface atoms of single crystal particles have specific arrangements, such as (111) plane arrangement, etc. These specific arrangements will endow the material with special mechanical, physical, and chemical properties, thereby producing beneficial effects.
  • the present invention realizes that T elements, M elements, D elements, and La are present in The solid solution alloying in the spherical or nearly spherical Fe-rich dispersed particle phase improves the corrosion resistance and oxidation resistance of the spherical or nearly spherical Fe-rich dispersed particle phase, and reduces the impurity content.
  • an ultra-fine spherical ferroalloy powder material with a particle size ranging from hundreds of nanometers to several microns is obtained.
  • Coatings, electric heating materials, wave-absorbing materials and other fields have good application prospects.
  • T contains at least one of Cr and V
  • M contains at least one of Al, Ni, Co, and Si
  • D contains at least one of Mo, W, and Ti. kind.
  • Fig. 1 is the backscattered SEM morphology of initial alloy solidification structure described in embodiment 1;
  • Fig. 2 is the SEM appearance of the ferroalloy powder material that embodiment 1 prepares
  • Fig. 3 is the backscattered SEM morphology of initial alloy solidification structure described in embodiment 2;
  • Fig. 4 is the backscattering high-magnification SEM morphology of the initial alloy solidification structure matrix described in embodiment 2;
  • Fig. 5 is the backscattered SEM morphology of initial alloy solidification structure described in embodiment 3;
  • Fig. 6 is the backscattering high-magnification SEM morphology of the initial alloy solidification structure matrix described in embodiment 3;
  • Fig. 7 is the backscattered SEM appearance of initial alloy solidification structure described in embodiment 4.
  • Fig. 8 is the backscattered SEM appearance of initial alloy solidification structure described in embodiment 5;
  • Fig. 9 is the backscattered SEM appearance of initial alloy solidification structure described in embodiment 6;
  • Fig. 10 is the backscattered SEM appearance of initial alloy solidification structure described in embodiment 7;
  • Fig. 11 is the backscattered SEM appearance of initial alloy solidification structure described in embodiment 8.
  • Fig. 12 is the SEM appearance of iron alloy powder material described in embodiment 8.
  • Fig. 13 is the backscattered SEM appearance of initial alloy solidification structure described in embodiment 10;
  • Fig. 14 is the backscattered SEM appearance of initial alloy solidification structure described in embodiment 11;
  • Fig. 15 is the SEM appearance of ferroalloy powder material described in embodiment 11;
  • Fig. 16 is the backscattered SEM appearance of initial alloy solidification structure described in embodiment 12;
  • Fig. 17 is the backscattered SEM appearance of initial alloy solidification structure described in embodiment 13;
  • Fig. 18 is the SEM appearance of iron alloy powder material described in embodiment 13;
  • Fig. 19 is the backscattered SEM morphology of the initial alloy solidification structure described in embodiment 14;
  • Figure 20 is the backscattered SEM morphology of the initial alloy solidification structure described in embodiment 15;
  • Fig. 21 is the backscattered SEM morphology of the initial alloy solidification structure described in embodiment 16;
  • Fig. 22 is the SEM appearance of the ferroalloy powder material described in embodiment 16;
  • Figure 23 is the backscattered SEM morphology of the initial alloy solidification structure described in Comparative Example 1;
  • Figure 24 is the SEM morphology of the iron-rich dendrites described in Comparative Example 1;
  • Figure 25 is the backscattered SEM morphology of the initial alloy solidification structure described in Comparative Example 2;
  • Figure 26 is the backscattered SEM morphology of the initial alloy solidification structure described in Comparative Example 3.
  • Figure 27 is the backscattered SEM morphology of the initial alloy solidification structure described in Comparative Example 4.
  • Fig. 28 is the high magnification backscattering SEM morphology of the initial alloy solidification structure described in Comparative Example 4.
  • the initial alloy melt whose main component is La 50 Fe 41 Cr 9 is smelted according to the nominal composition of La 50 Fe 41 Cr 9 in atomic percentage through commercially available La, Fe, Cr raw materials, and the uniform initial alloy melt is cooled at about 100K/s Rapidly solidified into an initial alloy plate with a thickness of about 5mm.
  • the solidification structure of the initial alloy plate is shown in Figure 1, including a dispersed particle phase whose main component is Fe 79 Cr 20 La 1 and a matrix phase whose main component is La, where the volume percentage of the matrix phase exceeds 65%; the dispersed particle phase Both Cr and La are dissolved in it; the dispersed particle phase includes spherical particle phase and dendritic particle phase, and the volume percentage of the spherical particle phase exceeds 50%; the particle size range of the spherical particle phase is 15nm-60 ⁇ m .
  • the La matrix phase in the initial alloy plate is removed by reaction corrosion with 0.5mol/L dilute hydrochloric acid solution, and the dispersed ferroalloy powder material whose main component is Fe 79 Cr 20 La 1 is obtained, which includes spherical particles and dendritic particles. And the volume percentage of the spherical particles exceeds 50%; the particle size range of the spherical particles is 15nm-60 ⁇ m, as shown in FIG. 2 .
  • the partially spherical or nearly spherical particle phase contains certain dendrite features, such as the dendrite small protrusion structure on the spherical particle as shown in the inset of Fig. 2.
  • the prepared ferroalloy powder material can be used in the fields of common powder metallurgy and metal injection molding (MIM).
  • the initial alloy melt whose main component is La 50 Fe 41 Cr 9 is smelted according to the nominal composition of La 50 Fe 41 Cr 9 in atomic percentage through commercially available La, Fe, Cr raw materials, and the uniform initial alloy melt is cooled at about 5000K/s
  • the initial alloy strips with a thickness of about 200 ⁇ m were rapidly solidified by the strip throwing method.
  • the solidification structure of the initial alloy strip is shown in Figure 3, including the dispersed particle phase whose main component is Fe 77 Cr 22 La 1 and the matrix phase whose main component is La, wherein the volume percentage of the matrix phase exceeds 65%;
  • the dispersed granular phase is almost all spherical particles; part of the spherical granular phase contains certain dendrite features, such as the small dendrite protrusion structure on the spherical granular phase as shown in the inset of Figure 3.
  • the particle size range of the spherical particle phase is 15nm-10 ⁇ m. Enlarge the matrix phase in Figure 3, and some nano-spherical particles can be found inside, as shown in Figure 4.
  • the La matrix phase in the initial alloy strip was corroded and removed by 0.5mol/L dilute sulfuric acid solution, and the dispersed ferroalloy powder material whose main component was Fe 77 Cr 22 La 1 was obtained, almost all of which were spherical particles, and some
  • the spherical particle phase contains certain dendrite characteristics; the particle size range of the spherical particles is 15nm-10 ⁇ m.
  • the prepared powder material can be used in the fields of common powder metallurgy and metal injection molding (MIM).
  • the initial alloy melt whose main component is La 67 Fe 30 V 3 is smelted according to the nominal composition of La 67 Fe 30 V 3 in atomic percentage by commercially available La, Fe, V raw materials, and the uniform initial alloy melt is cooled at about 1000K/s Rapidly solidified into initial alloy strips with a thickness of approximately 500 ⁇ m.
  • the solidification structure of the initial alloy strip is shown in Figure 5, including the dispersed particle phase whose main component is Fe 88.5 V 9 La 1.5 and the matrix phase whose main component is La, wherein the volume percentage of the matrix phase exceeds 70%;
  • the dispersed particle phase is mainly spherical; the particle size range of the spherical particle phase is 15nm-5 ⁇ m.
  • the La matrix phase in the initial alloy strip was corroded and removed by 0.5mol/L dilute hydrochloric acid, and the dispersed iron alloy powder material whose main component was Fe 88.5 V 9 La 1.5 was obtained, and its shape was mainly spherical particles, with only A small amount of granular phase is dendritic particles.
  • the particle size range of the spherical particles is 15nm-5 ⁇ m.
  • the main composition is about La 65 Fe 30 Cr 3 V according to the nominal composition of atomic percentage La 67 Fe 30 Cr 3 V 3 3 O 2 initial alloy melt, the homogeneous initial alloy melt is solidified at a cooling rate of about 250K/s into an initial alloy thick strip with a thickness of about 3mm.
  • the solidification structure of the initial alloy thick strip is shown in Figure 7, including the dispersed particle phase whose main component is Fe 82.3 V 8 Cr 8 La 1.5 O 0.2 and the matrix phase whose main component is La and enriched with oxygen impurities.
  • the volume percentage of the phase exceeds 70%; the dispersed particle phase is mainly spherical, including a small amount of dendrite; the particle size range of the spherical particle phase is 15nm-15 ⁇ m, and part of the spherical particle phase contains certain dendrite characteristics.
  • the La-rich matrix phase in the initial alloy thick strip is corroded and removed by 0.2mol/L dilute nitric acid, and the dispersed iron alloy powder material whose main component is Fe 82.3 V 8 Cr 8 La 1.5 O 0.2 is obtained, and its shape is mainly Spherical, including a small amount of dendrite, and some spherical particles contain certain dendrite characteristics.
  • the particle size range of the spherical particles is 15nm-15 ⁇ m.
  • the initial alloy melt whose main composition is La 50 Fe 40 Cr 0.5 Mo 9.5 is smelted according to the nominal composition La 50 Fe 40 Cr 0.5 Mo 9.5 in atomic percentage through commercially available La, Fe, Cr, Mo raw materials, and the uniform initial alloy melt
  • the cooling rate of about 250K/s solidifies into a thick strip of initial alloy with a thickness of about 3mm.
  • the solidification structure of the initial alloy thick strip is shown in Figure 8, including the dispersed particle phase whose main component is Fe 78 Mo 20 Cr 1 La 1 and the matrix phase whose main component is La, where the volume percentage of the matrix phase exceeds 70 %; the dispersed particle phase is mainly spherical; the particle size range of the spherical dispersed particle phase is 15nm-15 ⁇ m, and part of the spherical particle phase contains certain dendrite characteristics.
  • the La matrix phase in the initial alloy thick strip was corroded and removed by 0.5mol/L dilute hydrochloric acid, and the dispersed iron alloy powder material whose main component was Fe 78 Mo 20 Cr 1 La 1 was obtained, and its shape was mainly spherical particles. And some spherical particles contain certain dendrite characteristics; the particle size range of the spherical particles is 15nm-15 ⁇ m.
  • the initial alloy melt of La 34 Fe 40 Cr 2.5 Si 23.5 is smelted according to the nominal composition La 34 Fe 40 Cr 2.5 Si 23.5 according to the atomic percentage through commercially available raw materials, and the uniform initial alloy melt is about
  • the cooling rate of 100K/s solidifies into a thick initial alloy strip with a thickness of about 5mm.
  • the solidification structure of the initial alloy thick strip is shown in Figure 9, including the black dispersed particle phase whose main component is Fe 85.2 Cr 8 Si 6 La 0.8 , the white matrix phase whose main component is La 64 Si 36 and the main component La 34
  • the gray matrix phase of Si 33 Fe 33 in which the volume percentage of the two matrix phases exceeds 70%; the dispersed particle phase is mainly nearly spherical.
  • the particle size range of the nearly spherical particle phase is 50nm-5 ⁇ m.
  • the La 64 Si 36 matrix phase and the La 34 Si 33 Fe 33 matrix phase in the initial alloy thick ribbon are removed by reaction corrosion with a mixed solution of 0.5mol/L dilute hydrochloric acid and 1mol/L hydrofluoric acid, and the dispersed main components are
  • the iron alloy powder material of Fe 85.2 Cr 8 Si 6 La 0.8 is mainly in a nearly spherical shape, and the particle size range of the nearly spherical particles is 50nm-5 ⁇ m.
  • the prepared powder material can be used in the field of magnetic materials, such as magnetic powder cores.
  • the initial alloy melt of La 34 Fe 40 Cr 2.5 Si 23.5 is smelted according to the nominal composition La 34 Fe 40 Cr 2.5 Si 23.5 according to the atomic percentage through commercially available raw materials, and the uniform initial alloy melt is about
  • the initial alloy strips with a thickness of about 100 ⁇ m were solidified at a cooling rate of 10 5 K/s.
  • the solidification structure of the initial alloy strip is shown in Figure 10, including the black dispersed particle phase whose main composition is Fe 82.5 Cr 8 Si 8 La 1.5 and the matrix phase whose average composition is mainly La 60 Si 20 Fe 20.
  • the matrix phase The volume percentage is greater than 70%; the dispersed particle phase is mainly fine spherical.
  • the particle size range of the spherical particle phase is 15nm-2 ⁇ m.
  • the matrix phase whose average composition is mainly La 60 Si 20 Fe 20 in the initial alloy strip is removed by reactive corrosion, and the main dispersed composition is Fe 82.5 Cr
  • the Si-containing iron alloy powder material of 8 Si 8 La 1.5 is mainly in a nearly spherical shape, and the particle size range of the nearly spherical particles is 15nm-2 ⁇ m.
  • the prepared powder material can be used in the field of magnetic materials, such as magnetic powder cores.
  • the initial alloy melt whose main composition is La 50 Fe 40 Cr 5 Si 5 is smelted according to the nominal composition La 50 Fe 40 Cr 5 Si 5 in atomic percentage through commercially available La, Fe, Cr, Si raw materials, and the uniform initial alloy melt
  • the cooling rate of about 250K/s solidifies into a thick strip of initial alloy with a thickness of about 3mm.
  • the solidification structure of the initial alloy thick strip is shown in Figure 11, including the dispersed particle phase whose main component is Fe 86 Cr 12 Si 1 La 1 and the matrix phase whose main component is La 92 Si 8 , where the volume percentage of the matrix phase The content exceeds 70%; the dispersed particle phase is mainly spherical, including a small amount of dendrite; and some spherical particle phases contain certain dendrite characteristics.
  • the particle size range of the spherical particle phase is 15nm-40 ⁇ m.
  • the LaSi matrix phase in the initial alloy strip is corroded and removed by a mixed solution of 0.5mol/L dilute hydrochloric acid, 0.1mol/L dilute nitric acid, and 0.5mol/L hydrofluoric acid (hydrofluoric acid can remove Si), that is,
  • the dispersed main component is Fe 86 Cr 12 Si 1 La 1 iron alloy powder material, its shape is mainly spherical particles, and also includes a small amount of dendritic particles, and some spherical particles contain certain dendrite characteristics, the spherical particles The diameter ranges from 15nm to 40 ⁇ m. As shown in Figure 12.
  • the initial alloy melt whose main composition is La 50 Fe 41 Cr 4 Si 5 is smelted according to the nominal composition La 50 Fe 41 Cr 4 Si 5 in atomic percentage through commercially available La, Fe, Cr, Si raw materials, and the uniform initial alloy melt
  • the cooling rate of about 1000K/s solidifies into an initial alloy strip with a thickness of about 500 ⁇ m.
  • the solidification structure of the initial alloy ribbon includes the dispersed particle phase whose main component is Fe 90.5 Cr 8 Si 0.5 La 1 and the matrix phase whose main component is La 94 Si 6 , wherein the volume percentage of the matrix phase exceeds 70%; the dispersed particles
  • the phase is mainly spherical, including a small amount of dendrite; and part of the spherical particle phase contains certain dendrite characteristics.
  • the particle size range of the spherical particle phase is 15nm-10 ⁇ m.
  • the La in the LaSi matrix phase of the initial alloy strip is corroded and removed by dealloying reaction with 0.5mol/L dilute hydrochloric acid, while retaining most of the Si (Si generally does not react with dilute hydrochloric acid), that is, the main component of the dispersion is Fe 90.5 Cr 8 Si 0.5 La 1 ferroalloy powder and nanoporous Si composite powder; among them, nanoporous Si has a scattered porous structure, and the ferroalloy powder is mainly spherical particles, including a small amount of dendritic particles, and some spherical particles contain Certain dendrite characteristics, the particle size range of the spherical particles is 15nm-10 ⁇ m.
  • the composite powder of spherical ferroalloy powder and nanoporous Si is pressed and compacted, it is vacuum solid siliconized at 1000°C for 4 hours, and then the powder is dispersed to obtain a high-silicon compound with a composition of about Fe 82 Cr 7 Si 10 La 1 Content iron chromium silicon powder.
  • the powder with a particle size of 3 ⁇ m-10 ⁇ m is selected, which can be used in the field of soft magnetic materials, such as magnetic powder cores.
  • the initial alloy melt whose main composition is La 45 Fe 27.5 Cr 7.5 Al 20 is smelted according to the nominal composition of La 45 Fe 27.5 Cr 7.5 Al 20 in atomic percentage through commercially available La, Fe, Cr, Al raw materials, and the uniform initial alloy melt
  • the cooling rate of about 250K/s solidifies into a thick strip of initial alloy with a thickness of about 3mm.
  • the solidification structure of the initial alloy thick strip is shown in Figure 13, including the dispersed particle phase whose main component is Fe 72 Cr 20 Al 7 La 1 and the matrix phase whose main component is La 75 Al 25 , where the volume percentage of the matrix phase The content exceeds 70%; the dispersed particle phase is mainly spherical, including a small amount of dendrite; and some spherical particle phases contain certain dendrite characteristics.
  • the particle size range of the spherical particle phase is 15nm-10 ⁇ m.
  • the La 75 Al 25 matrix phase in the initial alloy thick strip was corroded and removed by 0.5mol/L dilute hydrochloric acid, and the dispersed iron alloy powder material whose main component was Fe 72 Cr 20 Al 7 La 1 was obtained, and its shape was mainly Spherical particles also include a small amount of dendrite particles, and some of the spherical particles contain certain dendrite characteristics, and the particle size range of the spherical particles is 15nm-10 ⁇ m.
  • the prepared powder material can be used in the fields of electric heating alloy, heat-resistant alloy and heat-resistant coating.
  • the initial alloy melt whose main composition is La 45 Fe 27.5 Cr 7.5 Al 20 is smelted according to the nominal composition of La 45 Fe 27.5 Cr 7.5 Al 20 in atomic percentage through commercially available La, Fe, Cr, Al raw materials, and the uniform initial alloy melt
  • a cooling rate of about 10 4 K/s solidifies into an initial alloy thin strip with a thickness of about 150 ⁇ m.
  • the solidification structure of the initial alloy thin strip is shown in Figure 14, including the dispersed particle phase whose main component is Fe 71 Cr 21 Al 7 La 1 and the matrix phase whose main component is La 75 Al 25.
  • the volume percentage of the matrix phase The content exceeds 70%; the dispersed particle phase is almost all spherical, and some spherical particle phases contain certain dendrite characteristics.
  • the particle size range of the spherical particle phase is 5nm-5 ⁇ m.
  • the La 75 Al 25 matrix phase in the initial alloy thick strip was removed by reaction corrosion with 0.5 mol/L dilute hydrochloric acid, and the dispersed iron alloy powder material whose main component was Fe 71 Cr 21 Al 7 La 1 was obtained, as shown in Figure 15 It is shown that the shape is almost all spherical, and some spherical particles contain certain dendrite characteristics, as shown in the inset of Figure 15, the particle size range of the spherical particles is 5nm-5 ⁇ m.
  • the prepared powder material can be used in the fields of electric heating alloy, heat-resistant alloy and heat-resistant coating.
  • the initial alloy melt whose main composition is La 38 Fe 25 Cr 10 Al 25 Mo 2 is smelted according to the nominal composition La 38 Fe 25 Cr 10 Al 25 Mo 2 in atomic percent through commercially available La, Fe, Cr, Al, Mo raw materials, and the The homogeneous initial alloy melt is cooled and solidified at about 500K/s into a thick initial alloy strip with a thickness of about 1mm.
  • the solidification structure of the initial alloy thick strip is shown in Figure 16, including the dispersed particle phase whose main composition is Fe 60 Cr 25 Al 8 Mo 6 La 1 and the main composition La 50 Al 50 (gray lath and fibrous phase respectively).
  • La 75 Al 25 (white phase) matrix phase in which the total volume percentage of the matrix phase exceeds 70%;
  • the dispersed particle phase is mainly spherical, including a small amount of dendrite; and some spherical particle phases contain certain dendrites feature.
  • the particle size range of the spherical particle phase is 15nm-40 ⁇ m.
  • the La 50 Al 50 and La 75 Al 25 matrix in the initial alloy thick strips are corroded and removed by 1mol/L dilute hydrochloric acid, and the dispersed iron alloy powder whose main component is Fe 60 Cr 25 Al 8 Mo 6 La 1 is obtained
  • the shape of the material is mainly spherical particles, and also includes a small amount of dendrite particles, and some of the spherical particles contain certain dendrite characteristics, and the particle size range of the spherical particles is 15nm-40 ⁇ m.
  • the prepared powder material can be used in the fields of electric heating alloy, heat-resistant alloy and heat-resistant coating. Due to containing Mo, the powder material has higher temperature resistance and corrosion resistance.
  • the initial alloy melt whose main composition is La 27.5 Fe 37.5 Cr 10 Co 25 is smelted according to the nominal composition La 27.5 Fe 37.5 Cr 10 Co 25 in atomic percentage through commercially available La, Fe, Cr, Co raw materials, and the uniform initial alloy melt
  • the cooling rate of about 250K/s solidifies into a thick strip of initial alloy with a thickness of about 3mm.
  • the solidification structure of the initial alloy thick strip is shown in Fig. 17, including the dispersed particle phase whose main component is Fe 63 Cr 19 Co 17 La 1 and the matrix phase whose main component is La 60 Co 40.
  • the total volume of the matrix phase is 100%
  • the content of the particles exceeds 50%; the dispersed particle phase is almost all spherical, including only a small amount of dendrite; and some spherical particle phases contain certain dendrite characteristics.
  • the particle size range of the spherical particle phase is 15nm-6 ⁇ m.
  • the La 60 Co 40 matrix phase in the initial alloy thick strip is corroded and removed by 1mol/L dilute hydrochloric acid, and the dispersed iron alloy powder material whose main component is Fe 63 Cr 19 Co 17 La 1 is obtained, as shown in Figure 18 , the shape of which is mainly spherical particles, and also includes a small amount of dendrite particles, and some spherical particles contain certain dendrite characteristics, and the particle size range of the spherical particles is 15nm-6 ⁇ m.
  • the prepared powder material can be used in the field of magnetic materials.
  • the initial alloy melt whose main composition is La 27.5 Fe 37.5 Cr 10 Ni 25 is smelted according to the nominal composition of atomic percentage La 27.5 Fe 37.5 Cr 10 Ni 25 through commercially available La, Fe, Cr, Ni raw materials, and the uniform initial alloy melt
  • the cooling rate of about 250K/s solidifies into a thick strip of initial alloy with a thickness of about 3mm.
  • the solidification structure of the initial alloy thick strip is shown in Figure 19, including the dispersed particle phase whose main composition is Fe 70 Cr 20 Ni 9 La 1 and the matrix phase whose main composition is about La 50 Ni 50 and La 75 Ni 25 , respectively.
  • the total volume percentage of the matrix phase exceeds 50%; the dispersed particle phase is mainly spherical, including a small amount of dendrite; and some spherical particle phases contain certain dendrite characteristics.
  • the particle size range of the spherical particle phase is 15nm-50 ⁇ m.
  • the matrix phase of La 50 Ni 50 and La 75 Ni 25 in the initial alloy ribbon was removed by reaction corrosion with 1mol/L dilute hydrochloric acid, and the dispersed iron alloy powder material whose main component was Fe 70 Cr 20 Ni 9 La 1 was obtained.
  • Its shape is mainly spherical particles, and also includes a small amount of dendritic particles, and some spherical particles contain certain dendrite characteristics, and the particle size range of the spherical particles is 15nm-50 ⁇ m.
  • the initial alloy melt is solidified at a cooling rate of about 50K/s into a button ingot with a thickness of 6mm and a diameter of 12mm.
  • the solidification structure of the initial alloy button ingot is shown in Figure 20, including the dispersed particle phase whose main composition is Fe 70 Cr 20 Ni 3 Mo 2 Ti 4 La 1 and the matrix phase whose average composition is mainly La 81 Ni 19 (by La Phase and La 3 Ni phase), in which the total volume percentage of the matrix phase exceeds 70%; the dispersed particle phase is almost all spherical, including only a small amount of dendrite; and some spherical particle phases contain certain dendrite characteristics.
  • the particle size range of the spherical particle phase is 15nm-50 ⁇ m.
  • the La 81 Ni 19 matrix phase in the initial alloy button ingot was removed by reaction corrosion with 1mol/L hydrochloric acid solution, while the corrosion-resistant dispersed particle phase was retained, that is, the dispersed main component was Fe 70 Cr 20 Ni 3 Mo 2 Ti 4 Spherical ferroalloy powder material of La 1 ;
  • the shape of ferroalloy powder is mainly spherical particles, including a small amount of dendrite particles, and some spherical particles contain certain dendrite characteristics, and the particle size range of the spherical particles is 15nm-50 ⁇ m .
  • the initial alloy melt whose main composition is La 27.5 Fe 37.5 Cr 10 Ni 25 is smelted according to the nominal composition of atomic percentage La 27.5 Fe 37.5 Cr 10 Ni 25 through commercially available La, Fe, Cr, Ni raw materials, and the uniform initial alloy melt
  • the cooling rate of about 5000K/s solidifies into an initial alloy strip with a thickness of about 200 ⁇ m.
  • the solidification structure of the initial alloy strip is shown in Fig. 21, including the dispersed particle phase whose main composition is Fe 70 Cr 20 Ni 9 La 1 and the matrix phase whose average composition is mainly La 60 Ni 40.
  • the total volume of the matrix phase is 100%
  • the content of the particles exceeds 50%; the dispersed particle phase is almost all spherical, including only a small amount of dendrite; and some spherical particle phases contain certain dendrite characteristics.
  • the particle size range of the spherical particle phase is 15nm-6 ⁇ m.
  • the La in the matrix phase of the initial alloy ribbon is corroded and removed by dealloying reaction, while retaining part of the nanoporous Ni, that is, the dispersed spherical iron alloy powder whose main component is Fe 70 Cr 20 Ni 9 La 1 is obtained
  • the composite powder of solid material and nanoporous Ni as shown in Figure 22, the floc outside the spherical particles is nanoporous Ni; the shape of the ferroalloy powder is mainly spherical particles, including a small amount of dendritic particles, and some of them are spherical.
  • the particles contain certain dendrite characteristics, and the particle size range of the spherical particles is 15nm-6 ⁇ m.
  • the composite powder of spherical iron alloy powder whose main component is Fe 70 Cr 20 Ni 9 La 1 and nanoporous Ni is pressed into a compact at 100MPa, and then heat treated at 1300°C for 4 hours in a protective atmosphere, and the detected composition is about Fe 52 Cr 15 Ni 33 La 1 high nickel content iron chromium nickel superalloy products.
  • the initial alloy melt whose main composition is La 45 Fe 40 Cr 15 is smelted according to the nominal composition of La 45 Fe 40 Cr 15 in atomic percentage by commercially available La, Fe, Cr raw materials, and the uniform initial alloy melt is about 10 6 K/s -10 7 K/s rapid solidification into initial alloy strips with a thickness of about 20 ⁇ m.
  • the solidified structure of the initial alloy strips consists of a Fe-rich dispersed nanoparticle phase (the particles are too small to detect the composition directly) and a matrix phase mainly composed of La, where the volume percentage of the matrix phase exceeds 60%; the dispersed particle phase is almost All of them are near-spherical nano particles; part of the spherical particle phase contains certain dendrite characteristics, and the particle size range of the spherical particle phase is 5nm-200nm.
  • the La matrix phase in the initial alloy strip was corroded and removed by 0.5mol/L dilute hydrochloric acid solution, and the dispersed detection component was mainly Fe 71 Cr 27 La 2 nano-iron alloy powder material (because of the presence of Cr, making Fe 71 Cr 27 La 2 nano-iron alloy powder particles are not easily dissolved by acid reaction), almost all of them are spherical particles, and some spherical particles contain certain dendrite characteristics, and the particle size range of the nano-iron alloy powder material is 5nm -200nm.
  • the initial alloy melt whose main composition is La 50 Fe 46 Cr 4 is smelted according to the nominal composition of La 50 Fe 46 Cr 4 in atomic percentage by commercially available La, Fe, Cr raw materials, and the uniform initial alloy melt is about 10 4 K/s
  • the rapid cooling solidifies into an initial alloy ribbon with a thickness of about 150 ⁇ m.
  • the solidification structure of the initial alloy ribbon includes a dispersed granular phase mainly composed of Fe 91 Cr 8 La 1 and a matrix phase mainly composed of La; both Cr and La are solid-dissolved in the dispersed granular phase; the iron-rich dispersed granular phase is mainly composed of spherical
  • the particle composition also includes a small amount of dendrite particle phase, and part of the spherical particle phase contains certain dendrite characteristics; the particle size range of the iron-rich spherical particle phase is 15nm-10 ⁇ m.
  • the La matrix phase in the initial alloy ribbon is removed by reaction corrosion with 0.5mol/L dilute hydrochloric acid solution, and the dispersed ferroalloy powder material whose main component is Fe 91 Cr 8 La 1 is obtained, which includes spherical particles and dendritic particles, And it is mainly composed of spherical particles, and some spherical particles contain certain dendrite characteristics; the particle size range of the spherical particles is 15nm-10 ⁇ m.
  • the iron alloy powder material obtained above is subjected to gas siliconization treatment in a mixed gas of silicon chloride (SiCl 4 , or Si 2 Cl 6 , or a mixture of SiCl 4 and Si 2 Cl 6 ) and hydrogen, and the treatment temperature is 400°C -1000°C, you can get spherical iron alloy powder material with high silicon content, its composition is about Fe 81.5 Cr 7 Si 10.5 La 1 , its shape remains roughly unchanged before siliconizing, including spherical particles and dendrite particles, And it is mainly composed of spherical particles, and some spherical particles contain certain dendrite characteristics; the particle size range of the spherical particles is 15nm-10 ⁇ m.
  • the initial alloy melt whose main component is La 35 Fe 50 Cr 15 is smelted according to the nominal composition of La 35 Fe 50 Cr 15 in atomic percentage by commercially available La, Fe, Cr raw materials, and the uniform initial alloy melt is heated at about 10 3 K
  • the cooling rate of /s-10 6 K/s is solidified into primary alloy powder with a particle size of 5 ⁇ m-300 ⁇ m through atomization powder making technology.
  • the solidification structure of the initial alloy powder includes a dispersed particle phase whose main component is Fe 75.5 Cr 23 La 1.5 and a matrix phase whose main component is La, wherein the volume percentage of the matrix phase exceeds 50%; the dispersed particle phase is almost spherical Granular; partly spherical granular phase with some dendritic character.
  • the particle diameter of the spherical particle phase ranges from 5 nm to 10 ⁇ m.
  • the La matrix phase in the initial alloy powder is corroded and removed by 0.5mol/L dilute hydrochloric acid solution, and the dispersed main component is Fe 75.5 Cr 23 La 1.5 finer iron alloy powder material, almost all of which are spherical particles , part of the spherical particle phase contains a certain dendrite feature; the particle size range of the spherical particle is 5nm-10 ⁇ m.
  • the prepared powder material can be used in the fields of common powder metallurgy and metal injection molding (MIM).
  • the initial alloy melt whose main composition is La 50 Fe 49 Cr 0.5 Mo 0.5 is smelted according to the nominal composition of La 50 Fe 49 Cr 0.5 Mo 0.5 in atomic percentage through commercially available La, Fe, Mo, Cr raw materials, and the uniform initial alloy melt
  • the cooling rate of about 10 7 K/s-10 8 K/s solidifies into initial alloy strips with a thickness of about 15 ⁇ m-20 ⁇ m.
  • the solidification structure of the initial alloy strips includes a Fe-rich dispersed nanoparticle phase and a matrix phase mainly composed of La, where the volume percentage of the matrix phase exceeds 65%; the dispersed particle phase is almost all nano-spherical particles; some spherical particles The phase contains certain dendrite characteristics, and the particle diameter of the spherical particle phase ranges from 5nm to 100nm.
  • the La matrix phase in the initial alloy strip was corroded and removed by 0.25mol/L dilute hydrochloric acid solution, and the dispersed detection component was mainly Fe 97 Cr 1 Mo 1 La 1 nano-iron alloy powder material (because Cr, Mo).
  • the existence of nanometer Fe 97 Cr 1 Mo 1 La 1 iron alloy powder particles is difficult to be dissolved by 0.25mol/L dilute hydrochloric acid reaction), almost all of them are spherical particles, and some spherical particles contain certain dendrite characteristics, said The particle size range of the nanometer Fe 97 Cr 1 Mo 1 La 1 iron alloy powder is 5nm-100nm.
  • the obtained nanometer Fe 97 Cr 1 Mo 1 La 1 iron alloy powder particles are used as magnetic solid particles, sodium dodecyl sulfate (SDS) and oleic acid are used as surfactants, and ethanol is used as carrier liquid to prepare magnetic fluid.
  • SDS sodium dodecyl sulfate
  • oleic acid oleic acid
  • ethanol is used as carrier liquid to prepare magnetic fluid.
  • the initial alloy melt whose main composition is La 50 Fe 47 Cr 3 is smelted according to the nominal composition of La 50 Fe 47 Cr 3 in atomic percentage through commercially available La, Fe, Cr raw materials, and the uniform initial alloy melt is about 10 6 K/s
  • the cooling rate of -10 8 K/s solidifies into initial alloy strips with a thickness of about 15 ⁇ m-20 ⁇ m.
  • the solidification structure of the initial alloy strips includes a Fe-rich dispersed nanoparticle phase and a matrix phase mainly composed of La, where the volume percentage of the matrix phase exceeds 65%; the dispersed particle phase is almost all nano-spherical particles; some spherical particles
  • the phase contains certain dendrite characteristics, and the particle size range of the spherical particle phase is 5nm-50nm.
  • the La matrix phase in the initial alloy strip was corroded and removed by 0.5mol/L dilute hydrochloric acid solution, and the dispersed detection component was mainly Fe 93 Cr 6 La 1 nano-iron alloy powder material (because of the presence of Cr, the Nano-Fe 93 Cr 6 La 1 iron alloy powder particles are not easily dissolved by 0.5mol/L dilute hydrochloric acid reaction), almost all of them are spherical particles, and some spherical particles contain certain dendrite characteristics, and the nano-Fe 93 Cr 6 La 1
  • the particle size range of iron alloy powder particles is 5nm-50nm.
  • the obtained nanometer Fe 93 Cr 6 La 1 iron alloy powder particles are used as magnetic solid particles, and mercury is used as carrier liquid to prepare magnetic fluid.
  • the initial alloy melt whose main component is La 50 Fe 50 is smelted according to the atomic percentage of the nominal composition La 50 Fe 50 , and the uniform initial alloy melt is solidified at a cooling rate of about 250K/s to a thickness of about 3mm initial alloy thick strip.
  • the solidification structure of the initial alloy thick ribbon is shown in Figure 23, including the dispersed dendrite phase mainly composed of Fe 99 La 1 and the matrix phase mainly composed of La, wherein the volume percentage of the matrix phase exceeds 70%; the dispersed dendrite phase Almost all of the phases are dendrites.
  • the parts that look like spheres arranged according to the rules in Figure 23 are actually the cross-sectional morphology of dendrite branches. Each row of cross-sectional branches actually belongs to a certain large dendrite.
  • the La matrix phase in the initial alloy thick strip is corroded and removed by 0.5mol/L dilute hydrochloric acid solution, and the dispersed ferroalloy dendrite powder material whose main component is Fe 99 La 1 is obtained, and its shape is mainly dendrite, see Less than spherical particles, as shown in Figure 24. It also clearly shows that there will be rows of secondary dendrites on a large dendrite, and the cross-section of these secondary dendrites corresponds to the regularly arranged "balls" shown in Figure 23 (actually a strip-shaped cross-section) shaped cross-sectional shape. Therefore, the La 50 Fe 50 alloy can only obtain large iron-rich dendritic particles that grow very fully through a slow cooling rate, and cannot obtain iron-rich spherical particles.
  • the initial alloy strips are about 100 ⁇ m.
  • the solidification structure of the initial alloy strip is shown in Figure 25, including a diffuse dendrite phase whose main component is Fe 99 La 1 and a matrix phase whose main component is La; the diffuse dendrite phase is almost all dendrites, adjacent to each other in Figure 25
  • the multiple iron-rich black phases that look like short rods actually belong to one or several dendrites, and the size of these dendrites is about 1-2 ⁇ m.
  • the initial alloy melt whose main composition is La 50 Fe 40 Hf 10 is smelted according to the nominal composition of La 50 Fe 40 Hf 10 in atomic percentage by commercially available La, Fe, Hf raw materials, and the uniform initial alloy melt is cooled at about 500K/s Rapidly solidified into a thick strip of initial alloy with a thickness of about 1 mm.
  • the solidification structure of the initial alloy thick ribbon is shown in Fig. 26, including a black diffuse dendrite phase whose main composition is about Fe 99 La 1 , a white diffuse dendrite phase whose main composition is about Fe 64 Hf 35 La 1 , and a main composition of The matrix phase of La.
  • Hf in the initial alloy melt cannot solid-solute into the iron-rich phase during the solidification process of the melt, but can only be precipitated in the form of Fe 2 Hf intermetallic compound.
  • the Fe-rich phase is still mainly precipitated in the form of dispersed dendrite phase of Fe 99 La 1 . Neither dendrite phase nor spherical particle phase can be obtained. Therefore, when Hf is added to La-Fe alloy, the iron-rich spherical particle phase cannot be obtained.
  • the initial alloy melt whose main component is La 50 Fe 40 Ta 10 is smelted according to the nominal composition of La 50 Fe 40 Ta 10 in atomic percentage through commercially available La, Fe, Ta raw materials, and the uniform initial alloy melt is cooled at about 500K/s Rapidly solidified into a thick strip of initial alloy with a thickness of about 1 mm.
  • the solidification structure of the initial alloy thick ribbon is shown in Figure 27, including a black diffuse dendrite phase with a main component of Fe 99 La 1 and a white flocculent dendrite phase with a main component of Fe 69 Ta 30 La 1 ( Figure 28 As shown by the arrow, it is Fe 7 Ta 3 intermetallic compound) and the matrix phase whose main component is La.
  • Ta in the initial alloy melt cannot solid-solute into the iron-rich phase, but can only be precipitated in the form of Fe 7 Ta 3 intermetallic compounds.
  • the Fe-rich phase is still mainly precipitated in the form of dispersed dendrite phase of Fe 99 La 1 . Neither dendrite phase nor spherical particle phase can be obtained. Therefore, when Ta is added to the La-Fe alloy, the iron-rich spherical particle phase cannot be obtained.

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Abstract

本发明涉及一种球形铁合金粉体材料及其制备方法与用途。通过选择Fe与La的主体合金体系，同时加入特殊的合金球化析出与耐蚀元素，实现了合金凝固过程中初始合金熔体中富Fe且固溶有球化析出元素的球形弥散颗粒相在富La基体相中的弥散析出。通过将富La基体相去除，获得了粒径从纳米级至数十微米的球形铁合金粉体材料。该方法工艺简单，可以制备包括纳米级、亚微米级、微米级的不同形貌的球形铁合金粉体材料，在粉末冶金、金属注射成型(MIM)、3D打印、磁性材料、耐热材料、高温合金、涂料、电热材料、吸波材料、磁流体等领域具有很好的应用前景。

Description

一种球形铁合金粉体材料及其制备方法与用途 技术领域
本发明涉及金属粉体材料技术领域，特别是涉及一种球形铁合金粉体材料及其制备方法与用途。
背景技术
Fe合金是应用最为广泛的金属材料。以微纳粒径的Fe合金粉体为原料，通过粉末冶金、金属注射成型(MIM)、或者3D打印等增材制造技术，可以制备大量性能各异的Fe合金材料。如Fe-Cr铁素体不锈钢，Fe-Cr-Ni奥氏体不锈钢，Fe-Cr-Al电热合金，Fe-Cr-Co永磁体，Fe-Cr-Si软磁材料等。
球形或近球形Fe合金颗粒因其优异的流动性、均匀性、粉体堆垛致密性等优点，是粉末冶金、粉末涂料、金属注射成型(MIM)、3D打印、磁性材料等应用领域的关键原材料。在不少情况下，必须通过球形或近球形颗粒为原料才能获得最终材料需要的应用效果。目前球形Fe合金粉体材料主要通过雾化法制备，即利用高速流体直接击碎液体金属或合金而获得金属粉末。但是由于雾化法雾化能力极限的限制，其一般只适合10μm～150μm的球形Fe合金粉体的制备。对于低于10μm，尤其粒度从纳米至数微米(10μm以下)的球形Fe合金粉体材料，雾化法均难以制备或不能制备。因此，开发粒度从纳米至数微米的超细球形铁合金粉体材料的制备方法，具有重要的应用意义。
发明内容
基于此，有必要针对上述技术问题，提供一种工艺简单、成本低，易于操作的球形铁合金粉体材料的制备方法。为解决上述技术问题，本发明的技术方案包括如下几个方面：
其一方面，一种球形铁合金粉体材料的制备方法，其特征在于，包括如下步骤：
步骤一，选择初始合金原料，按照初始合金成分配比将初始合金原料熔化，得到均匀的初始合金熔体；所述初始合金熔体的主要成分为La xFe yT zM aD b，其中T包含Cr、V中的至少一种，M包含Al、Ni、Co、Si中的至少一种，D包含Mo、W、Ti中的至少一种，x、y、z、a、b分别代表对应组成元素的原子百分比含量，且18％≤x≤95.8％，4％≤y≤81.8％，0.1％≤z≤35％，0≤a≤40％，0≤b≤15％；
步骤二，将初始合金熔体通过快速凝固技术凝固成初始合金固体；所述初始合金固体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的熔点，所述弥散颗粒相被包覆于所述基体相中；所述基体相在凝固组织中的体积百分数不低于40％；所述基体相的平均成分主要为La x1M a1；所述弥散颗粒相的成分主要为Fe y2T z2M a2D b2La x2，其中，x1、a1、x2、y2、z2、a2、b2分别代表对应组成元素的原子百分比含量，且45％≤x1≤100％，0％≤a1≤55％，50％≤y2≤98％，0.2％≤z2<50％，0％≤a2≤30％，0％≤b2≤35％，0<x2≤5％；所述弥散颗粒相中包括可观含量的球形或近球形弥散颗粒相，且部分球形或近球形弥散颗粒相含有一定的枝晶特征；所述弥散颗粒相的粒径大小为5nm～50μm；
步骤三，去除所述初始合金固体中的基体相并主要保留弥散颗粒相，即得到主要成分为Fe y2T z2M a2D b2La x2的铁合金粉体材料；其中，50％≤y2≤98％，0.2％≤z2<50％，0％≤a2≤30％，0％≤b2≤35％， 0<x2≤5％；所述铁合金粉体颗粒中包括可观含量的球形或近球形颗粒，且部分球形或近球形铁合金粉体颗粒含有一定的枝晶特征；所述铁合金粉体颗粒的粒径大小为5nm～50μm。
所述步骤一中，
进一步地，T包含Cr；进一步地，T包含V；
进一步地，M包含Al；进一步地，M包含Ni；进一步地，M包含Co；进一步地，M包含Si；
进一步地，0<a≤40％；进一步地，2.5％<a≤40％，18％≤x≤93.3％；进一步地，5％<a≤40％，18％≤x≤90.8％；
进一步地，10％<a≤40％，18％≤x≤85.8％；
进一步地，D包含Mo；进一步地，D包含W；进一步地，D包含Ti；
进一步地，0<b≤15％；进一步地，0.5％<b≤15％，18％≤x≤95％；
进一步地，18％≤x≤93.8％，6％≤y≤81.8％；作为优选，18％≤x≤89.8％，10％≤y≤81.8％；
进一步地，18％≤x≤95％，0.5％≤z≤35％；进一步地，18％≤x≤94％，1％≤z≤35％；作为优选，18％≤x≤92％，3％≤z≤35％；作为优选，18％≤x≤90％，5％≤z≤35％；
进一步地，18％≤x≤80％；进一步地，18％≤x≤70％；进一步地，18％≤x≤60％；进一步地，18％≤x≤50％；
由于稀土La为大原子，因此即使其在初始合金熔体中具有较低的原子百分比含量，其仍然对应着很大的体积百分含量，而体积百分含量才是弥散颗粒相能否弥散分布的关键。如原子百分比成分为La 20Fe 75Cr 5的合金，根据各元素的原子量与密度，可以计算出La基体的体积百分含量为44.35％。当M类元素也大部分进入基体相时，还可以进一步提高基体相的体积百分含量。
进一步地，y>z，即初始合金熔体中Fe的原子百分比含量高于T类元素的原子百分比含量；
所述步骤二中，
根据La-Fe、La-Cr、La-V、Fe-Cr、Fe-V、Cr-V相图，Fe、Cr、V的熔点均高于La的熔点，Fe、Cr、V均不和La形成金属间化合物，也不明显固溶，且Fe-Cr、Fe-V、Cr-V均为无限固溶合金体系，因此，初始合金熔体凝固过程中，主要由Fe、Cr、V组成的弥散颗粒相首先从合金熔体中析出，而主要由La组成的基体相最后凝固，且合金凝固组织中不含有由La与Fe、Cr、V组成的金属间化合物；也就是说，将初始合金熔体通过快速凝固技术凝固成初始合金固体的过程中，初始合金固体的凝固组织包括富La的基体相与富Fe、Cr或(和)V的弥散颗粒相，且基体相的熔点低于所述弥散颗粒相的熔点，弥散颗粒相被包覆于所述基体相中；
进一步地，所述初始合金熔体凝固速率高于20K/s；作为优选，所述初始合金熔体凝固速率高于50K/s；作为优选，所述初始合金熔体凝固速率高于100K/s；作为优选，所述初始合金熔体凝固速率高于250K/s；作为进一步优选，所述初始合金熔体凝固速率高于500K/s；
进一步地，所述初始合金固体的形状在三维方向上至少有一维的尺度小于10mm；作为优选，所述初始合金固体的形状在三维方向上至少有一维的尺度小于5mm；作为优选，所述初始合金固体的形状在三维方向上至少有一维的尺度小于2mm；作为优选，所述初始合金固体的形状在三维方向上至少有一维的尺度小于1mm；作为优选，所述初始合金固体的形状在三维方向上至少有一维的尺度小于500μm；作为优选，所述初始合金固体的形状在三维方向上至少有一维的尺度小于100μm；
所述初始合金熔体凝固速率越高，可获得的初始合金固体的形状在三维方向上的最小尺度就越小；例如，通过铜辊甩带法以约10 6K/s～10 7K/s的凝固速率，可以获得厚度约为25μm左右的初始合金固体薄带；通过铜模铸造法以约100K/s的凝固速率，可以获得直径约5mm的合金条棒或厚度约5mm的厚板；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。但不同元素不同的固溶或同一元素不同的固溶量可能通过不同的方式阻碍弥散颗粒相在某些方面的正常生长，其可能会引起该规律一定程度的变化；如球化趋势会导致颗粒相在凝固过程中的合并再球化；或抑制形核率，增加长大率等。例如，没有某些元素固溶时，某一冷速获得的弥散颗粒相平均粒径为1μm，但固溶某些元素后，同一冷速可获得球形弥散颗粒相，且颗粒相的平均粒径为5μm。
进一步地，所述初始合金固体的形状包括条状、带状、片状、丝状、颗粒状中的至少一种；作为优选，所述初始合金固体的形状包括条状、带状、片状中的至少一种；
进一步地，所述初始合金固体制备的凝固技术包括熔体甩带、速凝甩片、铸造、连铸、雾化制粉、熔体抽拉中的至少一种；
进一步地，所述初始合金固体为条带状，且条带厚度为5μm～5mm；
进一步地，所述基体相在凝固组织中的体积百分数不低于45％；进一步地，所述基体相在凝固组织中的体积百分数不低于50％；
进一步地，0<x2<x<x1，即初始合金熔体凝固过程中，La富集在基体相中，同时La在弥散颗粒相中有少量存在；
由于基体相中La为大原子，即使基体相中La的原子百分数低至为45％，按照体积百分数计算，La的体积百分含量仍远远大于50％，因此，基体相仍然主要由La组成。
进一步地，50％≤x1≤100％，0％≤a1≤50％；
进一步地，La元素通过固溶的方式存在于Fe y2T z2M a2D b2La x2弥散颗粒相中；
进一步地，0<x2≤3％；
进一步地，0<y<y2，即初始合金熔体凝固过程中，Fe富集在Fe y2T z2M a2D b2La x2弥散颗粒相中；
进一步地，50％≤y2≤95％；进一步地，50％≤y2≤90％；进一步地，50％≤y2≤85％；进一步地，50％≤y2≤75％；
进一步地，0<z<z2，即初始合金熔体凝固过程中，T类元素富集在Fe y2T z2M a2D b2La x2弥散颗粒相中；
进一步地，1％≤z2<50％；进一步地，3％≤z2<50％；进一步地，5％≤z2<50％；进一步地，10％≤z2<50％；
进一步地，y2>z2，即Fe y2T z2M a2D b2La x2弥散颗粒相中Fe的原子百分比含量高于T类元素的原子百分比含量；
进一步地，T类元素通过固溶方式存在于Fe y2T z2M a2D b2La x2弥散颗粒相中；
进一步地，当a＝0时，a2＝a1＝0；当0<a≤40％时，0<a2<a1，即初始合金熔体凝固过程中，M类元素富集在La x1M a1基体相中，同时M类元素在Fe y2T z2M a2D b2La x2弥散颗粒相中也具有一定含量。
进一步地，1％≤a2≤30％；进一步地，3％≤a2≤30％；进一步地，5％≤a2≤30％；进一步地，10％≤a2≤30％；
进一步地，M类元素通过固溶方式存在于Fe y2T z2M a2D b2La x2弥散颗粒相中；
M类元素的特点为：初始合金熔体凝固过程中，M类元素富集在La x1M a1基体相中，同时，M类元素在Fe y2T z2M a2D b2La x2弥散颗粒相中也固溶有相当的含量。
近一步地，当b＝0时，b2＝b＝0；当0<b≤15％时，0<b<b2，即初始合金熔体凝固过程中，D类元素富集在Fe y2T z2M a2D b2La x2弥散颗粒相中；
进一步地，0.5％≤b2≤35％；进一步地，1％≤b2≤35％；进一步地，3％≤b2≤35％；进一步地，5％≤b2≤35％；
进一步地，D类元素通过固溶方式存在于Fe y2T z2M a2D b2La x2弥散颗粒相中；
具体来说，当0<a≤40％时，根据Al-Fe、Si-Fe相图，Al、Si在铁中有很大固溶度，而Fe-Ni、Fe-Co完全固溶，因此M类元素可以固溶在富Fe的弥散颗粒相中。根据Al-La、Ni-La、Co-La、Si-La相图，Al、Ni、Co、Si均可以与La形成富La的金属间化合物。由于富La的金属间化合物熔点低于富Fe的弥散颗粒的熔点，因此初始合金熔体凝固过程中，富Fe的弥散颗粒相首先固溶一定量的M类元素，剩余的M类元素再与La结合形成富La的金属间化合物基体；如果La仍有富余，La x1M a1基体相除了包括M类元素与La形成的富La的金属间化合物外，还包括富余的La相。
当0<b≤15％时，根据La-Ti、La-W、La-Mo相图，Ti、W、Mo均不和La形成金属间化合物，也不明显固溶，因此初始合金熔体凝固过程中，Ti、W、Mo不会进入富La的基体相；根据Fe-Ti、Fe-Mo、Fe-W相图，Ti、W在Fe中有约10at.％的固溶度，Mo在Fe中有约20at.％的固溶度；同时，根据Cr-Ti、Cr-Mo、Cr-W相图，Cr与Ti、Mo、W完全互固溶；根据V-Ti、V-Mo、V-W相图，V与Ti、Mo、W完全互固溶；因此，D类元素Ti、W、Mo与La的元素亲和力极差，与Fe的亲和力不错，与Cr、V的元素亲和力极佳。当初始合金熔体中含有D类元素与Fe、Cr、V元素时，初始合金熔体凝固过程中，所选的D类元素将富集在Fe y2T z2M a2D b2La x2弥散颗粒相中；
需要说明的是，虽然Ti、Zr、Hf为同族元素，且Zr、Hf均不和La形成金属间化合物，也不明显固溶，但与Ti不同，由于Zr、Hf在Fe、Cr、V中同样均几乎没有固溶度，其相互之间只能形成金属间化合物；因此，若当初始合金熔体中含有Zr、Hf时，Zr、Hf几乎不会固溶于Fe y2T z2M a2D b2La x2弥散颗粒相中，而是在Fe y2T z2M a2D b2La x2弥散颗粒相之外，还会另外生成Zr、Hf与Fe、Cr、V的枝晶形金属间化合物相，见对比实施例3。这些金属间化合物均不是本申请所关注的以固溶合金化为主的铁合金相。
同理，Nb、Ta、V虽然为同族元素，且Nb、Ta均不和La形成金属间化合物，也不明显固溶，但与Mo、W、Ti、V不同，由于Nb、Ta在Fe、Cr、V中固溶度极低，其相互之间只能形成金属间化合物；因此，若当初始合金熔体中含有Nb、Ta时，Nb、Ta在Fe y2T z2M a2D b2La x2弥散颗粒相中的固溶度很低，仅能极少量存在或不存在。如果初始合金熔体中含有的Nb、Ta较多时，Nb、Ta在Fe y2T z2M a2D b2La x2弥散颗粒相可能有极少量存在之外，其还会生成Nb、Ta与Fe、Cr、V的枝晶形金属间化合物相，见对比实施例4。这些金属间化合物均不是本申请所关注的以固溶合金化为主的铁合金相。
当初始合金熔体只包含La和Fe，且合金熔体的凝固速率高于10 6K/s时，可以获得一定量的纳米尺度(90nm以下)的枝晶生长不充分的近球形Fe相颗粒。因为如此高的冷速下，即使Fe相颗粒有很强的枝晶化趋势，但由于来不及长大，从而在纳米尺度以枝晶生长不充分的近球形Fe相颗粒凝固析出。但是，由于La和Fe均容易氧化，也均极容易与酸溶液反应溶解。因此，即使通过超高凝固速率制备了90nm以下近球形Fe相颗粒与La基体组成的初始合金固体，也难以通过酸溶液反应溶解的方式将La基体与纳米近球形Fe相颗粒分离，并保留纳米近球形Fe相颗粒(纳米Fe相颗粒也会溶解)。
一般来说，单纯的La-Fe合金熔体的凝固速率低于10 6K/s时，其只能获得枝晶状的Fe相颗粒，难以获得球形或近球形的Fe相颗粒。例如，即使La-Fe合金熔体的凝固速率高至10 5K/s，获得100μm左右的的La-Fe合金条带，其中的弥散颗粒相的形状仍然主要为枝晶形，见对比实施例2。而如果La-Fe合金熔体的凝固速率低于500K/s，弥散颗粒相则为生长即为充分的粒度较大的枝晶相，且将基体相去掉后，获得的枝晶状的Fe相枝晶为交错缠绕在一起的树枝纤维状，见对比实施例1。
当初始合金熔体中包含La和Fe，同时含有高熔点的Cr、V、Mo、W、Ti元素，尤其是含有能和Fe形成完全固溶体的T类元素Cr或(和)V时，初始合金熔体凝固过程中首先析出的为富Fe且固溶有T类 元素的初晶颗粒。由于T类元素的特殊固溶，破坏了原有晶格的形成规律，阻碍了富Fe枝晶相的沿着特定晶面取向的生长，使得富Fe且固溶有T类元素的初晶颗粒产生了球化的倾向。固溶在富Fe初晶相中的T类元素含量越高，就可以在越低的熔体冷速下获得越大的球形或近球形弥散颗粒相。因此，T类元素是本发明发现的富Fe初晶颗粒可以球化的关键，尤其当富Fe弥散颗粒尺寸较大时。
而且，T类元素包括耐腐蚀的Cr、V元素中的至少一种，这些元素与Fe形成的固溶体，即为不锈钢(V的抗蚀能力甚至高于Cr)。因此，T类元素的固溶又使得富Fe弥散颗粒相的耐蚀性极大的提高。由于基体相主要由极易腐蚀的La组成，后续可以很容易地通过与一定浓度的酸溶液反应，将基体相反应腐蚀掉，从而得到分散的富Fe相弥散颗粒。在富Fe相弥散颗粒耐腐蚀性明显增强的情况下，可以采用大于10 6K/s的冷速，制备含有T、D类元素的纳米富铁球形颗粒相的初始合金固体，同时利用含有T、D类元素的纳米富铁球形颗粒相的高耐蚀性将其与富La基体进行酸反应分离，获得纳米级的富铁球形颗粒。
M类元素包括Al、Ni、Co、Si中的至少一种，这些元素均是商业用铁合金的关键元素。如，Al为Fe-Cr-Al电热合金、热喷涂涂层的关键元素之一；Ni为奥氏体不锈钢Fe-Cr-Ni的关键元素之一；Co为Fe-Cr-Co永磁体的关键元素之一；Si为Fe-Cr-Si软磁材料的关键元素之一。根据实际研究结果，初始合金熔体凝固过程中，由于基体也富集较多的M类元素，Si在富Fe相弥散颗粒中原子百分比固溶量一般不超过8％，且需要在初始合金熔体中加入大量Si才能实现；Ni在富Fe相弥散颗粒中原子百分比固溶量一般也不超过12％；Al、Co在富Fe相弥散颗粒中均具有相当可观的固溶量(见实施例)，原子百分比固溶量甚至可以超过20％；而多数上述商用铁合金对M类元素含量值的要求本身也不太高，使得满足上述相关成分的商用铁合金粉末的制备成为了可能。
初始合金熔体中含有M类元素时，部分M类元素也是通过固溶存在于富Fe相弥散颗粒中，因此M类元素对富Fe相弥散颗粒的球化作用也一般有积极作用，见实施例13与实施例14。而且，M类元素、La均较容易与酸溶液反应，因此可以通过酸腐蚀反应，将基体相中的M类元素与La去除，得到自由分散的富Fe相弥散颗粒。如果利用La与M类元素的化学活性差，通过合适的酸溶液依据脱合金原理仅仅主要去掉基体相中的La，则可得到自由分散的富Fe相弥散颗粒粉末与纳米多孔M的复合粉体。
D类元素包括高熔点的Mo、W、Ti元素，这些元素虽然没有T类元素在Fe中的固溶度高(T类元素在Fe中完全固溶)，但D类元素在Fe中有10％-20％的固溶度，且在T类元素中完全固溶。因此，初始合金熔体中适当的添加高熔点的Mo、W、Ti元素，一方面可以增强富Fe相弥散颗粒的球形度、耐腐蚀能力、同时还可以显著提高富Fe相弥散颗粒的熔点与耐热性。如Ti在商用奥氏体不锈钢1Cr18Ni9Ti中的作用，Mo在商用耐超高温Fe-Cr-Al-Mo电热合金中的作用。
综上所述，本申请在La-Fe合金的基础上，所述T类元素、M类元素、D类元素的种类均是通过精心设计与选择的结果。通过这种选择，确保初始合金熔体凝固过程中，Fe、T类元素、D类元素均主要存在于Fe y2T z2M a2D b2La x2弥散颗粒相中，M类元素部分存在于Fe y2T z2M a2D b2La x2弥散颗粒相中；La、M类元素主要存在于La x1M a1基体相中。同时，在Fe y2T z2M a2D b2La x2弥散颗粒相中，M类元素也有相当含量的固溶度，La有较低的固溶度。这种巧妙设计，通过T类元素保证了弥散颗粒的球化趋势，同时提高了其耐腐蚀能力，有利于弥散颗粒相与基体相通过腐蚀反应分离。
由于富Fe弥散颗粒相的球化是通过特殊元素固溶合金化与熔体冷速的调控来抑制富Fe枝晶相的形成与生长实现的。富Fe弥散颗粒相中固溶的T类元素含量越高，或包括T类元素在内的固溶元素总含量越高，或熔体的冷速越高，越容易生成球形或近球形富Fe弥散颗粒相。因此，达到相同的球化效果，当富Fe弥散颗粒相中固溶元素含量越高时，可采用较低的冷速；当固溶元素含量较低时，需要较高的冷速。实 际中，通过调控参数，球形或近球形弥散颗粒相在所有弥散颗粒相中的体积百分含量可以无限接近100％，但不能达到100％。
进一步地，所述球形或近球形弥散颗粒相的球形度(球度)超过50％；
进一步地，所述球形或近球形弥散颗粒相的球形度超过70％；
进一步地，所述球形或近球形弥散颗粒相的球形度超过85％；
进一步地，所述球形或近球形弥散颗粒相的球形度超过95％；
进一步地，球形或近球形弥散颗粒相在所有弥散颗粒相中的体积百分含量大于10％；
说明：为了表述方便，本申请某些地方用到了“球形”，某些地方用到了“球形或近球形”，其实本申请全篇所述“球形”即包括了球形与近球形的意思，因为现实中没有理想的球体。
由于单纯的La-Fe合金通过所述方法几乎得不到球形弥散颗粒相；或者需要通过极高冷速才能得到90nm以下近球形Fe相颗粒，且其也难以与La基体通过酸反应脱落获得这种纳米颗粒(纳米Fe颗粒也会与酸反应，被溶解)。因此，通过合金设计，加入耐腐蚀元素Cr或(和)V后，或者同时有较多D类元素加入后，如果使得球形或近球形弥散颗粒相在所有弥散颗粒相中的体积百分含量大于10％，可以认为获得了可观含量的球形或近球形弥散颗粒相；
进一步地，球形或近球形弥散颗粒相在所有弥散颗粒相中的体积百分含量大于25％；
进一步地，所述弥散颗粒相的形状主要为球形或近球形；
进一步地，球形或近球形弥散颗粒相在所有弥散颗粒相中的体积百分含量大于50％；
进一步地，球形或近球形弥散颗粒相在所有弥散颗粒相中的体积百分含量大于75％；
进一步地，球形或近球形弥散颗粒相在所有弥散颗粒相中的体积百分含量大于90％；
进一步地，球形或近球形弥散颗粒相在所有弥散颗粒相中的体积百分含量大于95％；
一般来说，当富Fe弥散颗粒相中固溶的T类元素含量超过2％，或包括T类元素在内的固溶元素总含量超过4％，熔体的冷速超过500K/s时，球形或近球形弥散颗粒相在所有弥散颗粒相中的体积百分含量大于50％；
进一步地，当富Fe弥散颗粒相中固溶的T类元素含量超过4％，或包括T类元素在内的固溶元素总含量超过8％，熔体的冷速超过250K/s时，球形或近球形弥散颗粒相在所有弥散颗粒相中的体积百分含量大于50％；
进一步地，当富Fe弥散颗粒相中固溶的T类元素含量超过8％，或包括T类元素在内的固溶元素总含量超过12％，熔体的冷速超过100K/s时，球形或近球形弥散颗粒相在所有弥散颗粒相中的体积百分含量大于50％；
进一步地，当富Fe弥散颗粒相中固溶的T类元素含量超过12％，或包括T类元素在内的固溶元素总含量超过18％，熔体的冷速超过50K/s时，球形或近球形弥散颗粒相在所有弥散颗粒相中的体积百分含量大于50％；
进一步地，当富Fe弥散颗粒相中固溶的T类元素含量超过16％，或包括T类元素在内的固溶元素总含量超过25％，熔体的冷速超过20K/s时，球形或近球形弥散颗粒相在所有弥散颗粒相中的体积百分含量大于50％；
进一步地，当富Fe弥散颗粒相中固溶的T类元素含量超过16％，或包括T类元素在内的固溶元素总含量超过25％，熔体的冷速超过100K/s时，球形或近球形弥散颗粒相在所有弥散颗粒相中的体积百分含量大于95％；
进一步地，当弥散颗粒相的平均粒径超过0.25μm时，仍然可以获得球形度超过85％的弥散颗粒相；
进一步地，当弥散颗粒相的平均粒径超过0.25μm时，仍然可以通过冷速与合金成分的调控获得球形度超过85％的弥散颗粒相；
进一步地，当弥散颗粒相的平均粒径超过0.5μm时，仍然可以通过冷速与合金成分的调控获得球形度超过85％的弥散颗粒相；
进一步地，当弥散颗粒相的平均粒径超过1μm时，仍然可以通过冷速与合金成分的调控获得球形度超过85％的弥散颗粒相；
进一步地，当弥散颗粒相的平均粒径超过3μm时，仍然可以通过冷速与合金成分的调控获得球形度超过85％的弥散颗粒相；
进一步地，所述部分球形或近球形弥散颗粒相含有一定的枝晶特征，是指部分球形或近球形弥散颗粒相上长出凸起状短枝晶，其使得整个球形或近球形弥散颗粒相具有类似“冠状”病毒的形状特性(在球形或近球形弥散颗粒相上长出的凸起状短枝晶即对应于“冠状”病毒球上的冠状凸起)；
进一步地，凸起状短枝晶的个数为一个或多个，其从球形表面算起进一步凸起的长度低于球形颗粒半径；具体形状见实施例；
进一步地，凸起状短枝晶的个数为一个或多个，其从球形表面算起进一步凸起的长度低于球形颗粒半径的一半；
虽然这种球化不充分的凸起状短枝晶对颗粒相的球形度有一定影响，但由于凸起状短枝晶依附生长的球形颗粒相的球形度本身很高，凸起状短枝晶较短，且一般在颗粒表面对称均匀分布，因此，即使部分球形或近球形弥散颗粒相含有球化不充分的凸起状短枝晶特征，但这种颗粒仍然属于球形度较高的球形或近球形颗粒，属于球形或近球形颗粒的统计范畴。
进一步地，所述弥散颗粒相的形状主要为球形或近球形；除此之外，弥散颗粒相中还含有少量典型的枝晶颗粒相。所述枝晶颗粒是典型的枝晶形貌，看不出球形的样子，不属于球形或近球形颗粒的统计范畴。
所述弥散颗粒相的形状主要为球形或近球形，且部分球形或近球形弥散颗粒相含有一定的枝晶特征；同时，弥散颗粒相中还含有少量典型的枝晶颗粒相。这两种枝晶形特征的存在，是通过本申请获得的富铁弥散颗粒相所拥有的独一无二的特征。
进一步地，凸起状短枝晶从球形表面算起进一步凸起的长度低于球形颗粒半径的三分一；
进一步地，凸起状短枝晶从球形表面算起进一步凸起的长度低于球形颗粒半径的五分一；
进一步地，所述弥散颗粒相的粒径大小为5nm～40μm；
进一步地，所述弥散颗粒相的粒径大小为5nm～30μm；进一步地，所述弥散颗粒相的粒径大小为5nm～20μm；进一步地，所述弥散颗粒相的粒径大小为5nm～10μm；
进一步地，所述弥散颗粒相的粒径大小为100nm～50μm；
进一步地，所述弥散颗粒相的粒径大小为250nm～50μm；
进一步地，所述弥散颗粒相的粒径大小为500nm～50μm；
进一步地，所述弥散颗粒相的粒径大小为5nm～100nm；
进一步地，所述弥散颗粒相的粒径大小为5nm～50nm；
由于弥散颗粒相的大小与初始合金熔体的凝固速率成负相关的关系，即凝固速率越高，弥散颗粒相粒径越小，因此，当弥散颗粒相的粒径越小时，初始合金熔体的凝固速率越高，所对应的弥散颗粒相的球化率也就越高，球形或近球形弥散颗粒相在所有弥散颗粒相中的体积百分含量也就越高；
进一步地，所述弥散颗粒相中单晶颗粒数目在所有颗粒数目中的占比不低于60％。
所述步骤三中，由于主要成分为Fe y2T z2M a2D b2La x2的铁合金粉体材料是通过去除所述初始合金固体中的基体相并保留弥散颗粒相得到的，因此，所述铁合金粉体材料的特征(包括颗粒形状)即为步骤二中所述弥散颗粒相对应的特征，这些特征详见步骤二所述。
进一步地，去除所述基体相并保留弥散颗粒相的方法包括酸溶液溶解反应去除、基体氧化-粉化去除中的至少一种。
当采用酸溶液反应去除时，选择合适的酸品种与浓度，其选择的标准是保证平均成分主要为La x1M a1的基体相变成离子进入溶液，而主要成分为Fe y2T z2M a2D b2La x2的弥散颗粒相几乎不与相应的酸反应，从而实现基体相的去除，得到主要成分为Fe y2T z2M a2D b2La x2的铁合金粉体材料；或者选择合适的酸品种与浓度，其选择的标准是保证平均成分主要为La x1M a1的基体相变纳米多孔M(只主要腐蚀La)，而主要成分为Fe y2T z2M a2D b2La x2的弥散颗粒相几乎不与相应的酸反应，得到纳米多孔M与Fe y2T z2M a2D b2La x2弥散颗粒的复合粉体；
当Fe中固溶含有Cr、V时，其即为铁素体不锈钢成分，主要成分为Fe y2T z2M a2D b2La x2的弥散颗粒相就有很好的耐酸腐蚀性，而La、M类元素则为极易与酸溶液反应的元素，因此可以非常容易地将富La基体相去除，得到主要成分为Fe y2T z2M a2D b2La x2的铁合金粉体材料。
由于La极易在空气下氧化-粉化，因此，除了酸溶液溶解反应去除外，还可以通过干法的方式去除初始合金固体中富La基体相。当富La基体氧化-粉化后，富Fe的弥散颗粒相就自动脱落出来，可通过其具有磁性的特征，通过磁场将富Fe粉体颗粒收集起来，实现其与富La基体相的分离。
进一步地，初始合金固体富La基体相的氧化-粉化过程在热处理的情况下加速进行；通过热处理加热，迅速将富La基体相氧化-粉化，从而提高分离效率。由于Cr、V等元素的添加，富Fe颗粒相的抗氧化性增强，控制好加热温度，不会导致富Fe颗粒的氧化。
进一步地，所述热处理温度为50℃～1000℃；作为优选，所述热处理温度为50℃～600℃；作为优选，所述热处理温度为50℃～200℃；
进一步地，球形或近球形铁合金粉体颗粒在所有铁合金粉体颗粒中的体积百分含量可以无限接近100％，但不能达到100％。也就是说，所述铁合金粉体颗粒的形状主要为球形或近球形，且部分球形或近球形铁合金粉体颗粒含有球化不充分的枝晶特征；
进一步地，所述球形或近球形铁合金粉体颗粒的球形度(球度)超过50％；
进一步地，所述球形或近球形铁合金粉体颗粒的球形度超过70％；
进一步地，所述球形或近球形铁合金粉体颗粒的球形度超过85％；
进一步地，所述球形或近球形铁合金粉体颗粒的球形度超过95％；
进一步地，球形或近球形铁合金粉体颗粒在所有铁合金粉体中的体积百分含量大于10％；
进一步地，球形或近球形铁合金粉体颗粒在所有铁合金粉体中的体积百分含量大于25％；
进一步地，所述铁合金粉体颗粒的形状主要为球形或近球形；
进一步地，球形或近球形铁合金粉体颗粒在所有铁合金粉体中的体积百分含量大于50％；
进一步地，球形或近球形铁合金粉体颗粒在所有铁合金粉体中的体积百分含量大于75％；
进一步地，球形或近球形铁合金粉体颗粒在所有铁合金粉体中的体积百分含量大于90％；
进一步地，球形或近球形铁合金粉体颗粒在所有铁合金粉体中的体积百分含量大于95％；
一般来说，当铁合金粉体颗粒中固溶的T类元素含量超过2％，或包括T类元素在内的固溶元素总含量超过4％，熔体的冷速超过500K/s时，球形或近球形铁合金粉体颗粒在所有铁合金粉体颗粒中的体积百分含量大于50％；
进一步地，当铁合金粉体颗粒中固溶的T类元素含量超过4％，或包括T类元素在内的固溶元素总含量超过8％，熔体的冷速超过250K/s时，球形或近球形铁合金粉体颗粒在所有铁合金粉体颗粒中的体积百分含量大于50％；
进一步地，当铁合金粉体颗粒中固溶的T类元素含量超过8％，或包括T类元素在内的固溶元素总含量超过12％，熔体的冷速超过100K/s时，球形或近球形铁合金粉体颗粒在所有铁合金粉体颗粒中的体积百分含量大于50％；
进一步地，当铁合金粉体颗粒中固溶的T类元素含量超过12％，或包括T类元素在内的固溶元素总含量超过18％，熔体的冷速超过50K/s时，球形或近球形铁合金粉体颗粒在所有铁合金粉体颗粒中的体积百分含量大于50％；
进一步地，当铁合金粉体颗粒中固溶的T类元素含量超过16％，或包括T类元素在内的固溶元素总含量超过25％，熔体的冷速超过20K/s时，球形或近球形铁合金粉体颗粒在所有铁合金粉体颗粒中的体积百分含量大于50％；
进一步地，当铁合金粉体颗粒中固溶的T类元素含量超过16％，或包括T类元素在内的固溶元素总含量超过25％，熔体的冷速超过100K/s时，球形或近球形铁合金粉体颗粒在所有铁合金粉体颗粒中的体积百分含量大于95％；
进一步地，所述部分球形或近球形铁合金粉体颗粒含有一定的枝晶特征，是指部分球形或近球形铁合金粉体颗粒上长出凸起状短枝晶，其使得整个球形或近球形铁合金粉体颗粒具有类似“冠状”病毒的形状特性(在球形或近球形铁合金粉体颗粒上长出的凸起状短枝晶即对应于“冠状”病毒球上的冠状凸起)；凸起状短枝晶具体形状见实施例；虽然这种球化不充分的凸起状短枝晶对铁合金粉体颗粒的球形度有一定影响，但由于凸起状短枝晶依附生长的铁合金粉体颗粒的球形度本身很高，因此，即使部分球形或近球形铁合金粉体颗粒含有一定的凸起状短枝晶特征，但这种颗粒仍然属于球形度较高的球形或近球形铁合金粉体颗粒。
进一步地，所述铁合金粉体颗粒的形状主要为球形或近球形；除此之外，铁合金粉体颗粒中还含有少量典型的枝晶粉体颗粒。
所述铁合金粉体颗粒的形状主要为球形或近球形，且部分球形或近球形铁合金粉体颗粒含有一定的枝晶特征；同时，铁合金粉体颗粒中还含有少量典型的枝晶颗粒。这两种枝晶形特征的存在，是通过本申请获得的铁合金粉体颗粒所拥有的独一无二的特征。
进一步地，所述铁合金粉体颗粒的粒径大小为5nm～40μm；进一步地，所述铁合金粉体颗粒的粒径大小为5nm～30μm；进一步地，所述铁合金粉体颗粒的粒径大小为5nm～20μm；进一步地，所述铁合金粉体颗粒的粒径大小为5nm～10μm；
进一步地，所述铁合金粉体颗粒的粒径大小为100nm～50μm；
进一步地，所述铁合金粉体颗粒的粒径大小为250nm～50μm；
进一步地，所述铁合金粉体颗粒的粒径大小为500nm～50μm；
进一步地，所述铁合金粉体颗粒的粒径大小为5nm～100nm；
进一步地，所述铁合金粉体颗粒的粒径大小为5nm～50nm；
进一步地，当铁合金粉体颗粒的平均粒度大于0.25μm的时候，粉体颗粒的形状仍然以球形为主；
进一步地，当铁合金粉体颗粒的平均粒度大于0.5μm的时候，粉体颗粒的形状仍然以球形为主；
进一步地，当铁合金粉体颗粒的平均粒度大于1μm的时候，粉体颗粒的形状仍然以球形为主；
进一步地，当铁合金粉体颗粒的平均粒度大于3μm的时候，粉体颗粒的形状仍然以球形为主；
进一步地，所述铁合金粉体颗粒中单晶颗粒数目在所有颗粒数目中的占比不低于60％。
在所有稀土元素中，La是一个特例，而所有铁系元素Fe、Co、Ni中，Fe也是一个特例，因为铁系元素与稀土元素的多种组合中，只有La-Fe合金不形成金属间化合物，两种元素也不明显相互固溶；针对这一特点的利用是本发明中初始合金固体的凝固组织中形成富La的基体相与富Fe的弥散颗粒相的基础。在此基础上，通过对T类元素、M类元素、D类元素的选择与含量控制，使得初始合金熔体凝固过程中原本的枝晶颗粒相改变生长规律变成球形或近球形颗粒相，获得成分大体与商用合金类似，但粒度又可以有明显不同(如粒度更小，氧杂质更低、固溶有稀土元素)的超细球形铁合金粉末，是本申请创造性的关键所在。如果没有通过对T类元素、M类元素、D类元素的选择与含量控制，发现并利用T类元素的球化作用，简单地通过La-Fe合金，只能获得枝晶状的易于腐蚀的Fe枝晶粉末，没有颗粒的流动性，粉末冶金的致密性也较低，则应用价值极大的受到限制。
实际过程中，作为稀土元素原料，La原料中也可以包含少量的其它稀土元素，只要其它稀土元素的原子百分比含量不超过La原料含量的25％，则对规律的影响不大。这些其它稀土都固溶在La中，替代部分La的作用。此时，本发明中La的意思就代表了La稀土与其它稀土了。
进一步地，步骤一所述初始合金熔体的组成还包括非金属杂质元素，所述非金属杂质元素包括O、N、H、P、S、Cl中的至少一种；所述非金属杂质元素在初始合金熔体中的原子百分比含量大于0，且小于10％；步骤二所述富Fe弥散颗粒相的形成过程中，所述非金属杂质元素被富集在富La基体相，从而对富Fe弥散颗粒相进行了提纯处理，即富Fe弥散颗粒相中所述非金属杂质元素的原子百分比含量低于初始合金熔体中所述非金属杂质元素的原子百分比含量；且所述富Fe弥散颗粒相中，非金属杂质元素的原子百分比含量低于1.5％；且步骤三所述球形或近球形铁合金粉体颗粒中非金属杂质元素含量也低于初始合金熔体中所述非金属杂质元素的含量。
进一步地，对所得铁合金粉体颗粒进行粒度分级，例如分离出10μm以上粉体，1μm-5μm粉体，5μm-10μm粉体，1μm以下粉体等，得到不同粒度的球形铁合金粉体材料，可应用于不同的领域。
其二方面，本发明还涉及一种球形铁合金粉体材料，其特征在于，通过其一方面所述的球形铁合金粉体材料的制备方法制备，其特征详见于其一方面所述；
所述球形铁合金粉体材料的部分特征包括：球形铁合金粉体材料的主要成分为Fe y2T z2M a2D b2La x2；其中，50％≤y2≤98％，0.2％≤z2<50％，0％≤a2≤30％，0％≤b2≤35％，0<x2≤5％；所述铁合金粉体颗粒的形状主要为球形或近球形，且部分球形或近球形铁合金粉体颗粒含有一定的枝晶特征；所述铁合金粉体颗粒的粒径大小为5nm～50μm。
进一步地，所述球形或近球形铁合金粉体颗粒的球形度超过65％；
进一步地，所述球形或近球形铁合金粉体颗粒在所有铁合金粉体中的体积百分含量大于25％；
进一步地，所述球形或近球形铁合金粉体颗粒中，O、N、H、P、S、Cl元素的原子百分比总含量低于1.5％。
进一步地，所述T包含Cr、V中的至少一种，M包含Al、Ni、Co、Si中的至少一种，D包含Mo、W、Ti中的至少一种；x1、a1、x2、y2、z2、a2、b2分别代表对应组成元素的原子百分比含量。
其三方面，本发明还涉及一种高硅含量球形铁铬硅粉体材料的制备方法，其特征在于，将其一方面步骤一至步骤三制备的主要组成元素为Fe-Cr的球形铁合金粉体材料或低Si含量的主要组成元素为Fe-Cr-Si的球形铁合金粉体材料进行渗Si处理，即得到高Si含量的主要组成为Fe-Cr-Si的球形粉体材料。
由于直接通过其一方面步骤一至步骤三获得的Fe-Cr-Si球形铁合金粉体材料中的Si原子百分比固溶度难以超过8％，且仅在初始合金熔体中含有大量Si时才能实现，而实际商用Fe-Cr-Si磁性铁合金粉体中Si的原子百分比一般要超过8％。为了获得更高的Si含量，可以通过对其一方面步骤一至步骤三制备的主要组成元素为Fe-Cr的球形铁合金粉体材料或低Si含量的主要组成元素为Fe-Cr-Si的球形铁合金粉体材料进行渗Si处理，得到高Si含量的球形Fe-Cr-Si粉体材料。
进一步地，所述渗Si处理包括固体渗Si、液体渗Si、气体渗Si工艺中的至少一种。
进一步地，固体渗Si的硅源包括Si或富硅合金中的至少一种；液体渗硅的硅源主要为含Si的液体；气体渗硅的硅源主要为含Si的气体；
进一步地，固体渗硅的处理温度为400℃～1200℃。
进一步地，本发明还提供一种渗硅的改进工艺：
进一步地，按照其一方面步骤一与步骤二，制备其一方面步骤二所述的初始合金固体；其中，T包含Cr，M包含Si，0<a≤40％；所述基体相的平均成分主要为La x1Si a1；所述弥散颗粒相的成分主要为低Si含量的Fe y2Cr z2Si a2D b2La x2；所述La x1Si a1基体相中Si通过金属间化合物的方式与La结合；0<a2≤8％；通过稀酸溶液将所述的初始合金固体La x1Si a1基体相中的La通过脱合金反应去除，同时保留原La x1Si a1基体相中的Si，得到纳米多孔Si与所述低Si含量的Fe y2Cr z2Si a2D b2La x2颗粒的复合粉体；所述纳米多孔Si即可以作为Fe y2Cr z2Si a2D b2La x2粉体进行渗Si的Si源。
进一步地，所述纳米多孔Si作为Si源对低Si含量的Fe y2Cr z2Si a2D b2La x2颗粒进行渗Si处理，即得到高Si含量的球形Fe-Cr-Si粉体材料；
进一步地，纳米多孔Si与所述低Si含量的Fe y2Cr z2Si a2D b2La x2颗粒固体渗Si的方式包括：直接进行固体渗Si，或首先将其压制密实后再进行固体渗Si操作；
进一步地，固体渗Si的处理温度为400℃～1200℃；
进一步地，所述获得的高Si含量的球形Fe-Cr-Si粉体材料的成分主要为Fe y3Cr z3Si a3D b3La x3；其中x3、y3、z3、a3、b3分别代表对应组成元素的原子百分比含量，且0<y3<y2，0<z3<z2，0<a2<a3，0≤b3≤b2，0<x3<x2。
进一步地，5％<a3；进一步地，10％<a3；
进一步地，所述高Si含量的球形Fe-Cr-Si粉体材料，除了Si含量通过渗硅处理提高，同时导致合金成分组成相应自动调整外，粉体材料的形貌、大小仍然基本保持与渗硅处理之前基本一致。
进一步地，由于Si为脆性，因此渗硅处理后，通过分散、破碎技术还能将渗硅处理后的高Si含量的球形Fe-Cr-Si粉体材料重新粉化成松散的颗粒状。即使高Si含量的球形Fe-Cr-Si粉体表面可能残留有未完全渗入的剩余纳米多孔Si，但其有时也是有益的存在。
进一步地，对所得高Si含量球形Fe-Cr-Si粉体颗粒进行粒度分级，例如分离出10μm以上粉体，1μm-5μm粉体，5μm-10μm粉体，1μm以下粉体等，得到不同粒度的高Si含量球形Fe-Cr-Si粉体材料，可应用于不同的领域。
其四方面，本发明还涉及一种高硅含量球形铁铬硅粉体材料，其特征在于，通过其三方面所述的高硅含量球形铁铬硅粉体材料的制备方法制备，其具体特征见其三方面所述。
其五方面，本发明还涉及一种纳米多孔Si与球形Fe-Cr-Si颗粒的复合粉体，其特征在于，通过其三方面渗硅改进工艺制备纳米多孔Si与低Si含量的Fe y2Cr z2Si a2D b2La x2颗粒的复合粉体，即得到纳米多孔Si与球形Fe-Cr-Si颗粒的复合粉体；其特征见其三方面渗硅改进工艺所述。
其六方面，本发明还涉及一种高镍含量铁铬镍粉末冶金制品的制备方法，其特征在于，包括如下步骤：
步骤1，按照其一方面的步骤一与步骤二，制备其一方面步骤二所述的初始合金固体；其中，T包含Cr，M包含Ni，0<a≤40％；所述基体相的平均成分主要为La x1Ni a1；所述弥散颗粒相的成分主要为低Ni含量的Fe y2Cr z2Ni a2D b2La x2；所述La x1Ni a1基体相中Ni通过金属间化合物的方式与La结合；0<a2≤12％；
步骤2，通过稀酸溶液将所述的初始合金固体La x1Ni a1基体相中的La通过脱合金反应去除，同时确保原La x1Ni a1基体相中大部分Ni不被反应去除，得到纳米多孔Ni与低Ni含量Fe y2Cr z2Ni a2D b2La x2颗粒的复合粉体；
步骤3，将纳米多孔Ni与所述低Ni含量Fe y2Cr z2Ni a2D b2La x2颗粒的复合粉体压制成型并进行热处理烧结，即获得高Ni含量的铁铬镍粉末冶金制品，其主要成分组成为Fe y3Cr z3Ni a3D b3La x3；其中，x3、y3、z3、a3、b3分别代表对应组成元素的原子百分比含量，且0<y3<y2，0<z3<z2，0<a2<a3，0≤b3≤b2，0<x3<x2。
其一方面初始合金熔体凝固过程中，由于基体富集较多的Ni元素，Ni在富Fe相弥散颗粒中的原子百分比固溶量一般不超过12％。一般来说，Fe-Ni基高温合金中的Ni含量需要达到30％-40％，因此，通过本方法提高低Ni含量的Fe y2Cr z2Ni a2D b2La x2颗粒中的Ni含量，可以获得高Ni含量的铁铬镍粉末冶金制品，适用于高温合金领域。
所述步骤1中，
进一步地，18％≤x≤85％，10％≤y≤81.8％，5％≤a≤40％；2％≤z≤35％，0≤b≤15％；45％≤x1≤100％，0％≤a1≤55％，50％≤y2≤85％，4％≤z2<50％；
进一步地，所述La x1Ni a1基体相中Ni通过金属间化合物与La结合的方式包括La 3Ni金属间化合物、La 7Ni 3金属间化合物、LaNi金属间化合物中的至少一种；
所述步骤2中，
虽然La和Ni均能与酸反应，但稀土La的反应活性更高，且金属间化合物中一般La含量更高。因此，可通过调整稀酸的品种与浓度，使得La可以被脱合金反应腐蚀去除，虽然有少量Ni不可避免地腐蚀溶解，但大部分Ni可以通过脱合金反应变成纳米多孔Ni而保留下来。而低Ni含量的Fe y2Cr z2Ni a2D b2La x2颗粒相含有Cr，耐腐蚀，可以完全保留下来；
进一步地，所述纳米多孔Ni系带尺寸低于200nm；
由于本申请脱合金反应后纳米多孔Ni碎化明显，不能作为完整基体保留，因此所获得的纳米多孔Ni与所述低Ni含量的Fe y2Cr z2Ni a2D b2La x2颗粒的复合粉体中，低Ni含量的Fe y2Cr z2Ni a2D b2La x2颗粒已经被自由脱离出来，只是其与纳米多孔Ni碎片混合在一起。
所述步骤3中，
进一步地，所述压制成型与热处理烧结可以先后进行，也可以同时进行；同时进行即为热压烧结；
进一步地，所述热处理烧结温度低于低Ni含量Fe y2Cr z2Ni a2D b2La x2颗粒的熔点；
进一步地，所述热处理烧结温度为400℃～1400℃；
进一步地，所述热处理烧结温度为400℃～1100℃；
进一步地，所述热处理烧结温度为400℃～900℃；
进一步地，所述热处理烧结过程中，纳米多孔Ni进入低Ni含量的Fe y2Cr z2Ni a2D b2La x2颗粒，并固溶于其中，使其镍含量提高；
进一步地，10％<a3；进一步地，15％<a3；进一步地，20％<a3；进一步地，30％<a3。
其七方面，本发明还涉及一种高镍含量铁铬镍粉末冶金制品，其特征在于，通过其六方面所述的高镍含量铁铬镍粉末冶金制品的制备方法制备；其特征见其六方面所述。
其八方面，本发明还涉及一种纳米多孔Ni与低Ni含量铁铬镍颗粒的复合粉体，其特征在于，通过其六方面所述方法的步骤1与步骤2制备；其特征见其六方面所述。
其九方面，本发明还涉及其二方面所述的球形铁合金粉体材料在以下任意一种领域的应用，所述应用领域包括普通粉末冶金、金属注射成型(MIM)、3D打印、磁性材料、耐热材料、高温合金、涂料、吸波材料。
在普通粉末冶金方面，本发明其一方面与其二方面所涉及的球形铁合金粉体材料均可用于普通粉末冶金领域。即通过所述粉体压制成坯，然后直接烧结出相应成分的块体粉末冶金制品，或将所述粉体与其它粉体复合，然后压制成坯，烧结出相应复合成分的块体粉末冶金制品。所述其它粉体包括其它成分的金属粉、合金粉、氧化物粉、碳化物粉、氮化物粉、碳粉、陶瓷粉中的至少一种；
在金属注射成型(MIM)方面，MIM理论上最佳的粉体材料粒径为0.5μm～10μm，但目前由于技术限制，MIM所用粉体材料的粒径一般大于10μm，甚超过50μm；本发明所述方法非常适合0.5μm～10μm粉体的制备，且粉体越细越容易制备。因此，本发明其一方面与其二方面所涉及的铁合金粉体材料均非常适用于金属注射成型(MIM)领域。MIM技术与普通粉末冶金技术的不同点在于，MIM通过粉末与有机粘接剂一起做坯，去掉有机粘接剂后，再进行烧结得到制品，由于去除了粘接剂，烧结制品相对坯体的体积有10％～20％的收缩。
在3D打印方面，细粉的铺粉3D打印需要粒径15μm～53μm左右的球形粉体。本发明中，当Fe中固溶的元素含量很高，且Cr、V含量很高时，可以获得这一粒径范围的球形铁合金粉，且通过进一步筛分，可以将这一粒径范围的粉体集中起来。因此，本发明其一方面与其二方面所涉及的球形铁合金粉体材料在某些情况下也可用于3D打印领域。
在磁性材料方面，本发明其一方面与其二方面所涉及部分成分的球形铁合金粉体材料还可用于软磁材料或硬磁材料(永磁体)。如主要元素组成为Fe-Cr、Fe-Cr-Si的粉体材料可以用于软磁材料(如磁粉芯)，而主要元素组成为Fe-Cr-Co的粉体材料则可以用于硬磁材料。
进一步地，当本发明所涉及的主要元素组成为Fe-Cr、Fe-Cr-Si的粉体材料用于软磁材料时，包括作为磁粉芯应用。
进一步地，所述磁粉芯通过主要元素组成为Fe-Cr、Fe-Cr-Si的粉体材料施加绝缘包覆材料进行包覆，然后在一定温度下压制而成；进一步地，所述压制温度为室温至800℃。
进一步地，所述绝缘包覆材料在磁粉芯中的重量百分比超过0.1％，低于15％；
进一步地，所述绝缘包覆材料包括树脂；作为优选，所述绝缘包覆材料包括硅树脂，酚醛树脂，环氧树脂，聚丙烯、尼龙中的至少一种。
在耐热材料方面，本发明其一方面与其二方面所涉及的含V、W、Mo、Ti等高熔点元素的球形铁合金粉体材料，或含有Al且在高温下可形成氧化铝耐热保护层的球形铁合金粉体材料，如主要元素组成为Fe-Cr-Al、Fe-Cr-Al-(V/W/Mo/Ti)的球形铁合金粉体材料制备的粉末材料或粉末冶金制品、MIM制品，可大大提升其耐热性，可用于耐热材料。在工业应用中，如加热炉、换热器、纤维燃烧器和热气体过滤系统等各个方面，特别是作为尾气催化剂金属蜂窝载体方面，铁铬铝粉冶合金制品相比传统的陶瓷蜂窝载体，优势更加明显。
在高温合金方面，本发明其一方面与其二方面所涉及的含V、W、Mo、Ti等高熔点元素的球形铁合金粉体材料，如主要元素组成为Fe-Cr-Ni-(V/W/Mo/Ti)的球形铁合金粉体材料制备的制品，具有很好的耐高温能力。当本发明其一方面与其二方面所涉及的含V、W、Mo、Ti等高熔点元素的球形铁合金粉体材料的成分与高温合金的成分相同或接近时，其可以用于高温合金领域。
在涂料方面，本发明其一方面与其二方面所涉及的球形铁合金粉体材料可作为关键组分，应用于涂料领域，包括热喷涂涂料、树脂基涂料、磁屏蔽涂料；
在吸波材料方面，本发明其一方面与其二方面所涉及的球形铁合金粉体材料可作为磁性金属粉应用于吸波材料领域。
其十方面，本发明还涉及其二方面所述的球形铁合金粉体材料在电热材料领域的应用，且所述球形铁合金粉体材料主要成分包括Fe-Cr-Al。
在电热材料领域，本发明其一方面与其二方面所涉及的主要元素组成为Fe-Cr-Al、Fe-Cr-Al-(V/W/Mo/Ti)的粉体材料，通过粉末冶金技术制成成品后，是非常优异的电热材料。如所述主要元素组成为Fe-Cr-Al、Fe-Cr-Al-(V/W/Mo/Ti)的粉体材料制备的铁铬铝电热合金元件，使用温度可以达到1400℃以上。由于主要元素组成为Fe-Cr-Al的合金中含铝量较高，使合金具有较高的电阻率，最高值达到1.6μΩ.m。高的电阻率可以有效地将电能转换为热能；同时铁铬铝合金的价格便宜，仅为镍铬合金的20％～25％，这就为其大量使用创造了条件。另外其具有良好的耐热性、比重低和优良的抗高温氧化性能，被大量的用于生产生活的各个方面。如在生活领域，铁铬铝粉末冶金合金应用的加热元件包括电炉丝、电炉棒、烹饪板、散热器、烤面包机、微波炉、热水器、洗衣机、锅炉、汽车中的精密电阻元件。
其十一方面，本发明还涉及其四方面所述的高硅含量球形铁铬硅粉体材料在磁性材料中的应用；
进一步地，当本发明其四方面所涉及的高硅含量球形铁铬硅粉体材料用于软磁材料时，其包括作为磁粉芯应用。
进一步地，所述磁粉芯通过所述高硅含量球形铁铬硅粉体材料施加绝缘包覆材料进行包覆，然后在一定温度下压制而成；进一步地，所述压制温度为室温至800℃。
进一步地，所述绝缘包覆材料在磁粉芯中的重量百分比超过0.1％，低于15％；
进一步地，所述绝缘包覆材料包括树脂；作为优选，所述绝缘包覆材料包括硅树脂，酚醛树脂，环氧树脂，聚丙烯、尼龙中的至少一种。
其十二方面，本发明还涉及其七方面所述的高镍含量铁铬镍粉末冶金制品在高温合金中的应用。
高温合金主要包括镍基、铁基、镍铁基高温合金，当本发明其七方面所述的高镍含量铁铬镍粉末冶金制品的成分与高温合金的成分相同或接近时，其可以用于高温合金领域。
其十三方面，本发明还涉及一种合金固体，其特征在于，通过其一方面步骤一与步骤二所述的初始合金固体的制备方法制备，其特征详见其一方面。
其具体特征包括，通过包括如下步骤制备：
步骤一，选择初始合金原料，按照初始合金成分配比将初始合金原料熔化，得到均匀的初始合金熔体；所述初始合金熔体的主要成分为La xFe yT zM aD b，其中T包含Cr、V中的至少一种，M包含Al、Ni、Co、Si中的至少一种，D包含Mo、W、Ti中的至少一种，x、y、z、a、b分别代表对应组成元素的原子百分比含量，且18％≤x≤95.8％，4％≤y≤81.8％，0.1％≤z≤35％，0≤a≤40％，0≤b≤15％；
步骤二，将初始合金熔体通过快速凝固技术凝固成初始合金固体；所述初始合金固体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的熔点，所述弥散颗粒相被包覆于所述基体相中；所述基体相在凝固组织中的体积百分数不低于40％；所述基体相的平均成分主要为La x1M a1；所述弥散颗粒相的成分主要为Fe y2T z2M a2D b2La x2，其中，x1、a1、x2、y2、z2、a2、b2分别代表对应组成元素的原子百分比含量，且45％≤x1≤100％，0％≤a1≤55％，50％≤y2≤98％，0.2％≤z2<50％，0％≤a2≤30％，0％≤b2≤35％，0<x2≤5％；所述弥散颗粒相中包括可观含量的球形或近球形弥散颗粒相，且部分球形或近球形弥散颗粒相含有一定的枝晶特征；所述弥散颗粒相的粒径大小为5nm～50μm。
进一步地，步骤一所述初始合金熔体的组成还包括非金属杂质元素，所述非金属杂质元素包括O、N、H、P、S、Cl中的至少一种；所述非金属杂质元素在初始合金熔体中的原子百分比含量大于0，且小于10％；步骤二所述富Fe弥散颗粒相的形成过程中，非金属杂质元素被富集在富La基体相，从而对富Fe弥散颗粒相进行了提纯处理，即富Fe弥散颗粒相中所述非金属杂质元素的原子百分比含量低于初始合金熔体中所述非金属杂质元素的原子百分比含量；且所述富Fe弥散颗粒相中，非金属杂质元素的原子百分比含量低于1.5％。
其十四方面，本发明还涉及其二方面所述的球形铁合金粉体材料在磁流体领域的应用。
所述球形球形铁合金粉体材料的特征详见其一方面与其二方面所述；所述球形铁合金粉体材料的部分特征包括：球形铁合金粉体材料的主要成分为Fe y2T z2M a2D b2La x2；其中，50％≤y2≤98％，0.2％≤z2<50％，0％≤a2≤30％，0％≤b2≤35％，0<x2≤5％；所述铁合金粉体颗粒的形状主要为球形或近球形，且部分球形或近球形铁合金粉体颗粒含有一定的枝晶特征；所述铁合金粉体颗粒的粒径大小为5nm～100nm；T包含Cr、V中的至少一种，M包含Al、Ni、Co、Si中的至少一种，D包含Mo、W、Ti中的至少一种；x1、a1、x2、y2、z2、a2、b2分别代表对应组成元素的原子百分比含量。
作为优选，所述球形铁合金粉体颗粒的粒径大小为5nm～50nm；
作为进一步优选，所述球形铁合金粉体颗粒的粒径大小为5nm～25nm；
进一步地，50％≤y2≤95％；
进一步地，1％≤z2+b2<50％；进一步地，2％≤z2+b2<50％；进一步地，3％≤z2+b2<50％；
进一步地，1％≤z2<50％；进一步地，2％≤z2<50％；进一步地，3％≤z2<50％；
在磁流体领域，本发明其一方面与其二方面所涉及的球形铁合金粉体材料可用于磁流体领域；具体包括：将所述球形铁合金粉体与载液及表面活性剂混合均匀，即得到磁流体；
进一步地，所述载液包括水、乙醇、碳水化合物、脂、二脂、水银中的至少一种；
进一步地，所述表面活性剂包括油酸、聚乙烯吡咯烷酮、聚乙二醇、乙二醇、十二烷基苯磺酸钠中的至少一种。
作为磁流体的磁性固体颗粒，其一般要求其粒径为纳米级；Fe是最好的磁性材料之一，但当纳米Fe颗粒作为磁流体的磁性固体颗粒时，由于纳米Fe颗粒极易氧化，会导致其性能不稳定，难以得到很好地应用。本申请很好地解决了这个问题，当所制备的球形Fe合金粉体颗粒固溶含有一定量的耐腐蚀的Cr、V、Mo、W、Ti元素时，其不仅可以使其球化更明显，还可以明显地提高纳米Fe合金粉体颗粒的耐腐蚀性。这种耐腐蚀性的提高，使得通过酸腐蚀液将合金固体中的基体腐蚀去掉的同时保留纳米Fe合金粉体颗粒成为可能；同时，也使得耐腐蚀的纳米Fe合金粉体颗粒作为磁流体的磁性固体颗粒应用成为可能。
其十五方面，本发明还涉及一种冠状病毒状球形铁合金粉体颗粒，其特征包括：所述冠状病毒状球形铁合金粉体颗粒的主要成分为Fe y2T z2M a2D b2La x2；其中，50％≤y2≤98％，0.2％≤z2<50％，0％≤a2≤30％，0％≤b2≤35％，0<x2≤5％；T包含Cr、V中的至少一种，M包含Al、Ni、Co、Si中的至少一种，D包含Mo、W、Ti中的至少一种，La为稀土La，且La主要固溶存在于主要成分为Fe y2T z2M a2D b2La x2的冠状病毒状球形铁合金颗粒中；x1、a1、x2、y2、z2、a2、b2分别代表对应组成元素的原子百分比含量；所述冠状病毒状球形铁合金粉体颗粒包括主体部分与附体部分；其中，主体部分为球形或近球形的球体，附体部分为原位生长在主体部分球体表面的多个凸起；所述球形铁合金粉体颗粒具有类冠状病毒的形状，其附体部分的多个凸起即对应于冠状病毒形状的多个冠状凸起；所述冠状病毒状球形铁合金粉体颗粒主体部分球体直径大小为20nm～50μm，且其附体部分凸起的高度低于主体部分球体直径的0.3倍。
进一步地，所述任意单一冠状病毒状球形铁合金粉体颗粒上的凸起数超过5个；
进一步地，所述任意单一冠状病毒状球形铁合金粉体颗粒上的凸起数超过10个；
所述冠状病毒状球形铁合金粉体颗粒主体部分球体直径大小为50nm～15μm；
所述冠状病毒状球形铁合金粉体颗粒主体部分球体直径大小为200nm～10μm；
所述冠状病毒状球形铁合金粉体颗粒主体部分球体直径大小为200nm～5μm；
进一步地，所述附体部分的任意单个凸起由不超过1个晶粒组成，且该晶粒的晶体结构与晶面取向和与其交界连接的球体部分的晶体结构与晶面取向相同；
进一步地，所述冠状病毒状球形铁合金粉体颗粒的主体部分与附体部分均属于一个大的单晶；
可以理解，由于主体部分与附体部分交界位置的晶体结构与晶面取向与主体部分及附体部分均一致，所以可以认为所述冠状病毒状球形铁合金粉体颗粒的主体部分球体与多个附体部分凸起均属于一个大的单晶。
进一步地，附体部分凸起的高度低于主体部分球体直径的0.2倍；
进一步地，所述凸起为枝晶凸起，即凸起为球状颗粒向枝晶状颗粒过渡的优先生长点；或者可以理解为：球状颗粒生长到一定阶段后，球面某些部位出现优先生长点，从而继续按照生长点原有的晶体结构与晶面取向优先生长为凸起；
进一步地，所述附体部分凸起的直径低于所述冠状病毒状球形铁合金粉体颗粒主体球体直径的0.25倍；
进一步地，所述冠状病毒状球形铁合金粉体颗粒的形貌特征可参考实施例中的图3，图11，图12，图15所示的冠状病毒状球形颗粒的形状；
进一步地，所述冠状病毒状球形铁合金粉体材料通过其一方面所述方法制备。
本发明的有益效果主要体现在以下几个方面：
1)通过T类元素的添加设计，实现了耐蚀、耐氧化球形或近球形富Fe弥散颗粒相在富La基体相中的析出与后续分离。对T类元素的选择，有诸多巧妙之处：T类元素与Fe完全互溶，可以大量添加；T类元素和Fe一样，也不与La生产任何金属间化合物，也几乎不进入富La相，只进入富Fe弥散颗粒相；T类元素的固溶存在，使得富Fe弥散颗粒相具有球化趋势，是制备球形或近球形Fe合金粉体的关键；T类元素与D类元素完全互溶，在D类元素在Fe中固溶度为10％-20％的情况下，因为T类元素的存在，富Fe弥散颗粒相中可以更容易地固溶更多的D类元素；T类元素Cr、V均为Fe合金中的耐腐蚀元素，其进入富Fe弥散颗粒相后，使得富Fe弥散颗粒相的耐腐蚀，耐氧化能力明显提高，使得富Fe弥散颗粒相与富La基体相通过酸腐蚀反应分离与氧化-粉化分离成为可能。否则，单纯的Fe相也容易与酸反应，也容易氧化，尤其颗粒相较为细小时。
2)球形或近球形Fe合金粉体中直接固溶有有益的稀土元素。铁合金中加入稀土元素，对材料的性能具有积极的促进作用。如Fe-Cr-Al电热合金中，加入少量稀土元素，会提高电热合金的性能。工业上，稀土元素加入Fe合金中，由于稀土元素容易氧化，当稀土元素少量添加时，稀土元素一般与合金中的氧等杂质结合，从而以氧化物颗粒的形式非均匀地存在于合金中，导致合金性能提高有限。但本申请初始合金熔体中含有较多的La(富La基体相体积百分含量高于40％)，因此，合金熔体中的氧主要存在于富La基体相中，而球形或近球形Fe合金粉体中则固溶有少量La。这种La以原子态的方式均匀地固溶在Fe合金粉体中，是严格意义上的合金化的稀土元素，对材料的性能具有更为积极作用。Fe合金粉体中固溶稀土元素(La)的存在，是本发明所制备的铁合金粉体材料的关键特征之一。
3)实现了主要由球形或近球形颗粒组成的超细铁合金粉体材料的制备。球形或近球形Fe合金颗粒因其优异的流动性、均匀性、粉体堆垛致密性等优点，是粉末冶金、粉末喷涂、粉末涂料、金属注射成型(MIM)、3D打印等应用领域的关键原材料。目前球形Fe合金粉体材料不能通过化学法制备，只能主要通过雾化法制备，即利用高速流体直接击碎液体金属或合金而获得金属粉末。但是由于雾化法雾化能力极限的限制，其一般只适合10μm～150μm的球形Fe合金粉体的制备。对于低于10μm，尤其1μm左右的球形Fe合金粉体材料，雾化法均难以制备或不能制备。本申请所提供的技术方案，实现了粒度从纳米级至数微米的超细球形铁合金粉体材料的制备，并可大规模低成本地获得这种超细的球形铁合金粉体材料，具有即为重要的应用意义。
4)所制备的部分球形或近球形铁合金粉体颗粒含有凸起状短枝晶特征。其对粉末冶金，尤其MIM来说，毛坯制品的强度是正常生产的关键因素之一。如金属注射成型MIM的毛坯制品，其由金属粉末与有机粘结剂压制而成，然后去除有机粘结剂获得。MIM毛坯制品通过烧结收缩后才是强度高的产品。MIM毛坯制品在去除有机粘结剂后且烧结之前，其需要靠颗粒之间的机械结合维持毛坯制品的形状。如果金属粉末全是理想的球形颗粒，则这种理想球形颗粒之间的机械-摩擦结合力极差，容易导致毛坯制品散架。本申请中，部分球形或近球形铁合金粉体颗粒含有凸起状短枝晶特征，这种特征对颗粒的球形度影响不大，但其可以极大地增强颗粒之间的机械结合力或摩擦力，从而增强毛坯制品的强度。如果所有颗粒都有这种凸起状短枝晶特征，则又会影响球形颗粒的粉末流行性。本申请制备的铁合金粉体颗粒，恰到好处的是，这种凸起状短枝晶特征仅仅在部分所制备的球形或近球形铁合金粉体颗粒表面出现。因此，部分球形铁合金粉体颗粒上的凸起状短枝晶，是本发明所制备Fe合金粉体的又一关键特征。
5)在富Fe弥散颗粒相的形成过程中，同时对富Fe弥散颗粒相进行了提纯处理。如果初始合金选择包含O、N、H、P、S、Cl等杂质元素、纯度较低的原料进行配制，或者初始合金熔炼过程中引入上述杂质进入熔体，均不会影响最终能够获得低上述杂质含量的富Fe的弥散颗粒相，也就能够进一步得到低上述杂质含量的球形铁合金粉体材料。因为原料中的上述杂质元素，或熔炼过程中引入的上述杂质元素，在初始合金熔体凝固过程中，大部分都会被富La基体相所捕获进而进入基体相中，从而使得富Fe弥散颗粒相得到提纯。
6)可以获得以单晶颗粒为主的铁合金粉体材料。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。通过控制基体相的体积百分含量，确保每个内生颗粒可以弥散分布的情况下，各个内生弥散颗粒之间难以发生粘结缠结。因此，最终获得的各个弥散分布的富Fe弥散颗粒相大体都是单晶相。即使球形颗粒上进一步长出的凸起状短枝晶，也是按照球体表面固定的晶向方向生长，即球体与凸起状短枝晶是一个晶粒。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。而当粉体材料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材料特殊的力学、物理、化学性能，从而产生有益的效果。
因此，本发明通过精心设计，通过T类元素、M类元素、D类元素加入主要由La，Fe组成的合金熔体中，实现了T类元素、M类元素、D类元素、以及La在球形或近球形富Fe弥散颗粒相中的固溶合金化，提高了球形或近球形富Fe弥散颗粒相的耐腐蚀性与耐氧化性，降低了杂质含量。通过富La基体相的去除，获得了粒度从数百纳米至数微米的超细球形铁合金粉体材料，在粉末冶金、金属注射成型(MIM)、3D打印、磁性材料、耐热材料、高温合金、涂料、电热材料、吸波材料等领域具有很好的应用前景。
说明：本申请其一方面至其十四方面，T包含Cr、V中的至少一种，M包含Al、Ni、Co、Si中的至少一种，D包含Mo、W、Ti中的至少一种。
附图说明
图1为实施例1所述初始合金凝固组织的背散射SEM形貌；
图2为实施例1制备的铁合金粉体材料的SEM形貌；
图3为实施例2所述初始合金凝固组织的背散射SEM形貌；
图4为实施例2所述初始合金凝固组织基体的背散射高倍SEM形貌；
图5为实施例3所述初始合金凝固组织的背散射SEM形貌；
图6为实施例3所述初始合金凝固组织基体的背散射高倍SEM形貌；
图7为实施例4所述初始合金凝固组织的背散射SEM形貌；
图8为实施例5所述初始合金凝固组织的背散射SEM形貌；
图9为实施例6所述初始合金凝固组织的背散射SEM形貌；
图10为实施例7所述初始合金凝固组织的背散射SEM形貌；
图11为实施例8所述初始合金凝固组织的背散射SEM形貌；
图12为实施例8所述铁合金粉体材料的SEM形貌；
图13为实施例10所述初始合金凝固组织的背散射SEM形貌；
图14为实施例11所述初始合金凝固组织的背散射SEM形貌；
图15为实施例11所述铁合金粉体材料的SEM形貌；
图16为实施例12所述初始合金凝固组织的背散射SEM形貌；
图17为实施例13所述初始合金凝固组织的背散射SEM形貌；
图18为实施例13所述铁合金粉体材料的SEM形貌；
图19为实施例14所述初始合金凝固组织的背散射SEM形貌；
图20为实施例15所述初始合金凝固组织的背散射SEM形貌；
图21为实施例16所述初始合金凝固组织的背散射SEM形貌；
图22为实施例16所述铁合金粉体材料的SEM形貌；
图23为对比实施例1所述初始合金凝固组织的背散射SEM形貌；
图24为对比实施例1所述富铁枝晶的SEM形貌；
图25为对比实施例2所述初始合金凝固组织的背散射SEM形貌；
图26为对比实施例3所述初始合金凝固组织的背散射SEM形貌；
图27为对比实施例4所述初始合金凝固组织的背散射SEM形貌；
图28为对比实施例4所述初始合金凝固组织的高倍背散射SEM形貌；
具体实施方式
下面结合实施例对本发明作进一步详细描述，需要指出的是，以下所述实施例旨在便于对本发明的理解，而对其不起任何限定作用。
实施例1
通过市售La、Fe、Cr原料，按照原子百分比名义成分La 50Fe 41Cr 9熔炼主要成分为La 50Fe 41Cr 9的初始合金熔体，将均匀的初始合金熔体约100K/s的冷速凝固成厚度约为5mm的初始合金板。初始合金板的凝固组织如图1所示，包括主要成分为Fe 79Cr 20La 1的弥散颗粒相与主要成分为La的基体相，其中基体相的体积百分含量超过65％；弥散颗粒相中Cr、La均固溶在其中；弥散颗粒相包括球形颗粒相与枝晶颗粒相，且球形颗粒相的体积百分含量超过50％；所述球形颗粒相的粒径大小范围为15nm-60μm。
通过0.5mol/L的稀盐酸溶液将初始合金板中的La基体相反应腐蚀去除，即得到分散的主要成分为Fe 79Cr 20La 1的铁合金粉体材料，其包括球形颗粒与枝晶颗粒，且球形颗粒的体积百分含量超过50％；所述球形颗粒的粒径大小范围为15nm-60μm，如图2所示。部分球形或近球形颗粒相含有一定的枝晶特征，如图2插图所示的在球形颗粒上的枝晶小凸起结构。所制备的铁合金粉体材料可用于普通粉末冶金、金属注射成型(MIM)领域。
实施例2
通过市售La、Fe、Cr原料，按照原子百分比名义成分La 50Fe 41Cr 9熔炼主要成分为La 50Fe 41Cr 9的初始合金熔体，将均匀的初始合金熔体约5000K/s的冷速通过甩带法凝固成厚度约为200μm的初始合金条带。初始合金条带的凝固组织如图3所示，包括检测结果主要成分为Fe 77Cr 22La 1的弥散颗粒相与主要成分为La的基体相，其中基体相的体积百分含量超过65％；弥散颗粒相几乎全部为球形颗粒；部分球形颗粒相含有一定的枝晶特征，如图3插图所示的在球形颗粒相上的枝晶小凸起结构。所述球形颗粒相的粒径大小范围为15nm-10μm。将图3的基体相放大，里面还可以发现部分纳米球形颗粒，如图4所示。
通过0.5mol/L的稀硫酸溶液将初始合金条带中的La基体相反应腐蚀去除，即得到分散的主要成分为Fe 77Cr 22La 1的铁合金粉体材料，其几乎全部为球形颗粒，部分球形颗粒相含有一定的枝晶特征；所述球形颗粒的粒径大小范围为15nm-10μm。所制备的粉体材料可用于普通粉末冶金、金属注射成型(MIM)领域。
实施例3
通过市售La、Fe、V原料，按照原子百分比名义成分La 67Fe 30V 3熔炼主要成分为La 67Fe 30V 3的初始合金熔体，将均匀的初始合金熔体约1000K/s的冷速凝固成厚度约为500μm的初始合金条带。初始合金条带的凝固组织如图5所示，包括检测结果主要成分为Fe 88.5V 9La 1.5的弥散颗粒相与主要成分为La的基体相，其中基体相的体积百分含量超过70％；弥散颗粒相主要为球形；所述球形颗粒相的粒径大小范围为15nm-5μm。将图5的基体相放大，里面还可以发现部分纳米球形颗粒，如图6所示(纳米球形颗粒之外的才是真正的基体相)，且少量颗粒相为枝晶颗粒相。
通过0.5mol/L的稀盐酸将初始合金条带中的La基体相反应腐蚀去除，即得到分散的主要成分为Fe 88.5V 9La 1.5的铁合金粉体材料，其形状主要为球形颗粒，仅有少量颗粒相为枝晶颗粒。所述球形颗粒的粒径大小范围为15nm-5μm。
实施例4
通过市售含高O杂质的低纯La、低纯Fe、低纯V、低纯Cr原料，按照原子百分比名义成分La 67Fe 30Cr 3V 3熔炼主要成分约为La 65Fe 30Cr 3V 3O 2的初始合金熔体，将均匀的初始合金熔体约250K/s的冷速凝固成厚度约为3mm的初始合金厚带。初始合金厚带的凝固组织如图7所示，包括检测结果主要成分为Fe 82.3V 8Cr 8La 1.5O 0.2的弥散颗粒相与主要成分为La并富集了氧杂质的基体相，其中基体相的体积百分含量超过70％；弥散颗粒相主要为球形，包括少量枝晶形；所述球形颗粒相的粒径大小范围为15nm-15μm，且部分球形颗粒相含有一定的枝晶特征。
通过0.2mol/L的稀硝酸将初始合金厚带中的富La基体相反应腐蚀去除，即得到分散的主要成分为Fe 82.3V 8Cr 8La 1.5O 0.2的铁合金粉体材料，其形状主要为球形，包括少量枝晶形，且部分球形颗粒含有一定的枝晶特征。所述球形颗粒的粒径大小范围为15nm-15μm。
实施例5
通过市售La、Fe、Cr、Mo原料，按照原子百分比名义成分La 50Fe 40Cr 0.5Mo 9.5熔炼主要成分为La 50Fe 40Cr 0.5Mo 9.5的初始合金熔体，将均匀的初始合金熔体约250K/s的冷速凝固成厚度约为3mm的初始合金厚带。初始合金厚带的凝固组织如图8所示，包括检测结果主要成分为Fe 78Mo 20Cr 1La 1的弥散颗粒相与主要成分为La的基体相，其中基体相的体积百分含量超过70％；弥散颗粒相主要为球形；所述球形弥散颗粒相的粒径大小范围为15nm-15μm，且部分球形颗粒相含有一定的枝晶特征。
通过0.5mol/L的稀盐酸将初始合金厚带中的La基体相反应腐蚀去除，即得到分散的主要成分为Fe 78Mo 20Cr 1La 1的铁合金粉体材料，其形状主要为球形颗粒，且部分球形颗粒含有一定的枝晶特征；所述球形颗粒的粒径大小范围为15nm-15μm。
实施例6
通过市售La、Fe、Cr、Si原料，按照原子百分比名义成分La 34Fe 40Cr 2.5Si 23.5熔炼主要成为La 34Fe 40Cr 2.5Si 23.5的初始合金熔体，将均匀的初始合金熔体约100K/s的冷速凝固成厚度约为5mm的初始合金厚带。初始合金厚带的凝固组织如图9所示，包括检测结果主要成分为Fe 85.2Cr 8Si 6La 0.8的黑色弥散颗粒 相与主要成分为La 64Si 36的白色基体相与主要成分为La 34Si 33Fe 33的灰色基体相，其中两种基体相的体积百分含量超过70％；弥散颗粒相主要为近球形。所述近球形颗粒相的粒径大小范围为50nm-5μm。
通过0.5mol/L的稀盐酸与1mol/L氢氟酸混合溶液将初始合金厚带中的La 64Si 36基体相与La 34Si 33Fe 33基体相反应腐蚀去除，即得到分散的主要成分为Fe 85.2Cr 8Si 6La 0.8的铁合金粉体材料，其形状主要为近球形，所述近球形颗粒的粒径大小范围为50nm-5μm。所制备的粉体材料可用于磁性材料领域，如磁粉芯。
实施例7
通过市售La、Fe、Cr、Si原料，按照原子百分比名义成分La 34Fe 40Cr 2.5Si 23.5熔炼主要成为La 34Fe 40Cr 2.5Si 23.5的初始合金熔体，将均匀的初始合金熔体约10 5K/s的冷速凝固成厚度约为100μm的初始合金条带。初始合金条带的凝固组织如图10所示，包括检测结果主要成分为Fe 82.5Cr 8Si 8La 1.5的黑色弥散颗粒相与平均成分主要为La 60Si 20Fe 20的基体相，其中基体相的体积百分含量大于70％；弥散颗粒相主要为细小的球形。所述球形颗粒相的粒径大小范围为15nm-2μm。
通过0.5mol/L的稀盐酸与1mol/L氢氟酸混合溶液将初始合金条带中平均成分主要为La 60Si 20Fe 20的基体相反应腐蚀去除，即得到分散的主要成分为Fe 82.5Cr 8Si 8La 1.5的含Si的铁合金粉体材料，其形状主要为近球形，所述近球形颗粒的粒径大小范围为15nm-2μm。所制备的粉体材料可用于磁性材料领域，如磁粉芯。
实施例8
通过市售La、Fe、Cr、Si原料，按照原子百分比名义成分La 50Fe 40Cr 5Si 5熔炼主要成分为La 50Fe 40Cr 5Si 5的初始合金熔体，将均匀的初始合金熔体约250K/s的冷速凝固成厚度约为3mm的初始合金厚带。初始合金厚带的凝固组织如图11所示，包括检测结果主要成分为Fe 86Cr 12Si 1La 1的弥散颗粒相与主要成分为La 92Si 8的基体相，其中基体相的体积百分含量超过70％；弥散颗粒相主要为球形，也包括少量枝晶形；且部分球形颗粒相含有一定的枝晶特征。所述球形颗粒相的粒径大小范围为15nm-40μm。
通过0.5mol/L的稀盐酸、0.1mol/L的稀硝酸、0.5mol/L氢氟酸(氢氟酸可以去除Si)混合溶液将初始合金条带中的LaSi基体相反应腐蚀去除，即得到分散的主要成分为Fe 86Cr 12Si 1La 1的铁合金粉体材料，其形状主要为球形颗粒，也包括少量枝晶形颗粒，且部分球形颗粒含有一定的枝晶特征，所述球形颗粒的粒径大小范围为15nm-40μm。如图12所示。
实施例9
通过市售La、Fe、Cr、Si原料，按照原子百分比名义成分La 50Fe 41Cr 4Si 5熔炼主要成分为La 50Fe 41Cr 4Si 5的初始合金熔体，将均匀的初始合金熔体约1000K/s的冷速凝固成厚度约为500μm的初始合金带。初始合金带的凝固组织包括检测结果主要成分为Fe 90.5Cr 8Si 0.5La 1的弥散颗粒相与主要成分为La 94Si 6的基体相，其中基体相的体积百分含量超过70％；弥散颗粒相主要为球形，也包括少量枝晶形；且部分球形颗粒相含有一定的枝晶特征。所述球形颗粒相的粒径大小范围为15nm-10μm。
通过0.5mol/L的稀盐酸将初始合金带LaSi基体相中的La通过脱合金反应腐蚀去除，同时保留大部分Si(Si一般不与稀盐酸反应)，即得到分散的主要成分为Fe 90.5Cr 8Si 0.5La 1的铁合金粉体与纳米多孔Si的复合粉体；其中，纳米多孔Si为碎散的多孔结构，铁合金粉体主要为球形颗粒，也包括少量枝晶形颗粒，且部分球形颗粒含有一定的枝晶特征，所述球形颗粒的粒径大小范围为15nm-10μm。
将球形铁合金粉体与纳米多孔Si的复合粉体压制密实后，在1000℃下真空固体渗硅4小时，然后将粉体分散，即得到成分约为Fe 82Cr 7Si 10La 1的高硅含量铁铬硅粉末。
所制备高硅含量铁铬硅粉体通过筛分后，选择粒径3μm-10μm的粉体，可用于软磁材料领域，如磁粉 芯。
实施例10
通过市售La、Fe、Cr、Al原料，按照原子百分比名义成分La 45Fe 27.5Cr 7.5Al 20熔炼主要成分为La 45Fe 27.5Cr 7.5Al 20的初始合金熔体，将均匀的初始合金熔体约250K/s的冷速凝固成厚度约为3mm的初始合金厚带。初始合金厚带的凝固组织如图13所示，包括检测结果主要成分为Fe 72Cr 20Al 7La 1的弥散颗粒相与主要成分为La 75Al 25的基体相，其中基体相的体积百分含量超过70％；弥散颗粒相主要为球形，也包括少量枝晶形；且部分球形颗粒相含有一定的枝晶特征。所述球形颗粒相的粒径大小范围为15nm-10μm。
通过0.5mol/L的稀盐酸将初始合金厚带中的La 75Al 25基体相反应腐蚀去除，即得到分散的主要成分为Fe 72Cr 20Al 7La 1的铁合金粉体材料，其形状主要为球形颗粒，也包括少量枝晶形颗粒，且部分球形颗粒含有一定的枝晶特征，所述球形颗粒的粒径大小范围为15nm-10μm。所制备的粉体材料可用于电热合金、耐热合金，耐热涂层领域。
实施例11
通过市售La、Fe、Cr、Al原料，按照原子百分比名义成分La 45Fe 27.5Cr 7.5Al 20熔炼主要成分为La 45Fe 27.5Cr 7.5Al 20的初始合金熔体，将均匀的初始合金熔体约10 4K/s的冷速凝固成厚度约为150μm的初始合金薄带。初始合金薄带的凝固组织如图14所示，包括检测结果主要成分为Fe 71Cr 21Al 7La 1的弥散颗粒相与主要成分为La 75Al 25的基体相，其中基体相的体积百分含量超过70％；弥散颗粒相几乎全为球形，且部分球形颗粒相含有一定的枝晶特征。所述球形颗粒相的粒径大小范围为5nm-5μm。
通过0.5mol/L的稀盐酸将初始合金厚带中的La 75Al 25基体相反应腐蚀去除，即得到分散的主要成分为Fe 71Cr 21Al 7La 1的铁合金粉体材料，如图15所示，其形状几乎全为球形，且部分球形颗粒含有一定的枝晶特征，如图15插图所示，所述球形颗粒的粒径大小范围为5nm-5μm。所制备的粉体材料可用于电热合金、耐热合金，耐热涂层领域。
实施例12
通过市售La、Fe、Cr、Al、Mo原料，按照原子百分比名义成分La 38Fe 25Cr 10Al 25Mo 2熔炼主要成分为La 38Fe 25Cr 10Al 25Mo 2的初始合金熔体，将均匀的初始合金熔体约500K/s的冷速凝固成厚度约为1mm的初始合金厚带。初始合金厚带的凝固组织如图16所示，包括检测结果主要成分为Fe 60Cr 25Al 8Mo 6La 1的弥散颗粒相与主要成分分别为La 50Al 50(灰色板条与纤维状相)与La 75Al 25(白色相)的基体相，其中基体相的总体积百分含量超过70％；弥散颗粒相主要为球形，也包括少量枝晶形；且部分球形颗粒相含有一定的枝晶特征。所述球形颗粒相的粒径大小范围为15nm-40μm。
通过1mol/L的稀盐酸将初始合金厚带中的La 50Al 50与La 75Al 25基体相反应腐蚀去除，即得到分散的主要成分为Fe 60Cr 25Al 8Mo 6La 1的铁合金粉体材料，其形状主要为球形颗粒，也包括少量枝晶形颗粒，且部分球形颗粒含有一定的枝晶特征，所述球形颗粒的粒径大小范围为15nm-40μm。所制备的粉体材料可用于电热合金、耐热合金，耐热涂层领域。由于含有Mo，所述粉体材料具有更高的耐温、耐腐蚀性能。
实施例13
通过市售La、Fe、Cr、Co原料，按照原子百分比名义成分La 27.5Fe 37.5Cr 10Co 25熔炼主要成分为La 27.5Fe 37.5Cr 10Co 25的初始合金熔体，将均匀的初始合金熔体约250K/s的冷速凝固成厚度约为3mm的初始合金厚带。初始合金厚带的凝固组织如图17所示，包括检测结果主要成分为Fe 63Cr 19Co 17La 1的弥散颗粒 相与主要成分为La 60Co 40的基体相，其中基体相的总体积百分含量超过50％；弥散颗粒相几乎全部为球形，仅包括少量枝晶形；且部分球形颗粒相含有一定的枝晶特征。所述球形颗粒相的粒径大小范围为15nm-6μm。
通过1mol/L的稀盐酸将初始合金厚带中的La 60Co 40基体相反应腐蚀去除，即得到分散的主要成分为Fe 63Cr 19Co 17La 1的铁合金粉体材料，如图18所示，其形状主要为球形颗粒，也包括少量枝晶形颗粒，且部分球形颗粒含有一定的枝晶特征，所述球形颗粒的粒径大小范围为15nm-6μm。所制备的粉体材料可用于磁性材料领域。
实施例14
通过市售La、Fe、Cr、Ni原料，按照原子百分比名义成分La 27.5Fe 37.5Cr 10Ni 25熔炼主要成分为La 27.5Fe 37.5Cr 10Ni 25的初始合金熔体，将均匀的初始合金熔体约250K/s的冷速凝固成厚度约为3mm的初始合金厚带。初始合金厚带的凝固组织如图19所示，包括检测结果主要成分为Fe 70Cr 20Ni 9La 1的弥散颗粒相与主要成分分别约为La 50Ni 50与La 75Ni 25的基体相，其中基体相的总体积百分含量超过50％；弥散颗粒相主要为球形，包括少量枝晶形；且部分球形颗粒相含有一定的枝晶特征。所述球形颗粒相的粒径大小范围为15nm-50μm。
通过1mol/L的稀盐酸将初始合金带中的La 50Ni 50与La 75Ni 25的基体相反应腐蚀去除，即得到分散的主要成分为Fe 70Cr 20Ni 9La 1的铁合金粉体材料，其形状主要为球形颗粒，也包括少量枝晶形颗粒，且部分球形颗粒含有一定的枝晶特征，所述球形颗粒的粒径大小范围为15nm-50μm。
实施例15
通过市售La、Fe、Cr、Ni、Mo、Ti原料，按照原子百分比名义成分La 35Fe 36Cr 10Ni 15Mo 1Ti 2熔炼主要成分为La 35Fe 36Cr 10Ni 15Mo 1Ti 2的初始合金熔体，将均匀的初始合金熔体约50K/s的冷速凝固成厚度6mm，直径12mm的纽扣锭。初始合金纽扣锭的凝固组织如图20所示，包括检测结果主要成分为Fe 70Cr 20Ni 3Mo 2Ti 4La 1的弥散颗粒相与平均成分主要为La 81Ni 19的基体相(由La相与La 3Ni相组成)，其中基体相的总体积百分含量超过70％；弥散颗粒相几乎全部为球形，仅包括少量枝晶形；且部分球形颗粒相含有一定的枝晶特征。所述球形颗粒相的粒径大小范围为15nm-50μm。
通过1mol/L的盐酸溶液将初始合金纽扣锭中的La 81Ni 19基体相反应腐蚀去除，同时保留耐腐蚀的弥散颗粒相，即得到分散的主要成分为Fe 70Cr 20Ni 3Mo 2Ti 4La 1的球形铁合金粉体材料；其中铁合金粉体形状主要为球形颗粒，也包括少量枝晶形颗粒，且部分球形颗粒含有一定的枝晶特征，所述球形颗粒的粒径大小范围为15nm-50μm。
实施例16
通过市售La、Fe、Cr、Ni原料，按照原子百分比名义成分La 27.5Fe 37.5Cr 10Ni 25熔炼主要成分为La 27.5Fe 37.5Cr 10Ni 25的初始合金熔体，将均匀的初始合金熔体约5000K/s的冷速凝固成厚度约为200μm的初始合金带。初始合金带的凝固组织如图21所示，包括检测结果主要成分为Fe 70Cr 20Ni 9La 1的弥散颗粒相与平均成分主要为La 60Ni 40的基体相，其中基体相的总体积百分含量超过50％；弥散颗粒相几乎全部为球形，仅包括少量枝晶形；且部分球形颗粒相含有一定的枝晶特征。所述球形颗粒相的粒径大小范围为15nm-6μm。
通过0.2mol/L的稀盐酸将初始合金带基体相中的La通过脱合金反应腐蚀去除，同时保留部分纳米多孔Ni，即得到分散的主要成分为Fe 70Cr 20Ni 9La 1的球形铁合金粉体材料与纳米多孔Ni的复合粉体，如图 22所示，球形颗粒外部的絮状物即为纳米多孔Ni；其中铁合金粉体形状主要为球形颗粒，也包括少量枝晶形颗粒，且部分球形颗粒含有一定的枝晶特征，所述球形颗粒的粒径大小范围为15nm-6μm。
将主要成分为Fe 70Cr 20Ni 9La 1的球形铁合金粉体材料与纳米多孔Ni的复合粉体在100MPa下压制成坯，然后在保护气氛、1300℃下热处理4h，即得到检测成分约为Fe 52Cr 15Ni 33La 1的高镍含量铁铬镍高温合金制品。
实施例17
通过市售La、Fe、Cr原料，按照原子百分比名义成分La 45Fe 40Cr 15熔炼主要成分为La 45Fe 40Cr 15的初始合金熔体，将均匀的初始合金熔体约10 6K/s-10 7K/s的冷速凝固成厚度约为20μm的初始合金条带。初始合金条带的凝固组织包括富Fe的弥散纳米颗粒相(颗粒太小导致成分不能直接检测)与主要成分为La的基体相，其中基体相的体积百分含量超过60％；弥散颗粒相几乎全部为纳米近球形颗粒；部分球形颗粒相含有一定的枝晶特征，所述球形颗粒相的粒径大小范围为5nm-200nm。
通过0.5mol/L的稀盐酸溶液将初始合金条带中的La基体相反应腐蚀去除，即得到分散的检测成分主要为Fe 71Cr 27La 2的纳米铁合金粉体材料(因为Cr的存在，使得Fe 71Cr 27La 2纳米铁合金粉体颗粒不易被酸反应溶解)，其几乎全部为球形颗粒，且部分球形颗粒含有一定的枝晶特征，所述纳米铁合金粉体材料的粒径大小范围为5nm-200nm。
实施例18
通过市售La、Fe、Cr原料，按照原子百分比名义成分La 50Fe 46Cr 4熔炼主要成分为La 50Fe 46Cr 4的初始合金熔体，将均匀的初始合金熔体约10 4K/s的冷速凝固成厚度约为150μm的初始合金带。初始合金带的凝固组织包括主要成分为Fe 91Cr 8La 1的弥散颗粒相与主要成分为La的基体相；弥散颗粒相中Cr、La均固溶在其中；富铁弥散颗粒相主要由球形颗粒组成，也包括少量枝晶颗粒相，且部分球形颗粒相含有一定的枝晶特征；所述富铁球形颗粒相的粒径大小范围为15nm-10μm。
通过0.5mol/L的稀盐酸溶液将初始合金带中的La基体相反应腐蚀去除，即得到分散的主要成分为Fe 91Cr 8La 1的铁合金粉体材料，其包括球形颗粒与枝晶颗粒，且主要由球形颗粒组成，且部分球形颗粒含有一定的枝晶特征；所述球形颗粒的粒径大小范围为15nm-10μm。
将上述所得铁合金粉体材料在氯化硅(SiCl 4，或Si 2Cl 6，或SiCl 4与Si 2Cl 6两种混合)与氢气的混合气体中进行气体渗硅处理，处理温度为400℃-1000℃，即可获得高硅含量的球形铁合金粉体材料，其成分约为Fe 81.5Cr 7Si 10.5La 1，其形状仍然保持渗硅前的大致不变，包括球形颗粒与枝晶颗粒，且主要由球形颗粒组成，且部分球形颗粒含有一定的枝晶特征；所述球形颗粒的粒径大小范围为15nm-10μm。
通过筛分后，选择1μm-10μm的Fe 81.5Cr 7Si 10.5La 1粉体进行绝缘包覆，然后制备磁粉芯。
实施例19
通过市售La、Fe、Cr原料，按照原子百分比名义成分La 35Fe 50Cr 15熔炼主要成分为分La 35Fe 50Cr 15的初始合金熔体，将均匀的初始合金熔体以约10 3K/s-10 6K/s的冷速通过雾化制粉技术凝固成粒度5μm-300μm的初始合金粉。初始合金粉的凝固组织包括检测结果主要成分为Fe 75.5Cr 23La 1.5的弥散颗粒相与主要成分为La的基体相，其中基体相的体积百分含量超过50％；弥散颗粒相几乎全部为球形颗粒；部分球形颗粒相含有一定的枝晶特征。所述球形颗粒相的粒径大小范围为5nm-10μm。
通过0.5mol/L的稀盐酸溶液将初始合金粉中的La基体相反应腐蚀去除，即得到分散的主要成分为Fe 75.5Cr 23La 1.5的更细的铁合金粉体材料，其几乎全部为球形颗粒，部分球形颗粒相含有一定的枝晶特征； 所述球形颗粒的粒径大小范围为5nm-10μm。所制备的粉体材料可用于普通粉末冶金、金属注射成型(MIM)领域。
实施例20
通过市售La、Fe、Mo、Cr原料，按照原子百分比名义成分La 50Fe 49Cr 0.5Mo 0.5熔炼主要成分为La 50Fe 49Cr 0.5Mo 0.5的初始合金熔体，将均匀的初始合金熔体约10 7K/s-10 8K/s的冷速凝固成厚度约为15μm-20μm的初始合金条带。初始合金条带的凝固组织包括富Fe的弥散纳米颗粒相与主要成分为La的基体相，其中基体相的体积百分含量超过65％；弥散颗粒相几乎全部为纳米近球形颗粒；部分球形颗粒相含有一定的枝晶特征，所述球形颗粒相的粒径大小范围为5nm-100nm。
通过0.25mol/L的稀盐酸溶液将初始合金条带中的La基体相反应腐蚀去除，即得到分散的检测成分主要为Fe 97Cr 1Mo 1La 1的纳米铁合金粉体材料(因为Cr、Mo的存在，使得纳米Fe 97Cr 1Mo 1La 1铁合金粉体颗粒不易被0.25mol/L的稀盐酸反应溶解)，其几乎全部为球形颗粒，且部分球形颗粒含有一定的枝晶特征，所述纳米Fe 97Cr 1Mo 1La 1铁合金粉体颗粒的粒径大小范围为5nm-100nm。
将所得的纳米Fe 97Cr 1Mo 1La 1铁合金粉体颗粒作为磁性固体颗粒，将十二烷基硫酸钠(SDS)和油酸为表面活性剂，将乙醇作为载液，制备磁流体。
实施例21
通过市售La、Fe、Cr原料，按照原子百分比名义成分La 50Fe 47Cr 3熔炼主要成分为La 50Fe 47Cr 3的初始合金熔体，将均匀的初始合金熔体约10 6K/s-10 8K/s的冷速凝固成厚度约为15μm-20μm的初始合金条带。初始合金条带的凝固组织包括富Fe的弥散纳米颗粒相与主要成分为La的基体相，其中基体相的体积百分含量超过65％；弥散颗粒相几乎全部为纳米近球形颗粒；部分球形颗粒相含有一定的枝晶特征，所述球形颗粒相的粒径大小范围为5nm-50nm。
通过0.5mol/L的稀盐酸溶液将初始合金条带中的La基体相反应腐蚀去除，即得到分散的检测成分主要为Fe 93Cr 6La 1的纳米铁合金粉体材料(因为Cr的存在，使得纳米Fe 93Cr 6La 1铁合金粉体颗粒不易被0.5mol/L的稀盐酸反应溶解)，其几乎全部为球形颗粒，且部分球形颗粒含有一定的枝晶特征，所述纳米Fe 93Cr 6La 1铁合金粉体颗粒的粒径大小范围为5nm-50nm。
将所得的纳米Fe 93Cr 6La 1铁合金粉体颗粒作为磁性固体颗粒，以水银为载液制备磁流体。
对比实施例1
通过市售La、Fe原料，按照原子百分比名义成分La 50Fe 50熔炼主要成分为La 50Fe 50的初始合金熔体，将均匀的初始合金熔体约250K/s的冷速凝固成厚度约为3mm的初始合金厚带。初始合金厚带的凝固组织如图23所示，包括主要成分为Fe 99La 1的弥散枝晶相与主要成分为La的基体相，其中基体相的体积百分含量超过70％；弥散枝晶相几乎全部为枝晶形，图23上按照规律排列的看似圆球的部分其实时枝晶的枝条横截面形貌，每一排横截面枝条其实属于某一个大的枝晶。
通过0.5mol/L的稀盐酸溶液将初始合金厚带中的La基体相反应腐蚀去除，即得到分散的主要成分为Fe 99La 1的铁合金枝晶粉体材料，其形状主要为枝晶，见不到球形颗粒，如图24所示。其也清楚地显示了一个大的枝晶上会有一排排的次级枝晶，这些次级枝晶的横截面即对应图23所示的规律排列的“球”(实际为条形截面)形横截面形貌。因此，La 50Fe 50合金通过较慢冷速只能获得生长极为充分的大的富铁枝晶颗粒，得不到富铁球形颗粒。
对比实施例2
通过市售La、Fe原料，按照原子百分比名义成分La 50Fe 50熔炼主要成分为La 50Fe 50的初始合金熔体，将均匀的初始合金熔体约10 5K/s的冷速凝固成厚度约为100μm的初始合金条带。初始合金条带的凝固组织如图25所示，包括主要成分为Fe 99La 1的弥散枝晶相与主要成分为La的基体相；弥散枝晶相几乎全部为枝晶形，图25上相邻的多个看似短棒状的富铁黑色相其实属于某个或某几个枝晶，且这些枝晶的大小约为1-2μm。由于枝晶的次级结构为纳米级，且Fe 99La 1不耐酸腐蚀，当采用酸腐蚀时，纳米级富铁枝晶也会被反应腐蚀，难以获得原始的富铁颗粒。因此，即使采用很高的冷速，当初始合金熔体中不含T、D类元素时，一方面难以获得球形富铁颗粒相，另一方面不能将富铁颗粒的耐蚀性提高，从而易于酸反应分离。
对比实施例3
通过市售La、Fe、Hf原料，按照原子百分比名义成分La 50Fe 40Hf 10熔炼主要成分为La 50Fe 40Hf 10的初始合金熔体，将均匀的初始合金熔体约500K/s的冷速凝固成厚度约为1mm的初始合金厚带。初始合金厚带的凝固组织如图26所示，包括主要成分约为Fe 99La 1的黑色弥散枝晶相、主要成分约为Fe 64Hf 35La 1的白色弥散枝晶相，以及主要成分为La的基体相。因此，初始合金熔体中的Hf在熔体凝固过程中，不能固溶进入富铁相，只能以Fe 2Hf金属间化合物的方式析出。而富Fe相则主要仍然以Fe 99La 1的弥散枝晶相的方式析出。两种枝晶相，都不能获得球形颗粒相。因此，Hf添加在La-Fe合金中，不能获得富铁球形颗粒相。
对比实施例4
通过市售La、Fe、Ta原料，按照原子百分比名义成分La 50Fe 40Ta 10熔炼主要成分为La 50Fe 40Ta 10的初始合金熔体，将均匀的初始合金熔体约500K/s的冷速凝固成厚度约为1mm的初始合金厚带。初始合金厚带的凝固组织如图27所示，包括主要成分约为Fe 99La 1的黑色弥散枝晶相、主要成分约为Fe 69Ta 30La 1的白色絮状枝晶相(如图28箭头所示，为Fe 7Ta 3金属间化合物)，以及主要成分为La的基体相。因此，初始合金熔体中的Ta在凝固过程中，不能固溶进入富铁相，只能以Fe 7Ta 3金属间化合物的方式析出。而富Fe相则主要仍然以Fe 99La 1的弥散枝晶相的方式析出。两种枝晶相，都不能获得球形颗粒相。因此，Ta添加在La-Fe合金中，不能获得富铁球形颗粒相。
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。
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。

Claims (19)

  1. 一种球形铁合金粉体材料的制备方法，其特征在于，包含如下步骤：
    步骤一，选择初始合金原料，按照初始合金成分配比将初始合金原料熔化，得到均匀的初始合金熔体；所述初始合金熔体的主要成分为La xFe yT zM aD b，其中T包含Cr、V中的至少一种，M包含Al、Ni、Co、Si中的至少一种，D包含Mo、W、Ti中的至少一种，x、y、z、a、b分别代表对应组成元素的原子百分比含量，且18％≤x≤95.8％，4％≤y≤81.8％，0.1％≤z≤35％，0≤a≤40％，0≤b≤15％；
    步骤二，将初始合金熔体通过快速凝固技术凝固成初始合金固体；所述初始合金固体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的熔点，所述弥散颗粒相被包覆于所述基体相中；所述基体相在凝固组织中的体积百分数不低于40％；所述基体相的平均成分主要为La x1M a1；所述弥散颗粒相的成分主要为Fe y2T z2M a2D b2La x2，其中，x1、a1、x2、y2、z2、a2、b2分别代表对应组成元素的原子百分比含量，且45％≤x1≤100％，0％≤a1≤55％，50％≤y2≤98％，0.2％≤z2<50％，0％≤a2≤30％，0％≤b2≤35％，0<x2≤5％；所述弥散颗粒相中包括可观含量的球形或近球形弥散颗粒相，且部分球形或近球形弥散颗粒相含有一定的枝晶特征；所述弥散颗粒相的粒径大小为5nm～50μm；
    步骤三，去除所述初始合金固体中的基体相并主要保留弥散颗粒相，即得到主要成分为Fe y2T z2M a2D b2La x2的铁合金粉体材料；其中，50％≤y2≤98％，0.2％≤z2<50％，0％≤a2≤30％，0％≤b2≤35％，0<x2≤5％；所述铁合金粉体颗粒中包括可观含量的球形或近球形颗粒，且部分球形或近球形铁合金粉体颗粒含有一定的枝晶特征；所述铁合金粉体颗粒的粒径大小为5nm～50μm。
  2. 根据权利要求1所述的球形铁合金粉体材料的制备方法，其特征在于，所述弥散颗粒相的形状主要为球形或近球形。
  3. 根据权利要求1所述的球形铁合金粉体材料的制备方法，其特征在于，步骤一所述初始合金熔体的组成还包括非金属杂质元素，所述非金属杂质元素包括O、N、H、P、S、Cl中的至少一种；所述非金属杂质元素在初始合金熔体中的原子百分比含量大于0，且小于10％；步骤二所述富Fe弥散颗粒相的形成过程中，非金属杂质元素被富集在富La基体相，从而对富Fe弥散颗粒相进行了提纯处理，即富Fe弥散颗粒相中所述非金属杂质元素的原子百分比含量低于初始合金熔体中所述非金属杂质元素的原子百分比含量；且所述富Fe弥散颗粒相中，非金属杂质元素的原子百分比含量低于1.5％；且步骤三所述球形或近球形铁合金粉体颗粒中非金属杂质元素含量也低于初始合金熔体中非金属杂质元素的含量。
  4. 一种球形铁合金粉体材料，其特征在于，通过权利要求1-3任一项所述的球形铁合金粉体材料的制备方法制备；
    所述球形铁合金粉体材料的部分特征包括：球形铁合金粉体材料的主要成分为Fe y2T z2M a2D b2La x2；其中，50％≤y2≤98％，0.2％≤z2<50％，0％≤a2≤30％，0％≤b2≤35％，0<x2≤5％；所述铁合金粉体颗粒的形状主要为球形或近球形，且部分球形或近球形铁合金粉体颗粒含有一定的枝晶特征；所述铁合金粉体颗粒的粒径大小为5nm～50μm；所述T包含Cr、V中的至少一种，M包含Al、Ni、Co、Si中的至少一种，D包含Mo、W、Ti中的至少一种；x1、a1、x2、y2、z2、a2、b2分别代表对应组成元素的原子百分比含量。
  5. 一种高硅含量球形铁铬硅粉体材料的制备方法，其特征在于，将权利要求1所述步骤一至步骤三制备的主要组成元素为Fe-Cr的球形铁合金粉体材料或低Si含量的主要组成元素为Fe-Cr-Si的球形铁合金粉体材料进行渗Si处理，即得到高Si含量的主要组成为Fe-Cr-Si的球形粉体材料。
  6. 根据权利要求5所述的高硅含量球形铁铬硅粉体材料的制备方法，其特征在于，按照权利要求1所述步骤一与步骤二，制备权利要求1步骤二所述的初始合金固体；其中，T包含Cr，M包含Si，0<a≤40％；所述基体相的平均成分主要为La x1Si a1；所述弥散颗粒相的成分主要为低Si含量的Fe y2Cr z2Si a2D b2La x2；所述La x1Si a1基体相中Si通过金属间化合物的方式与La结合；0<a2≤8％；通过稀酸溶液将所述的初始合金固体La x1Si a1基体相中的La通过脱合金反应去除，同时保留原La x1Si a1基体相中的Si，得到纳米多孔Si与所述低Si含量的Fe y2Cr z2Si a2D b2La x2颗粒的复合粉体；所述纳米多孔Si作为Si源对低Si含量的Fe y2Cr z2Si a2D b2La x2颗粒进行渗Si处理，即得到高Si含量的球形Fe-Cr-Si粉体材料，其成分组成主要为Fe y3Cr z3Si a3D b3La x3；其中x3、y3、z3、a3、b3分别代表对应组成元素的原子百分比含量，且0<y3<y2，0<z3<z2，0<a2<a3，0≤b3≤b2，0<x3<x2。
  7. 一种高硅含量球形铁铬硅粉体材料，其特征在于，通过权利要求5所述的高硅含量球形铁铬硅粉体材料的制备方法制备。
  8. 一种纳米多孔Si与球形Fe-Cr-Si颗粒的复合粉体，其特征在于，通过权利要求6所述方法制备纳米多孔Si与低Si含量的Fe y2Cr z2Si a2D b2La x2颗粒的复合粉体，即得到纳米多孔Si与球形Fe-Cr-Si颗粒的复合粉体。
  9. 一种高镍含量铁铬镍粉末冶金制品的制备方法，其特征在于，包括如下步骤：
    步骤1，按照权利要求1的步骤一与步骤二，制备权利要求1步骤二所述的初始合金固体；其中，T包含Cr，M包含Ni，0<a≤40％；所述基体相的平均成分主要为La x1Ni a1；所述弥散颗粒相的成分主要为低Ni含量的Fe y2Cr z2Ni a2D b2La x2；所述La x1Ni a1基体相中Ni通过金属间化合物的方式与La结合；0<a2≤12％；
    步骤2，通过稀酸溶液将所述的初始合金固体La x1Ni a1基体相中的La通过脱合金反应去除，同时确保原La x1Ni a1基体相中大部分Ni不被反应去除，得到纳米多孔Ni与低Ni含量Fe y2Cr z2Ni a2D b2La x2颗粒的复合粉体；
    步骤3，将纳米多孔Ni与所述低Ni含量Fe y2Cr z2Ni a2D b2La x2颗粒的复合粉体压制成型并进行热处理烧结，即获得高Ni含量的铁铬镍粉末冶金制品，其主要成分组成为Fe y3Cr z3Ni a3D b3La x3；其中，x3、y3、z3、a3、b3分别代表对应组成元素的原子百分比含量，且0<y3<y2，0<z3<z2，0<a2<a3，0≤b3≤b2，0<x3<x2。
  10. 一种高镍含量铁铬镍粉末冶金制品，其特征在于，通过权利要求9所述的高镍含量铁铬镍粉末冶金制品的制备方法制备。
  11. 一种纳米多孔Ni与低Ni含量铁铬镍颗粒的复合粉体，其特征在于，通过权利要求9所述方法的步骤1与步骤2制备。
  12. 根据权利要求4所述的球形铁合金粉体材料在以下任意一种领域的应用，所述应用领域包括普通粉末冶金、金属注射成型(MIM)、3D打印、磁性材料、耐热材料、高温合金、涂料、吸波材料。
  13. 根据权利要求4所述的球形铁合金粉体材料在电热材料领域的应用，且所述球形铁合金粉体材料主要成分包括Fe-Cr-Al。
  14. 根据权利要求7所述的高硅含量球形铁铬硅粉体材料在磁性材料中的应用。
  15. 根据权利要求10所述的高镍含量铁铬镍粉末冶金制品在高温合金中的应用。
  16. 一种合金固体，其特征在于，通过权利要求1步骤一与步骤二所述的初始合金固体的制备方法制备；其具体特征包括，通过包括如下步骤制备：
    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，得到均匀的初始合金熔体；所述初始合金熔体的主要成分为La xFe yT zM aD b，其中T包含Cr、V中的至少一种，M包含Al、Ni、Co、Si中的至少一种，D包含Mo、W、Ti中的至少一种，x、y、z、a、b分别代表对应组成元素的原子百分比含量，且18％≤x≤95.8％，4％≤y≤81.8％，0.1％≤z≤35％，0≤a≤40％，0≤b≤15％；
    将初始合金熔体通过快速凝固技术凝固成初始合金固体；所述初始合金固体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的熔点，所述弥散颗粒相被包覆于所述基体相中；所述基体相在凝固组织中的体积百分数不低于40％；所述基体相的平均成分主要为La x1M a1；所述弥散颗粒相的成分主要为Fe y2T z2M a2D b2La x2，其中，x1、a1、x2、y2、z2、a2、b2分别代表对应组成元素的原子百分比含量，且45％≤x1≤100％，0％≤a1≤55％，50％≤y2≤98％，0.2％≤z2<50％，0％≤a2≤30％，0％≤b2≤35％，0<x2≤5％；所述弥散颗粒相中包括可观含量的球形或近球形弥散颗粒相，且部分球形或近球形弥散颗粒相含有一定的枝晶特征；所述弥散颗粒相的粒径大小为5nm～50μm。
  17. 根据权利要求4所述的球形铁合金粉体材料在磁流体领域的应用。
  18. 根据权利要求17所述的球形铁合金粉体材料在磁流体领域的应用，其特征在于，包括如下步骤：将所述球形铁合金粉体与载液及表面活性剂混合均匀，即得到磁流体；所述球形铁合金粉体材料的部分特征包括：球形铁合金粉体材料的主要成分为Fe y2T z2M a2D b2La x2；其中，50％≤y2≤98％，0.2％≤z2<50％，0％≤a2≤30％，0％≤b2≤35％，0<x2≤5％；1％≤z2+b2<50％；所述铁合金粉体颗粒的形状主要为球形或近球形，且部分球形或近球形铁合金粉体颗粒含有一定的枝晶特征；所述铁合金粉体颗粒的粒径大小为5nm～100nm；所述T包含Cr、V中的至少一种，M包含Al、Ni、Co、Si中的至少一种，D包含Mo、W、Ti中的至少一种；x1、a1、x2、y2、z2、a2、b2分别代表对应组成元素的原子百分比含量。
  19. 一种冠状病毒状球形铁合金粉体颗粒，其特征包括：所述冠状病毒状球形铁合金粉体颗粒的主要成分为Fe y2T z2M a2D b2La x2；其中，50％≤y2≤98％，0.2％≤z2<50％，0％≤a2≤30％，0％≤b2≤35％，0<x2≤5％；T包含Cr、V中的至少一种，M包含Al、Ni、Co、Si中的至少一种，D包含Mo、W、Ti中的至少一种，La为稀土La，且La主要固溶存在于主要成分为Fe y2T z2M a2D b2La x2的冠状病毒状球形铁合金颗粒中；x1、a1、x2、y2、z2、a2、b2分别代表对应组成元素的原子百分比含量；所述冠状病毒状球形铁合金粉体颗粒包括主体部分与附体部分；其中，主体部分为球形或近球形的球体，附体部分为原位生长在主体部分球体表面的多个凸起；所述球形铁合金粉体颗粒具有类冠状病毒的形状，其附体部分的多个凸起即对应于冠状病毒形状的多个冠状凸起；所述冠状病毒状球形铁合金粉体颗粒主体部分球体直径大小为20nm～50μm，且其附体部分凸起的高度低于主体部分球体直径的0.3倍。
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06163228A (ja) * 1992-11-18 1994-06-10 Asahi Chem Ind Co Ltd 窒化物磁性粉とその製造法
CN112143926A (zh) * 2019-11-28 2020-12-29 刘丽 一种含铝合金粉体的制备方法及其应用及一种合金条带
CN112207285A (zh) * 2020-03-12 2021-01-12 赵远云 粉体材料的制备方法及其应用
CN112276101A (zh) * 2020-08-19 2021-01-29 赵远云 一种高纯粉体材料的制备方法及其应用及一种合金条带
CN112404445A (zh) * 2020-08-19 2021-02-26 赵远云 高纯粉体材料的制备方法及其应用及一种双相粉体材料
CN113649565A (zh) * 2020-09-30 2021-11-16 赵远云 一类合金粉及其制备方法与用途

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06163228A (ja) * 1992-11-18 1994-06-10 Asahi Chem Ind Co Ltd 窒化物磁性粉とその製造法
CN112143926A (zh) * 2019-11-28 2020-12-29 刘丽 一种含铝合金粉体的制备方法及其应用及一种合金条带
CA3159866A1 (en) * 2019-11-28 2021-06-03 Yuanyun ZHAO Method for preparing aluminum-containing alloy powder, use thereof and alloy strip
CN112207285A (zh) * 2020-03-12 2021-01-12 赵远云 粉体材料的制备方法及其应用
WO2021179677A1 (zh) * 2020-03-12 2021-09-16 赵远云 粉体材料的制备方法及其应用
CN112276101A (zh) * 2020-08-19 2021-01-29 赵远云 一种高纯粉体材料的制备方法及其应用及一种合金条带
CN112404445A (zh) * 2020-08-19 2021-02-26 赵远云 高纯粉体材料的制备方法及其应用及一种双相粉体材料
CN113649565A (zh) * 2020-09-30 2021-11-16 赵远云 一类合金粉及其制备方法与用途

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