Alloy powder, preparation method therefor, and use thereof

Abstract

The present disclosure relates to a method for preparing a category of alloy powder and an application thereof. By selecting a suitable alloy system and melting initial alloy melt through low-purity raw materials, high-purity alloy powder, and matrix phase wrapping high-purity alloy powder are precipitated during the solidification process of the initial alloy melt, and the solid solution alloying of the high-purity alloy powder is achieved at the same time. Alloy powder can be obtained by removing the matrix phase wrapping the high-purity alloy powder; high-purity alloy powder can also be obtained by removing the matrix phase wrapping the high-purity alloy powder at an appropriate time. The method is simple and can prepare a variety of alloy powder materials with different morphology at nano-scale, sub-micron level, micron level, and even millimeter level, which has a good application prospect in the fields such as catalysis, powder metallurgy, composite materials, magnetic materials, sterilization, metal injection molding, metal powder 3D printing, coatings and composite materials.

Description

A kind of alloy powder and its preparation method and use Technical Field

[0001] The present invention relates to the technical field of metal materials, in particular to a type of alloy powder and a preparation method and application thereof. Background Art

[0002] Metal powders with micro-nano particle sizes have special surface effects, quantum size effects, quantum tunneling effects, and Coulomb blockade effects. They exhibit many unique properties different from traditional materials in optics, electricity, magnetism, catalysis, etc., and are therefore widely used in optoelectronic devices, absorbing materials, high-efficiency catalysts and other fields.

[0003] Currently, metal powder preparation methods are categorized by their physical state into solid-phase, liquid-phase, and vapor-phase methods. Solid-phase methods primarily include mechanical pulverization, ultrasonic pulverization, thermal decomposition, and explosion. Liquid-phase methods primarily include precipitation, alkoxide, carbonylation, spray drying, freeze drying, electrolysis, and chemical coagulation. Vapor-phase methods primarily include gas-phase reaction, plasma, high-temperature plasma, evaporation, and chemical vapor deposition. While there are numerous methods for preparing metal powders, each has its limitations. For example, liquid-phase methods suffer from low yields, high costs, and complex processes. Mechanical methods also suffer from difficulties in post-production powder classification, and the product's purity, fineness, and morphology cannot be guaranteed. Rotating electrode and gas atomization methods are currently the primary methods for preparing high-performance metal and alloy powders, but they suffer from low production efficiency, low yields of ultrafine powders, and relatively high energy consumption. Jet milling and hydrodehydrogenation methods are suitable for large-scale industrial production but are more selective for the raw metals and alloys. Furthermore, the impurity content of metal or alloy powders, particularly oxygen content, significantly impacts their performance. Currently, controlling the impurity content of metal or alloy powders primarily involves controlling the purity of the raw materials and the degree of vacuum, which is costly. Therefore, developing new methods for preparing high-purity metal powder materials is of great significance.

[0004] Summary of the Invention

[0005] Based on this, it is necessary to provide a method for preparing high-purity alloy powder materials with simple process, low cost and easy operation to address the above technical problems.

[0006] In order to solve the above technical problems, the technical solution of the present invention is:

[0007] A metal material composed of endogenous alloy powder and a coating, characterized in that it is prepared by solidification of an alloy melt, and its composition includes a dispersed particle phase endogenously precipitated during the initial alloy solidification process and a matrix phase coating the dispersed particles, the two phases corresponding to the endogenous alloy powder and the coating respectively; the elemental composition of the endogenous alloy powder is mainly Ma1 A b1 T c1 The element composition of the coating is mainly A b2 T c2 , wherein M and A each contain one or more metal elements, T is an impurity element including oxygen, a1, b1, c1, b2, c2 represent the atomic percentage content of the corresponding element composition, and a1+b1+c1=100%,b2+c2=100%,c2>c1>0,b1>0; the melting point of the endogenous alloy powder is higher than the melting point of the coating; the endogenous alloy powder M a1 A b1 T c1 A element is solid-dissolved therein; between the M and the A, one or more groups of M that do not form intermetallic compounds are included. 1 -A 1 element combination, where M 1 Represents any element in M, A 1 represents any element in A, and the main elements in M ​​are those that satisfy M 1 -A 1 Each M of the element combination condition 1 Elements, the main elements in A are composed of 1 -A 1 Each A of the element combination conditions 1 The metal material composed of the endogenous alloy powder and the coating is completely melted and then re-solidified, but does not generate an intermetallic compound composed of the main element in M ​​and the main element in A, but generates the endogenous alloy powder M a1 A b1 T c1 With the coating A b2 T c2 .

[0008] Supplementary explanation: T is an impurity element including oxygen, which means that T is an impurity element and T includes O;

[0009] The solidification method of the initial alloy melt includes conventional casting, continuous casting, melt spinning, melt pulling, and the like. The particle size of the endogenous alloy powder is related to the solidification rate of the initial alloy melt. Generally speaking, the particle size of the endogenous alloy powder is negatively correlated with the solidification rate of the initial alloy melt, that is, the greater the solidification rate of the initial alloy melt, the smaller the particle size of the endogenous alloy powder.

[0010] Furthermore, the solidification method of the initial alloy melt does not include the solidification method corresponding to the atomization powder making technology;

[0011] Supplementary explanation: The solidification rate of the initial alloy melt ranges from 0.001K / s to 108 K / s;

[0012] Furthermore, the solidification rate of the initial alloy melt ranges from 0.001K / s to 10 7 K / s;

[0013] Furthermore, the particle size of the endogenous alloy powder ranges from 3 nm to 10 mm.

[0014] Supplementary explanation: The particle size range of the endogenous alloy powder is 3nm~1mm;

[0015] Preferably, the particle size of the endogenous alloy powder is in the range of 3 nm to 500 μm;

[0016] Preferably, the particle size of the endogenous alloy powder is in the range of 3 nm to 99 μm;

[0017] Preferably, the particle size of the endogenous alloy powder is in the range of 3 nm to 25 μm;

[0018] Preferably, the particle size of the endogenous alloy powder is in the range of 3 nm to 10 μm;

[0019] Furthermore, the particle shape of the endogenous alloy powder is not limited and may include at least one of dendritic, spherical, nearly spherical, square, pie, and rod shapes; when the particle shape is rod-shaped, the particle size specifically refers to the diameter of the rod cross section.

[0020] The shape of the metal material composed of the endogenous alloy powder and the coating is related to the solidification method: when the solidification method is continuous casting, its shape is generally mainly lamellar; when the solidification method is melt stripping, its shape is generally mainly strip-shaped or thin plate-shaped; when the solidification method is melt pulling, its shape is generally mainly wire-shaped. When the solidification rate is higher, the cross-section of the metal material composed of the endogenous alloy powder and the coating becomes thinner, finer, and narrower; conversely, the cross-section becomes thicker, coarser, and wider.

[0021] Furthermore, the shape of the metal material composed of the endogenous alloy powder and the coating does not include the powder shape of the product corresponding to the atomization powder making technology;

[0022] Furthermore, when the initial alloy melt is solidified by a method including melt stripping, and the solidification rate is 100K / s to 10 7 K / s, a metal material strip consisting of endogenous alloy powder and a coating with a thickness of about 10 μm to 5 mm can be obtained, and the particle size of the endogenous alloy powder contained therein ranges from 3 nm to 200 μm.

[0023] Furthermore, when the initial alloy melt is solidified by a method including ordinary casting or continuous casting, and the solidification rate is 0.001K / s to 100K / s, a metal material composed of endogenous alloy powder and a coating in the form of a block with at least one dimension exceeding 5mm in the three-dimensional scale direction can be obtained, and the particle size range of the endogenous alloy powder is 200μm to 10mm.

[0024] Supplementary explanation: Furthermore, the metal material composed of the endogenous alloy powder and the coating is in the shape of a strip, and the thickness of the strip is 5 μm to 5 mm;

[0025] Furthermore, the metal material composed of the endogenous alloy powder and the coating is in the shape of a strip, and the thickness of the strip is 10 μm to 1 mm;

[0026] Furthermore, the lower limit of the volume percentage content of the endogenous alloy powder in the metal material composed of the endogenous alloy powder and the coating is 1%, and the upper limit is the volume percentage content corresponding to the dispersion distribution of the endogenous alloy powder in the coating.

[0027] When considering how much dispersed endogenous alloy powder can be coated in the coating, it is necessary to accurately evaluate it by the volume percentage content of the endogenous alloy powder, because the volume relationship is directly related to whether the endogenous alloy powder can be dispersed. The volume percentage content can be converted by the density, atomic weight and other relationships of each element and the atomic percentage content. When the coating matrix element is a large atomic element, the matrix can obtain a higher volume percentage content through a smaller atomic percentage content, thereby significantly increasing the content of the endogenous alloy powder that can be coated. For example, if the atomic percentage composition is Ce 50 Ti 50 The alloy melt has a Ce and Ti weight percentage of 74.53wt% and 25.47wt% respectively, and the combined density is 6.7g / cm 3 and 4.5g / cm 3 , it can be calculated that Ce and Ti have an atomic percentage of Ce 50 Ti 50 The volume percentages of Ti in the melt of Ce-Ti are 66 vol% and 34 vol%, respectively. If Ti precipitates from the melt, its volume percentage is only about 34 vol%, ignoring solid solution and impurities. This indicates that even if the atomic percentage of Ti in the Ce-Ti alloy exceeds 50%, its volume percentage can still be significantly lower than 50%, which is conducive to obtaining dispersed Ti particles.

[0028] Since the application of the metal material composed of endogenous alloy powder and a coating mainly relies on the application effect of the endogenous alloy powder, and the coating needs to be removed later, when the volume percentage of endogenous alloy powder is less than 1%, it will cause a great waste of coating material, which will lose the practical significance of the material application.

[0029] Due to different alloy systems and different solidification rates, the size and morphology of the generated endogenous alloy powder vary. For example, when the cooling rate is fast and the endogenous alloy powder is mainly fine spherical or near-spherical nanopowder, its particle growth is limited, and a certain space and distance between particles are easily maintained. While ensuring the endogenous alloy powder is dispersed, it can achieve a high volume percentage content. When the cooling rate is slow and the endogenous alloy powder is mainly coarse dendrites, its particle growth is very sufficient, and different particles are prone to meet, merge, and entangle during growth. While ensuring the endogenous dendrite alloy particles are dispersed, the endogenous dendrite alloy powder can only achieve a relatively low volume percentage content.

[0030] Preferably, the volume percentage content of the endogenous alloy powder in the metal material composed of the endogenous alloy powder and the coating body is in the range of 5% to 50%;

[0031] As a further preference, the volume percentage content of the endogenous alloy powder in the metal material composed of the endogenous alloy powder and the coating is in the range of 5% to 40%; the preferred lower limit ensures economy, and the preferred upper limit fully ensures that the endogenous alloy powder can be dispersed in the coating.

[0032] The endogenous alloy powder solidifies and precipitates from the initial melt. According to the nucleation and growth theory, whether it is a nearly spherical nanoparticle that has just nucleated and grown, or a fully grown micron-sized dendrite particle, its crystal growth has a fixed orientation relationship, so that the precipitated single particles are mainly composed of a single crystal.

[0033] When the volume percentage of the endogenous alloy powder is high, it is not ruled out that two or more particles may merge during the endogenous precipitation process of the single crystal particles. If two or more single crystal particles are only softly agglomerated, mutually adsorbed, or only connected together at a few locations, and are not fully combined into one particle through normal grain boundaries like polycrystalline materials, they are still two single crystal particles. Its characteristic is that after the coating is removed in the subsequent process, these single crystal particles can be easily separated by technologies including ultrasonic dispersion treatment and airflow grinding. However, it is difficult to separate the grain boundaries of normal ductile metal polycrystalline materials using technologies including ultrasonic dispersion treatment and airflow grinding.

[0034] Preferably, the number of single crystal particles in the endogenous alloy powder accounts for no less than 60% of the total number of particles.

[0035] As a further preference, the number of single crystal particles in the endogenous alloy powder accounts for no less than 75% of the total number of particles.

[0036] As a further preference, the number of single crystal particles in the endogenous alloy powder accounts for no less than 90% of the total number of particles.

[0037] Supplementary explanation: In the metal material composed of endogenous alloy powder and coating, both the endogenous alloy powder and coating are crystalline;

[0038] The element composition of the endogenous alloy powder is mainly M a1 A b1 T c1 The element composition of the coating is mainly A b2 T c2 , where M and A each contain one or more metal elements, T is an impurity element including oxygen, where a1, b1, c1, b2, and c2 represent the atomic percentage content of the corresponding element composition, and a1+b1+c1=100%, b2+c2=100%;

[0039] Characterizing the composition of each element by its atomic percentage content can accurately express the increase or decrease of the element content through the concept of the amount of substance, such as the increase or decrease and change of impurity elements. If the mass percentage content (or ppm concept) of the element is used to characterize the content of each element, it is easy to produce wrong conclusions due to the different atomic weights of each element. For example, if the atomic percentage content of Ti is 45 Gd 45 O 10 The alloy contains 100 atoms, and the atomic percentage of O is 10at%. These 100 atoms are divided into Ti 45 O4 (atomic percentage composition is Ti 91.8 O 8.2 ) and Gd 45 O6 (atomic percentage composition of Gd 88.2 O 11.8 ) two parts, Gd 45 The atomic percentage of oxygen in O6 increases to 11.8at%, Ti 45 The atomic percentage of oxygen in O4 is reduced to 8.2at%, which can accurately express that Gd is enriched with O. However, if the mass percentage of O is used to measure, Ti 45 Gd 45 O 10 The mass percentage of O is 1.70wt%, Ti 45 O4 and Gd 45The mass percentage content of O in O6 is 2.9 wt.% and 1.34 wt.% respectively, and Ti will be obtained. 40 The O content in Ti 40 O4 is significantly higher than that in Gd

[0040] Furthermore, the melting point of the internal alloy powder M a1 A b1 T c1 is higher than that of the coating A b2 T c2 . After meeting this condition, when the initial alloy solidifies, its matrix phase solidifies last and coats the internal alloy powder.

[0041] Furthermore, the internal alloy powder M a1 A b1 T c1 dissolves element A, that is, 0 < b1.

[0042] Preferably, 0 < b1 ≤ 15%; that is, M a1 A b1 T c1 can dissolve up to 15% of element A (atomic percentage content) at most. According to the differences in the main element composition of the specific alloy melt, the impurity content, and the solidification rate, the solubility of A in M a1 A b1 T c1 the internal alloy powder is also different. Generally speaking, when the solidification rate of the melt is relatively high and smaller internal alloy powders are formed, such as nanopowders, it can dissolve more element A.

[0043] Furthermore, the internal alloy powder contains a certain amount of impurity T, and the content of T impurity element in the internal alloy powder is lower than that of the corresponding T impurity element in the coating, that is, c2 > c1 > 0. This indicates that for the metal material composed of the internal alloy powder and the coating prepared by the alloy melt solidification method, the impurity elements will be enriched in the coating A b2 T c2 , and at the same time, M a1 A b1 T c1 the internal alloy powder is purified.

[0044] Furthermore, T is impurity elements such as O, H, N, P, S, F, Cl including oxygen, and 0 < c1 ≤ 1.5%.

[0045] Supplementary explanation: That is to say, T contains O, and the content of O is greater than zero; when a specific element among the above-listed H, N, P, S, F, and Cl elements is not contained, its content is zero, and when it is contained, its content is greater than zero; the content of T is the total content of O, H, N, P, S, F, and Cl elements.

[0046] Preferably, T is an impurity element including oxygen, such as O, H, N, P, S, F, Cl, etc., and 0.01%≤c1≤1.5%.

[0047] The M and A both contain one or more metal elements. The selection of M and A is the key to preparing the metal material composed of the endogenous alloy powder and the coating. In order to ensure that the intermetallic compound composed of the main element in M ​​and the main element in A will not be generated during the solidification of the alloy melt, but the endogenous alloy powder M will be generated. a1 A b1 T c1 With the coating A b2 T c2 , M and A need to satisfy the following relationship:

[0048] The M and the A contain one or more groups of M that do not form intermetallic compounds. 1 -A 1 element combination; among them, M 1 Represents any element in M, A 1 represents any element in A, and the main elements in M ​​are those that satisfy M 1 -A 1 Each M of the element combination condition 1 Elements, the main elements in A are composed of 1 -A 1 Each A of the element combination conditions 1 Element composition.

[0049] Furthermore, in M ​​or A, when each M that meets the above combination conditions 1 Elements or A 1 When the atomic percentage content of an element accounts for more than 30% of M or A, it can be called the main element in M ​​or A, respectively.

[0050] Furthermore, when M contains at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti, Fe, Co, Ni, Mn, Cu, and Ag, and A contains at least one of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mg, Ca, Li, Na, K, In, Pb, and Zn, it can be satisfied that no intermetallic compound composed of the main element in M ​​and the main element in A will be generated during the solidification of the alloy melt. According to the alloy phase diagram, among the elements listed above, any one of the elements in M ​​can find a corresponding M in A that does not generate an intermetallic compound. 1 -A 1 Combination pairs, such as Cr-Y, Ti-Ce, Fe-Mg, Co-K, Ni-Li, Mn-Mg, Cu-Li, Ag-Pb, etc. When there are multiple groups of M between M and A 1 -A 1 When the combination is paired, each M 1 The set of A 1 The set of M will still meet the condition that no corresponding intermetallic compound will be generated when the alloy melt solidifies. For example, Ti-Ce, Ti-Gd, Nb-Ce, Nb-Gd all meet the M 1 -A 1 If the combination pair condition is met, then (Ti-Nb)-(Ce-Gd) will still meet the combination pair condition of no intermetallic compound formation during solidification of the corresponding alloy melt. In this case, the main elements in M ​​include Ti and Nb, and the main elements in A include Ce and Gd.

[0051] In addition, when the main elements in M ​​and the main elements in A satisfy one or more groups of M 1 -A 1 Under the condition of combination pair, if M also contains elements that can be combined with the main element M in M 1 Elements M that form stable high melting point intermetallic compounds 2 When M 1 With M 2 It will form a high melting point and stable M 1 -M 2 Intermetallic compound, and M 1 With M 2 They do not form intermetallic compounds with the main elements in A. In this case, the endogenous alloy powder is M 1 -M 2 Intermetallic compound powder.

[0052] Preferably, M comprises at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, and Ti, and A comprises at least one of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

[0053] Preferably, when M contains at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, and Ti, and at the same time contains at least one of Fe, Co, and Ni, a high-melting-point intermetallic compound can be formed between the two subclass elements in M. When A contains at least one of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, an endogenous intermetallic compound powder mainly composed of the two subclass elements in M ​​can be formed.

[0054] Preferably, when M contains at least one of the sub-class elements W, Cr, Mo, V, Ta, Nb, Zr, Hf, and Ti, and at the same time contains at least one of the sub-class elements Fe, Co, and Ni, and the molar ratio of the two sub-class elements is about 1:1, a stable high-melting-point intermetallic compound can be formed between the two sub-class elements in M. When A contains at least one of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, an endogenous intermetallic compound powder mainly composed of the two sub-class elements in M ​​and with a molar ratio of about 1:1, and a coating mainly composed of the A element are formed during the solidification process of the alloy melt.

[0055] Preferably, M includes at least one of Mn, Fe, Ni, Cu, and Ag, and A includes at least one of Mg, La, In, Na, K, Li, and Pb.

[0056] Furthermore, M includes at least one of Ir, Ru, Re, Os, Tc, W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti, and Fe, and A includes at least one of Cu and Zn.

[0057] Supplementary explanation: Furthermore, the M includes at least one of Ir, Ru, Re, Os, Tc, W, Cr, Mo, V, Ta, and Nb, and A includes Cu.

[0058] Furthermore, the M includes at least one of Ir, Ru, Re, Os, and Tc, and A includes Cu.

[0059] It should be noted that the A, M, or T may also contain other alloying elements or impurity elements in addition to the elements listed above. As long as the change in the content of these elements does not cause a "qualitative change" in the initial alloy solidification process and laws, it will not affect the implementation of the above-mentioned technical solutions of the present invention.

[0060] The present invention also relates to an alloy powder prepared by removing the coating from the metal material composed of the endogenous alloy powder and the coating, characterized in that the elemental composition thereof is mainly M a3A b3 T c3 , a3, b3, c3 respectively represent the atomic percentage content of the corresponding element composition, b3>0, a3+b3+c3=100%, and the T element content in the alloy powder is higher than the T element content in the endogenous alloy powder, that is, c3>c1>0.

[0061] The alloy powder is prepared by removing the coating from the metal material composed of the endogenous alloy powder and the coating. Therefore, most of the characteristics of the alloy powder are consistent with those of the endogenous alloy powder. The difference is that the endogenous alloy powder is coated in the coating, eliminating the influence of impurities such as oxygen in the environment. However, when the alloy powder has a fine particle size, such as nano alloy powder, the surface or surface atoms of the alloy powder will combine with impurity elements such as oxygen during the exposure process, resulting in an increase in its T element content, that is, c3>c1>0.

[0062] Preferably, the number of single crystal particles in the alloy powder accounts for no less than 60% of the total number of particles.

[0063] As a further preference, the number of single crystal particles in the alloy powder accounts for no less than 75% of the total number of particles.

[0064] As a further preference, the number of single crystal particles in the alloy powder accounts for no less than 90% of the total number of particles.

[0065] Preferably, the particle size of the alloy powder is in the range of 3 nm to 10 mm.

[0066] Supplementary explanation: The particle size range of the alloy powder is 3nm~1mm;

[0067] Preferably, the particle size of the alloy powder is in the range of 3 nm to 500 μm;

[0068] Preferably, the particle size of the alloy powder ranges from 3 nm to 99 μm;

[0069] Preferably, the particle size of the alloy powder is in the range of 3 nm to 25 μm;

[0070] Preferably, the particle size of the alloy powder is in the range of 3 nm to 10 μm;

[0071] Preferably, the particle size of the alloy powder is in the range of 3 nm to 5 μm;

[0072] The present invention also relates to a spherical or nearly spherical alloy powder, characterized in that the alloy powder is subjected to plasma spheroidization treatment to obtain a spherical or nearly spherical alloy powder. a4 A b4 Tc4 a4, b4, and c4 respectively represent the atomic percentage contents of the corresponding elements, b4 > 0, a4 + b4 + c4 = 100%, and the content of element T in the spherical or near-spherical alloy powder is higher than that in the alloy powder without plasma spheroidization treatment, that is, c4 > c3 > c1 > 0.

[0073] Furthermore, before the plasma spheroidization treatment, the selected particles are pre-crushed by a jet mill to disperse and crush the possibly entangled particles, which is beneficial for the subsequent spheroidization treatment.

[0074] Furthermore, the alloy powder is sieved before the plasma spheroidization treatment;

[0075] Furthermore, the particle size range of the alloy powder for plasma spheroidization treatment is 5 μm - 200 μm.

[0076] Supplementary note, the particle size range of the alloy powder for plasma spheroidization treatment is 5 μm - 100 μm.

[0077] The present invention also relates to a preparation method of a metal material composed of an endogenic alloy powder and a coating body, which is characterized in that it is prepared by the following steps:

[0078] (1) Melting an initial alloy melt with the main element composition of M a0 A b0 T c0 where M and A each contain one or more metal elements, T is an impurity element including oxygen element, a0, b0, and c0 represent the atomic percentage contents of the corresponding constituent elements, a0 + b0 + c0 = 100%, 0 < c0 ≤ 15%; there are one or more groups of M 1 -A 1 element combinations that do not form intermetallic compounds between the M 1 represents any one element in M, A 1 represents any one element in A; and the main element in M is composed of each M 1 -A 1 element that satisfies the element combination condition, and the main element in A is composed of each A 1 element that satisfies the M 1 -A 1 element combination condition; 1

[0079] [[ID=四十八]](2) Solidifying the M a0 A b0 T c0 initial alloy melt into a solid state to obtain the M a1 A b1 T c1 ​Dispersed particle phase and A coating the dispersed particles b2 T c2 Matrix phase, which is the metal material composed of the in-situ alloy powder and the coating; where 0 < c1 < c0 < c2, that is, M a0 A b0 T c0 The content of element T in the initial alloy melt is higher than M a1 A b1 T c1 The content of element T in the dispersed particle phase, while lower than A b2 T c2 The content of element T in the matrix phase.

[0080] The solidification methods of the initial alloy melt include methods such as ordinary casting, continuous casting, melt spinning, and melt drawing. The particle size of the in-situ alloy powder is related to the solidification rate of the initial alloy melt. Generally, the particle size of the in-situ alloy powder is negatively correlated with the solidification rate of the initial alloy melt, that is: the greater the solidification rate of the initial alloy melt, the smaller the particle size of the in-situ alloy powder.

[0081] Furthermore, the solidification method of the initial alloy melt does not include the solidification method corresponding to the atomization powder making technology;

[0082] Supplementary note: The solidification rate range of the initial alloy melt is 0.001 K / s to 10 8 K / s;

[0083] Furthermore, the solidification rate range of the initial alloy melt includes 0.001 K / s to 10 7 K / s;

[0084] Furthermore, the particle size range of the in-situ alloy powder includes 3 nm to 10 mm.

[0085] Furthermore, the particle shape of the in-situ alloy powder is not limited, and may include at least one of dendritic, spherical, near-spherical, square, cake-shaped, and rod-shaped; when the particle shape is rod-shaped, the particle size specifically refers to the diameter size of the rod cross-section.

[0086] The shape of the metal material composed of the in-situ alloy powder and the coating is related to the solidification method: when the solidification method is continuous casting, its shape is generally mainly plate-shaped; when the solidification method is melt spinning, its shape is generally mainly strip-shaped or thin plate-shaped; when the solidification method is melt drawing, its shape is generally mainly filamentous. When the solidification rate is higher, the cross-section of the metal material composed of the in-situ alloy powder and the coating obtained is thinner, finer, and narrower; conversely, its cross-section is thicker, coarser, and wider;

[0087] Furthermore, the shape of the metal material composed of the endogenous alloy powder and the coating does not include the powder shape of the product corresponding to the atomization powder making technology;

[0088] As an example, when the initial alloy melt is solidified by melt stripping, and the solidification rate is 100K / s to 10 7 K / s, a metal strip consisting of endogenous alloy powder and a coating with a thickness of about 10 μm to 5 mm can be obtained, and the particle size of the endogenous alloy powder included is in the range of 3 nm to 200 μm.

[0089] Preferably, when the initial alloy melt is solidified by ordinary casting or continuous casting, and the solidification rate is 0.001K / s to 100K / s, a block-shaped metal material with at least one dimension exceeding 5mm in the three-dimensional scale direction and composed of endogenous alloy powder and a coating can be obtained, and the particle size range of the endogenous alloy powder is 200μm to 10mm.

[0090] Supplementary explanation: Furthermore, the metal material composed of the endogenous alloy powder and the coating is in the shape of a strip, and the thickness of the strip is 5 μm to 5 mm;

[0091] Furthermore, the metal material composed of the endogenous alloy powder and the coating is in the shape of a strip, and the thickness of the strip is 10 μm to 1 mm;

[0092] Furthermore, the metal material composed of the endogenous alloy powder and the coating is in a strip shape, and the thickness of the strip is 10 μm to 500 μm;

[0093] Furthermore, the metal material composed of the endogenous alloy powder and the coating is in a strip shape, and the thickness of the strip is 10 μm to 100 μm;

[0094] Furthermore, the lower limit of the volume percentage content of the endogenous alloy powder in the metal material composed of the endogenous alloy powder and the coating is 1%, and the upper limit is the volume percentage content corresponding to the dispersion distribution of the endogenous alloy powder in the coating.

[0095] Preferably, the volume percentage content of the endogenous alloy powder in the metal material composed of the endogenous alloy powder and the coating body is in the range of 5% to 50%;

[0096] As a further preference, the volume percentage content of the endogenous alloy powder in the metal material composed of the endogenous alloy powder and the coating is in the range of 5% to 40%; the preferred lower limit ensures economy, and the preferred upper limit fully ensures that the endogenous alloy powder can be dispersed in the coating.

[0097] Preferably, the number of single crystal particles in the endogenous alloy powder accounts for no less than 60% of the total number of particles.

[0098] As a further preference, the proportion of single crystal particles in the in-situ alloy powder in all the particle numbers is not less than 75%.

[0099] As a further preference, the proportion of single crystal particles in the in-situ alloy powder in all the particle numbers is not less than 90%.

[0100] Furthermore, the in-situ alloy powder M a1 A b1 T c1 has a melting point higher than that of the coating A b2 T c2 ; after meeting this condition, when the initial alloy solidifies, its matrix phase solidifies last and coats the in-situ alloy powder.

[0101] Furthermore, the in-situ alloy powder M a1 A b1 T c1 dissolves element A, that is, 0 < b1.

[0102] As a preference, 0 < b1 ≤ 15%; that is, M a1 A b1 T c1 can dissolve at most 15% of element A (atomic percentage content). According to the differences in the main element composition of the specific alloy melt, the impurity content, and the solidification rate, the solubility of A in M a1 A b1 T c1 in-situ alloy powder is also different. Generally speaking, when the solidification rate of the melt is relatively high and smaller in-situ alloy powder is formed, such as nano-powder, it can dissolve more element A.

[0103] Supplementary note: Furthermore, 0.01% < b1 ≤ 15%; furthermore, 0.05% < b1 ≤ 15%; furthermore, 0.1% < b1 ≤ 15%;

[0104] Furthermore, T is impurity elements such as O, H, N, P, S, F, Cl including oxygen, and 0 < c1 ≤ 1.5%.

[0105] [[ID=​​​​​More A elements can be dissolved in the endogenous alloy powder. The possible reason is that the A, M, and T elements in the initial alloy melt are uniformly mixed at the beginning. During the cooling and solidification process of the initial alloy melt, the dispersed particle phase mainly composed of M is first precipitated from the melt. During the precipitation process, the T element atoms are expelled. When the T element atoms are expelled, some vacancies may be formed. Such vacancies can be replaced by M atoms and can also be replaced by A atoms. Therefore, under the same conditions, when the content of T elements is higher, there are more vacancies that can be replaced, and M atoms are more likely to be replaced. a1 A b1 T c1 The higher the content of A element in the solid solution of the endogenous alloy powder, the higher the content of A element in the solid solution of the endogenous alloy powder. a1 A b1 T c1 The amount of dissolved A element in the endogenous alloy powder is also affected by the thermodynamics and kinetics of the initial alloy melt during solidification. From a thermodynamic point of view, when the T content is high, M a1 A b1 T c1 More A elements can be dissolved in the endogenous alloy powder; from a kinetic point of view, when the initial alloy melt solidifies at a high rate and forms smaller endogenous alloy powder, M a1 A b1 T c1 Endogenous alloy powder can dissolve more A elements;

[0106] Furthermore, the M a0 A b0 T c0 The initial alloy melt is formed by melting an alloy raw material comprising a first raw material and a second raw material; wherein the main element composition of the first raw material is M d1 T e1 The main element composition of the second raw material is A d2 T e2 , d1, e1, d2, e2 represent the atomic percentage content of the corresponding elements, and 0 <e1≤10%,0<e2≤10%,d1+e1=100%,d2+e2=100%。

[0107] As a preference, 0 <c0≤10%,0<e1≤7.5%,0<e2≤7.5%。

[0108] More preferably, 0.01%≤c0≤10%, 0.01%≤e1≤7.5%, and 0.01%≤e2≤7.5%.

[0109] This indicates that a metal material consisting of an endogenous alloy powder and a coating containing a high-purity target endogenous alloy powder can be prepared from a low-purity raw material.

[0110] Supplementary explanation: Further, in a plurality of embodiments, in the metal material composed of the endogenous alloy powder and the coating, the endogenous M a1 A b1 T c1 The content of T impurities in alloy powder is higher than that of M d1 T e1 The raw materials have been greatly reduced, that is, endogenous M a1 A b1 T c1 The T impurity content in the alloy powder is lower than M d1 T e1 The T content in the raw material, that is, c1 is less than e1.

[0111] Supplementary explanation: Further, in a plurality of embodiments, in the metal material composed of the endogenous alloy powder and the coating, the endogenous M a1 A b1 T c1 The volume percentage of alloy powder and the raw material preparation M d1 T e1 The volume percentage of the raw materials is similar; similar means close. Therefore, the internal M content of the metal material composed of the target internal alloy powder and the coating can be designed according to the need. a1 A b1 T c1 The volume percentage of alloy powder can be roughly reversed to obtain the melting M a0 A b0 T c0 Initial alloy melt time M d1 T e1 Raw materials and A d2 T e2 The volume percentage of each raw material required; when M d1 T e1 Raw materials and A d2 T e2 When the volume percentage of each raw material is determined, the relative ratio of a0 and b0 can be calculated using data such as the atomic weight and density of each element.

[0112] It should be noted that, since impurity elements such as O in the atmosphere may enter the melt during the smelting process, the situation of c0>e1, c0>e2 may occur, that is, M a0 A b0 T c0 The impurity content in the initial alloy melt increases relative to the total impurity content in the alloy raw materials.

[0113] Supplementary note: Meanwhile, during the initial alloy melting process, some of the T element may form a small amount of slag floating on the melt surface with M or A. Since the slag is generally solid and does not belong to the initial alloy melt part, the content of the T element in the initial alloy melt may also show the situation of c0 < e1, c0 < e2, that is, M a0 A b0 T c0 The impurity content in the initial alloy melt is reduced compared with the total impurity content in the alloy raw materials.

[0114] The present invention also relates to a method for preparing alloy powder, which is characterized in that the coating part in the metal material composed of the endogenetic alloy powder and the coating is removed, and the endogenetic alloy powder that cannot be removed simultaneously is retained.

[0115] Furthermore, the method for removing the coating and retaining the endogenetic alloy powder includes at least one of acid solution dissolution reaction removal, alkali solution dissolution reaction removal, vacuum volatilization removal, and coating natural oxidation - pulverization removal.

[0116] When using acid solution reaction removal, appropriate acid varieties and concentrations are selected, and the selection criterion is to ensure that the coating A b2 T c2 becomes ions and enters the solution, while the endogenetic alloy powder M a1 A b1 T c1 hardly reacts with the corresponding acid, thereby achieving the removal of the coating.

[0117] Furthermore, the acid solution is degassed to make it contain a lower dissolved amount of oxygen and nitrogen.

[0118] When using alkali solution reaction removal, appropriate alkali varieties and concentrations are selected, and the selection criterion is to ensure that the coating A b2 T c2 becomes ions and enters the solution, while the endogenetic alloy powder M a1 A b1 T c1 hardly reacts with the corresponding alkali, thereby achieving the removal of the coating.

[0119] Furthermore, the alkali solution is degassed to make it contain a lower dissolved amount of oxygen and nitrogen.

[0120] When using vacuum volatilization removal, appropriate vacuum degree and temperature conditions are selected, and the selection criterion is to ensure that the coating A with a lower melting point b2 T c2 volatilizes, while the endogenetic alloy powder M with a higher melting point a1 ]>A b1 T c1 [[ID=]57]does not volatilize and is retained, thereby achieving the removal of the coating.

[0121] When the coating is very easy to be naturally oxidized and pulverized, the naturally oxidized and pulverized coating can be preliminarily removed, and then other methods can be used to completely remove the coating.

[0122] Supplementary explanation: Furthermore, in a certain embodiment, the M contains Fe, the A contains La, and the metal material composed of the endogenous alloy powder and the coating is a metal strip composed of endogenous Fe alloy powder and a La coating, and La is solid-dissolved in the endogenous Fe alloy powder; the endogenous Fe alloy powder and the oxide powder of the matrix La are pre-separated by natural oxidation and pulverization of the La coating, and the Fe alloy powder and the oxide of the matrix La are separated by a magnetic field through the magnetic properties of the Fe alloy powder.

[0123] The invention also relates to the application of the alloy powder in powder metallurgy, metal injection molding, magnetic materials and coatings.

[0124] Furthermore, when the particle size of the alloy powder is larger, it can be used in the fields of powder metallurgy and metal injection molding; when the particle size of the alloy powder is smaller, such as nanometer level, it can be used in the field of coatings, mainly as a coating additive with special functions.

[0125] Furthermore, when the alloy powder is a soft magnetic alloy powder, it can also be used in the field of magnetic materials.

[0126] The present invention also relates to the application of spherical or nearly spherical alloy powder in powder metallurgy, metal injection molding, and metal powder 3D printing.

[0127] The present invention also relates to the application of a metal material consisting of endogenous alloy powder and a coating in coatings and composite materials.

[0128] Furthermore, it is characterized in that a metal material consisting of endogenous alloy powder and a coating having an average particle size of less than 1000 nm is selected, and the coating is removed; while removing the coating or immediately after the coating is removed, the obtained alloy powder is mixed with other components of a coating or a composite material to reduce the content of impurities including O newly introduced into the surface or surface layer of the powder after the surface of the alloy powder is exposed, thereby obtaining an alloy powder with high surface activity and enabling other components of the coating or composite material to be well combined with the surface of the alloy powder at the atomic scale, thereby obtaining a coating or composite material added with high-purity ultrafine high-activity alloy powder, which can be applied to various fields including antibacterial coatings, weather-resistant coatings, stealth coatings, absorbing coatings, wear-resistant coatings, anti-corrosion coatings, resin-based composite materials, etc.

[0129] Furthermore, after the coating is removed, the cleaning and drying processes of the alloy powder, as well as the mixing process of the alloy powder with the coating or other components of the composite material are all carried out in a vacuum environment or a protective atmosphere.

[0130] Furthermore, after the coating is removed, the obtained alloy powder is mixed with the coating or other components of the composite material within 20 minutes.

[0131] As a further preference, after the coating is removed, the obtained alloy powder is mixed with the coating or other components of the composite material within 5 minutes.

[0132] In summary, the greatest advantage of the technical solution involved in the present invention is that during the process of alloy powder formation, the alloy powder is simultaneously purified and solid-solution alloyed; and the invention of the metal material composed of high-purity endogenous alloy powder and the coating body also proposes a new idea for the preparation, preservation and application of high-purity alloy powder.

[0133] Supplementary explanation: Although the present invention uses the basic concept of selective corrosion in principle, it is essentially different from the selective corrosion of the dealloying method in principle. Specifically, the precursor alloy selected by the dealloying method must be a single amorphous phase, or one or more intermetallic compound phases, or a mixture of one or more intermetallic compound phases and an amorphous phase. Before the dealloying reaction, the target atoms are uniformly dispersed in the various phases of the alloy in an atomic manner (whether in the intermetallic compound phase or the amorphous phase, the target atoms and other target atoms do not aggregate to form a target phase); after the dealloying reaction, the active atoms are corroded and removed, and the target atoms are freed. The target atoms are rearranged and aggregated together through redispersion to form a nanoporous structure. Therefore, the materials prepared by dealloying are generally nanoporous materials rather than powder materials, and the macroscopic shape of the materials before and after the dealloying reaction remains roughly unchanged. That is, the shape of alloy strips after the dealloying reaction remains nanoporous strips, and the shape of alloy blocks after the dealloying reaction remains nanoporous blocks (see the literature Generalized fabrication of nanoporous metals (Au, Pd, Pt, Ag and Cu) through chemical dealloying, J. Phys Chem C. 113 (2009) 12629-12636). Only when ultrasound or other fragmentation methods are applied can the obtained nanoporous structure be further broken into loose nanoporous fragments or nanoparticles.

[0134] The present invention selects a special alloy component pair to convert the bulk M d1 T e1 Raw materials and A d2 T e2 The raw materials are heated to above the melting point of the two raw materials to obtain M a0 A b0 T c0 Initial alloy melt. During the solidification process of the initial alloy melt, the element composition is mainly Ma1 A b1 T c1 The dispersed particle phase precipitates from the melt, and the final elemental composition is mainly A b2 T c2 The matrix phase finally solidifies and covers the dispersed particle phase. This dispersed particle phase can be nanoparticles when the cooling rate is fast enough, submicron particles when the cooling rate is slightly slower, micron particles when the cooling rate is even slower, and millimeter-sized particles when the cooling rate is even slower. a1 A b1 T c1 The intrinsic alloy powder is formed during the solidification of the initial alloy melt, not during a process such as acid reaction removal. The subsequent removal only removes the coating to obtain freely dispersed alloy nanoparticles.

[0135] Specifically, the beneficial effects of the present invention are mainly reflected in the following aspects:

[0136] First, it has achieved the goal of obtaining high-purity endogenous alloy powder from low-purity raw materials, and pointed out a new way to prepare high-purity metal powder materials from low-purity raw materials, which is of positive significance. The improvement of the purity of high-purity endogenous alloy powder is mainly achieved through the following two mechanisms:

[0137] 1) Element A's "absorption" of impurity elements. Since the selected A elements are all low-melting-point, highly reactive elements compared to element M, they have a stronger affinity for impurity element T than element M. This allows the impurity element T to either enter and dissolve in the matrix phase primarily composed of element A, or to form a slag with element A in the melt and separate from the alloy melt. This process is possible, for example, when element A includes rare earth elements or calcium, which have a strong affinity for oxygen.

[0138] 2) During the nucleation and growth of the endogenous alloy powder (the dispersed particle phase that precipitates endogenously), impurity elements are expelled into the remaining melt. As long as the endogenous alloy powder precipitates no later than the matrix phase during solidification, its impurities will be concentrated in the last portion of the melt to solidify, i.e., the portion of the melt that is primarily composed of element A and solidifies to form the matrix phase.

[0139] Second, in M a1 A b1 T c1 During the nucleation, growth and purification process of the endogenous alloy powder, the solid solution alloying of the A element in the endogenous alloy powder that cannot form an intermetallic compound with M is simultaneously achieved in M, and this solid solution alloying will have a positive effect.

[0140] Through the study of the examples, it was found that the M prepared by using raw materials containing higher impurity elements a1 A b1 T c1There is often a considerable amount of A dissolved in the endogenous alloy powder. Depending on the main element composition of the specific alloy melt, the impurity content, and the solidification rate, the A content in the M a1 A b1 T c1 The solid solubility in the endogenous alloy powder will also be different. For a given MAT alloy melt, generally speaking, when the T content is high and the melt solidification rate is high and forms smaller endogenous alloy powders, such as nanopowders, the M a1 A b1 T c1 The endogenous alloy powder can dissolve more A elements. a1 A b1 T c1 The solid solution in the endogenous alloy powder makes the endogenous alloy powder have certain properties of solid solution alloyed alloy powder, which has positive significance.

[0141] It should be noted that the A element in M a1 A b1 T c1 Solid solution alloying in endogenous alloy powder is the result obtained when the corresponding initial alloy melt contains enough A elements (most of the other A elements form the matrix phase A). b2 T c2), which is completely different from the case where a small amount of A element is directly added to M to obtain MA alloy. For example, in industry, a trace amount (such as 0.3wt%) of Y is generally added to Ti metal (supplementary note: the corresponding atomic percentage content of Y is 0.16at%) to improve the strength and plasticity of Ti-Y alloy. The mechanism is that after the trace amount of Y added enters the Ti metal, it generally combines with impurity elements such as O in the Ti metal to form Y2O3 oxide. The presence of Y2O3 oxide can act as a particle for heterogeneous nucleation to increase the nucleation rate, so that the Ti metal obtains finer grains during the solidification process, thereby improving the strength and plasticity of the Ti metal at the same time through the principle of grain refinement. This alloying is not strictly alloying, because a small amount of Y is added to the Ti metal of non-absolute purity in the form of Y2O3 oxide. The present invention can obtain a Ti-YT alloy melt by smelting a Ti raw material containing T as an impurity and a Y raw material containing T as an impurity. After solidification of the alloy melt, a Ti-YT endogenous alloy powder containing a small amount of Y in the solid solution can be obtained, where Y is the actual alloying element involved in the solid solution alloying. This difference can enable the Ti-YT endogenous alloy powder to achieve significantly different and beneficial application effects. For example, when a Ti-YT alloy micron powder after removing the coating matrix phase and undergoing a spheroidization treatment is used in the field of metal 3D printing, during the laser remelting process of the powder, the Y element "stored" in the solid solution in the Ti-YT alloy powder can absorb the O element on the surface or surface layer of the Ti-YT alloy powder (introduced during the removal of the coating matrix phase and the spheroidization process) to form Y2O3 oxide. Using Y2O3 oxide as a particle for heterogeneous nucleation can significantly refine the grains in the Ti-YT alloy structure after laser remelting and solidification, thereby improving the strength and plasticity of the 3D printed device. In Ti-Y powder prepared through traditional Ti-Y alloy atomization, Y has already been bonded to O to form Y2O3 oxide. Furthermore, new O is introduced into the powder during the powder-making process, leaving no "free" Y to further bond with O during the powder laser remelting process. Alternatively, to achieve this goal, more Y must be added to the traditional Ti-Y alloy powder to allow some "free" Y to be dissolved in the Ti-Y alloy powder in addition to Y2O3 oxide. This undoubtedly does not offer the superior performance of the Ti-YT alloy powder described in the present invention, which only contains the Y element dissolved in it.

[0142] Third, alloy powder mainly composed of single crystal particles can be obtained. Compared with polycrystalline powder, single crystal powder can obtain many significant and beneficial effects. During the solidification process of the initial alloy melt, each endogenous particle is nucleated at a certain position in the melt and grows according to a specific atomic arrangement. By controlling the volume percentage of the matrix phase, it is ensured that each endogenous particle can be dispersed and distributed, and it is difficult for each endogenous particle to merge and grow. Therefore, the various dispersed particle phases finally obtained are generally single crystal phases. Even if the dendrite particles are as large as tens of microns, the growth direction of each secondary dendrite maintains a certain phase relationship with the growth direction of the main dendrite, and it is still a single crystal particle.

[0143] For polycrystalline materials, their grain boundaries are often prone to containing impurity elements expelled from the crystals during solidification, making it difficult to obtain high-purity polycrystalline powder materials. However, when the powder material is primarily composed of single crystal particles, its purity is guaranteed. Moreover, the atoms on the surface of single crystal particles have specific arrangements, such as the (111) plane arrangement. These specific arrangements can give the material unique mechanical, physical, and chemical properties, thereby producing beneficial effects.

[0144] Fourth, the metal material composed of endogenous alloy powder and a coating creatively utilizes an in-situ generated coating to encapsulate the endogenous alloy powder, maintaining the high purity and activity of the endogenous alloy powder. Metal or alloy powders produced by both traditional chemical and physical methods, especially nanopowders with extremely large specific surface areas, are highly susceptible to natural oxidation and face difficulties in powder storage. To address this issue, the present invention, after preparing a metal material composed of endogenous alloy powder and a coating, does not rush to remove the coating and then find other ways to protect the endogenous alloy powder from contamination by impurities such as oxygen. Instead, the coating is directly used to protect the endogenous alloy powder. This metal material composed of endogenous alloy powder and a coating can be directly used as raw material for downstream production. When downstream production requires the endogenous alloy powder, the endogenous alloy powder can be released at an appropriate time and under a suitable environment based on the characteristics of the next process. The released endogenous alloy powder can then be introduced into the next production process in the shortest possible time, significantly reducing the chance of alloy powder contamination. For example, when the endogenous alloy powder is nano-sized, it can be compounded with resin at the same time as the alloy powder is released or immediately thereafter to prepare a resin-based composite material with the addition of highly active nano-alloy powder.

[0145] Fifth, by controlling the solidification rate of the initial alloy melt, it is possible to produce endogenous alloy powders of varying and continuous particle sizes, including nanopowders, submicron powders, micron powders, and even millimeter-scale powders. Compared to traditional top-down (fragmentation of a bulk material into small particles) or bottom-up (aggregation of atoms into large particles) physical or chemical methods, the "primary crystal phase precipitation-dephase method" involved in this invention represents a novel approach for preparing powder materials with particle sizes ranging from nanometers to millimeters.

[0146] Supplementary explanation: In the field of powder material preparation, nanoparticles of several nanometers or tens of nanometers can be easily prepared from the atomic or ionic scale through a bottom-up approach (such as ion reduction); micron particles of tens of microns can be easily prepared through a top-down approach (such as ball milling). However, whether it is a bottom-up approach or a top-down approach, it is difficult to prepare powder materials of about 1 μm. This is because it is too difficult to grow from atoms to the 1 μm level from the bottom up, and it is also extremely difficult to crush bulk materials to the 1 μm level from the top down. Traditional methods for preparing powder materials are only suitable within a certain particle size range. For example, ion reduction prepares nanoparticles below 100 nm, and atomization prepares micron particles above 10 μm. However, the method involved in the present invention is very suitable for preparing powder materials ranging from several nanometers to several millimeters. It only needs to control the solidification rate of the initial alloy melt, which perfectly solves the difficulty in preparing powder materials with a particle size of about 1 μm.

[0147] In particular, the present invention is also particularly suitable for large-scale, low-cost preparation of certain special nano-metal powders (such as nano-Ti powder). Due to the particularity of the Ti element, it is difficult or impossible to prepare it through Ag or Cu. + , Cu 2+ The chemical reduction of Ag or Cu nanopowders is typically only possible in small batches using physical methods such as the explosion method, which is extremely expensive. Even though nano-Ti powder has a wide range of uses, the cost of several thousand yuan per kilogram significantly limits its industrial application. However, the present invention cleverly solves the problem of large-scale, low-cost production of high-purity, solid-solution alloyed nano-Ti powders using low-purity raw materials, and is of inestimable value.

[0148] Sixth, additional explanation: Through careful design of AM element combinations, the use of low-purity A and M raw materials, and the clever use of T elements (O, H, N, P, S, F, Cl), especially the necessary characteristic O element, on the thermodynamic influence of the diffusion and phase distribution laws of A, M, and T elements during the solidification process of the MAT initial alloy melt, not only the purification of T in the MAT endogenous alloy powder is achieved, but also the considerable solid solubility of A in the MAT endogenous alloy powder is cleverly achieved and increased.

[0149] Seventh, Supplementary Note: The M and A of the present invention contain one or more groups of M that do not form intermetallic compounds. 1 -A 1 In order to meet this key requirement, careful design is required in the selection of alloy components. 1 -A 1 The solidification structure of the element combination does not form M 1 -A 1 Intermetallic compound; A contains at least one of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mg, Ca, Li, Na, K, In, Pb, Zn, and Cu; although the above elements seem to be relatively numerous, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu are all rare earth elements. If the rare earth elements are replaced by RE Instead, A only contains at least one of RE, Mg, Ca, Li, Na, K, In, Pb, Zn, and Cu; among them, RE, Mg, Ca, Li, Na, K, In, Pb, and Zn are extremely active, or have extremely low melting points, or are extremely soft metal elements. They generally do not form alloys with other elements to improve strength or corrosion resistance (the alloy formed with M, A is a coating and cannot achieve this effect). They are also rarely used and are unpopular academic research and industrial application elements. Cu is rarely alloyed with unpopular precious metals Ir, Ru, Re, Os, and Tc. Even if it is alloyed with W, Cr, Mo, V, Ta, and Nb, it is generally made by powder metallurgy, and the corresponding material is obtained by mixing Cu powder with W, Cr, Mo, V, Ta, and Nb powder and sintering. Therefore, the M selected in the present invention 1 -A 1 These element combinations are rarely explored in academia and industry. However, the present invention takes a different approach, turning the disadvantages of these unpopular element combinations into advantages and applying them to the preparation of powder materials, demonstrating significant creativity.

[0150] The present invention cleverly exploits the characteristics of this unpopular element combination. By taking advantage of the separation of A and M during alloy solidification, and the initial precipitation of primary crystal particles dominated by M, followed by the subsequent precipitation of a matrix phase dominated by A, it successfully achieves the preparation of a metal material composed of endogenous alloy powder and a coating. The extremely active, low melting point, or soft properties of elements such as RE, Mg, Ca, Li, Na, K, In, Pb, and Zn facilitate the removal of coatings primarily composed of these elements. Therefore, this ingenious utilization of this unpopular element combination to achieve the preparation of a class of alloy powders has significant positive implications.

[0151] Therefore, the present invention creatively adopts low-purity raw materials and integrates multiple beneficial technical solutions such as single crystal alloy powder generation, alloy powder purification and preservation, and powder solid solution alloying. It can realize the preparation of high-purity nano-scale, submicron-scale, micron-scale, and millimeter-scale solid solution alloy powders, and has good application prospects in catalysis, powder metallurgy, composite materials, magnetic materials, sterilization, metal injection molding, metal powder 3D printing, coatings, composite materials and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0152] FIG1 is a backscattered SEM image of a portion of the endogenous nano-Ti alloy powder and the Gd coating according to Example 3 of the present invention;

[0153] FIG2 is a SEM image of the nano-Ti alloy powder of Example 3 of the present invention;

[0154] FIG3 is a backscattered SEM image of a portion of the endogenous Ti-Co dendrite alloy powder and its Gd coating according to Example 6 of the present invention;

[0155] FIG4 is a SEM image of the Ti-Co dendrite alloy powder of Example 6 of the present invention; DETAILED DESCRIPTION

[0156] The present invention will be further described in detail below with reference to the examples. It should be noted that the examples described below are intended to facilitate understanding of the present invention and do not have any limiting effect on the present invention.

[0157] Example 1

[0158] This embodiment provides a metal strip composed of endogenous nano-Ti alloy powder and a Ce coating, a nano-Ti alloy powder, and a preparation method and application thereof, including the following steps:

[0159] (1) Low-purity titanium is selected, which contains 0.3wt%, 0.1wt%, 0.3wt%, and 0.03wt% of Cl, N, O, and H, respectively. When converted into atomic percentages, the atomic percentages of Cl, N, O, and H are 0.4at%, 0.33at%, 0.88at%, and 1.39at%, respectively, i.e., the total content is 3at%. Low-purity rare earth Ce is selected, which contains 0.3wt% of O. When converted into atomic percentages, the O content in Ce is 2.57at%. Since Ti-Ce is an element pair that does not form intermetallic compounds, and the melting point of Ti is higher than that of Ce, Ti alloy powder can be prepared based on this element pair.

[0160] The low-purity Ti and low-purity Ce raw materials are mixed in a volume ratio of 1:3, and other trace elements that may exist in the raw materials are classified as main elements to facilitate calculation. According to the element density and atomic weight data, the composition of the alloy raw materials can be expressed in terms of atomic percentage (Ti 97 Cl 0.4 N 0.33 O 0.88 H 1.39 ) 39 (Ce 97.43 O 2.57 ) 61 , the specific expansion is Ti 37.83 Ce 59.435 Cl 0.156 N 0.129 H 0.54 O 1.91 , where the total content of impurity elements T such as Cl, N, H, and O is about 2.735at%.

[0161] (2) The above low-purity alloy raw materials are subjected to induction melting to obtain a composition of about Ti 37.83 Ce 59.435 T 2.735 The initial alloy melt (T represents impurity elements such as Cl, N, H, and O). Some impurity elements in the initial alloy melt may become slag and separate from the melt, reducing the impurity content; while some impurities in the environment and atmosphere, such as oxygen, may also enter the melt, causing the impurity content in the melt to increase.

[0162] (3) The initial alloy melt is rapidly solidified into a strip with a thickness of about 100 μm by a copper roller spinning method. During the solidification process, the dispersed particles mainly composed of Ti are embedded and precipitated in the matrix phase mainly composed of Ce, thus obtaining a metal strip composed of endogenous nano-Ti alloy powder and Ce coating. Among them, the atomic percentage composition of the endogenous Ti alloy powder is approximately Ti 99.1 Ce 0.5 T 0.4 , primarily composed of single-crystal particles with a particle size range of 3nm to 300nm. A small amount of Ce is dissolved in the endogenous Ti alloy powder, and the T impurity content is significantly reduced compared to low-purity Ti raw materials, while other large amounts of T impurities are concentrated in the Ce coating. In the resulting metal strip composed of endogenous nano-Ti alloy powder and Ce coating, the volume percentage of endogenous Ti alloy powder is comparable to the volume percentage of the Ti raw material during raw material formulation, still approximately 25 vol%, ensuring the dispersed distribution of the Ti alloy powder in the Ce-dominant matrix phase.

[0163] (4) The Ce coating in the metal strip composed of endogenous nano-Ti alloy powder and Ce coating is removed using a dilute hydrochloric acid solution. Since the Ti alloy powder does not react with the dilute hydrochloric acid solution, Ti-Ce-T alloy powder can be obtained after separation, cleaning, and drying. Due to the absorption of oxygen and other impurities by the surface layer and surface atoms of the exposed Ti-Ce-T alloy powder, the T impurity content in the obtained Ti-Ce-T alloy powder is higher than that in the endogenous Ti-Ce-T alloy powder.

[0164] After step (3), you can also directly proceed to step (5):

[0165] (5) The Ce coating in the metal strip composed of endogenous nano-Ti alloy powder and Ce coating was removed by using a dilute hydrochloric acid solution with dissolved oxygen removed. Within 20 minutes, the Ti alloy powder was separated under a protective atmosphere and mixed with epoxy resin and other coating components to prepare a titanium alloy nano-modified polymer anti-corrosion coating.

[0166] Example 2

[0167] This embodiment provides a metal sheet composed of endogenous micronized Ti alloy powder and a Ce coating, a micronized Ti alloy powder, and a preparation method and application thereof, including the following steps:

[0168] (1) Low-purity titanium is selected, containing 0.3wt%, 0.1wt%, 0.3wt%, and 0.03wt% of Cl, N, O, and H, respectively. Converted into atomic percentages, the atomic percentages of Cl, N, O, and H are 0.4at%, 0.33at%, 0.88at%, and 1.39at%, respectively. The total content is 3at%. Low-purity rare earth element Ce is selected, containing 0.3wt% of O. Converted into atomic percentages, the O content in Ce is 2.57at%. Since Ti-Ce is an element pair that does not form intermetallic compounds, and Ti has a higher melting point than Ce, this element pair can be used as a basis for preparing Ti alloy powder.

[0169] The low purity Ti and low purity Ce raw materials are mixed in a volume ratio of 1:3, and other trace elements that may exist in the raw materials are classified as main elements to facilitate calculation. According to the element density and atomic weight data, the composition of the alloy raw materials is expressed in atomic percentages as (Ti 97 Cl 0.4 N 0.33 O 0.88 H 1.39 ) 39 (Ce 97.43 O 2.57 ) 61 , that is, the atomic percentage is about Ti 37.83 Ce59.435 Cl 0.156 N 0.129 H 0.54 O 1.91 , where the total content of impurity elements T such as Cl, N, H, and O is about 2.735at%.

[0170] (2) The above low-purity alloy raw materials are subjected to induction melting to obtain a composition of about Ti 37.83 Ce 59.435 T 2.735 The initial alloy melt (T represents impurity elements such as Cl, N, H, and O). Some impurity elements in the initial alloy melt may become slag and separate from the melt, reducing the impurity content; while some impurities in the environment and atmosphere, such as oxygen, may also enter the melt, causing the impurity content in the melt to increase.

[0171] (3) The initial alloy melt is solidified into a thin plate with a thickness of about 4 mm. During the solidification process, the meso-dendrite dispersed particle phase mainly composed of Ti is embedded in the matrix phase mainly composed of Ce, and a metal thin plate consisting of endogenous micron Ti alloy powder and Ce coating is obtained. Among them, the atomic percentage composition of the endogenous Ti alloy dendrite powder is approximately Ti 99.4 Ce 0.3 T 0.3 , primarily composed of single-crystal dendrite particles with particle sizes ranging from 1μm to 150μm. Ce is dissolved in the endogenous Ti alloy powder, and the T impurity content is significantly reduced compared to low-purity Ti raw materials, while other large amounts of T impurities are enriched in the Ce coating. In the resulting metal sheet composed of endogenous micronized Ti alloy powder and Ce coating, the volume percentage of the endogenous Ti alloy powder is comparable to the volume percentage of the titanium raw material during raw material formulation, still approximately 25 vol%, ensuring the dispersed distribution of the Ti alloy dendrite powder in the Ce-dominated matrix phase.

[0172] (4) The Ce coating in the metal sheet composed of endogenous micron Ti alloy powder and Ce coating is removed by dilute hydrochloric acid solution. Since the Ti alloy dendrite powder does not react with the dilute hydrochloric acid solution, Ti-Ce-T alloy dendrite powder can be obtained after separation, cleaning and drying.

[0173] (5) The Ti-Ce-T alloy dendrite powder is subjected to air flow milling to disperse the entangled dendrite particles during the solidification process and to break the larger dendrite particles into smaller dendrite particle fragments.

[0174] (6) The Ti alloy dendrite powder obtained above is sieved, and Ti alloy dendrite powder with a particle size range of 15 μm to 53 μm is selected for plasma spheroidization treatment to obtain spherical or nearly spherical Ti alloy powder with a small particle size range.

[0175] (7) The spherical or nearly spherical Ti alloy powder is used in the field of metal powder 3D printing.

[0176] Example 3

[0177] This embodiment provides a metal strip composed of endogenous nano-Ti alloy powder and a Gd coating, a nano-Ti alloy powder, and a preparation method thereof, comprising the following steps:

[0178] (1) Low-purity Ti raw material and rare earth raw material composed mainly of Gd are selected. The impurity T content in both types of raw materials is about 3at%. Since Ti-Gd is an element combination that does not form intermetallic compounds, and the melting point of Ti is higher than that of Gd, Ti alloy powder can be prepared based on this element combination.

[0179] (2) Low-purity Ti raw material and rare earth raw material mainly composed of Gd are alloyed in a volume ratio of 15:85, and the alloy raw material is induction melted to obtain a Ti with an atomic percentage of about 24 Gd 73 T3 initial alloy melt, in which the T content is about 3at%.

[0180] (3) The initial alloy melt is rapidly solidified into a strip with a thickness of about 100 μm by a copper roller spinning method. During the solidification process, the dispersed particle phase composed mainly of Ti is embedded in the matrix phase composed mainly of Gd, and a metal strip composed of endogenous nano-Ti alloy powder and Gd coating is obtained. Its microscopic morphology is shown in Figure 1. Among them, the atomic percentage composition of the endogenous Ti alloy powder is approximately Ti 99.2 Gd 0.5 T 0.3 The resulting endogenous Ti alloy powder is primarily composed of Ti nanocrystals containing a small amount of Gd in a solid solution, with particle sizes ranging from 3 nm to 300 nm. The T impurity content in the endogenous Ti alloy powder is significantly reduced compared to the Ti raw material, while the remaining large amounts of T impurities are concentrated in the Gd coating. The volume percentage of the endogenous Ti alloy powder in the resulting endogenous Ti alloy powder and its Gd-coated ribbons is comparable to the volume percentage of the Ti raw material during raw material preparation, remaining approximately 15 vol%, ensuring a dispersed distribution of the Ti alloy powder within the Gd-dominated matrix phase, as shown in Figure 1.

[0181] (4) The Gd coating in the metal strip composed of endogenous nano-Ti alloy powder and Gd coating is removed by dilute hydrochloric acid solution. Since the Ti alloy powder does not react with the dilute hydrochloric acid solution, after separation, cleaning and drying, Ti-Gd-Ti alloy powder with Ti as the main component can be obtained, and its particle size ranges from 3nm to 300nm, as shown in Figure 2.

[0182] Example 4

[0183] This embodiment provides a metal strip composed of endogenous nano-Ti-Nb-V alloy powder and a Ce-La-Nd-Pr coating, a nano-Ti-Nb-V alloy powder, and a preparation method thereof, comprising the following steps:

[0184] (1) Low-purity Ti, Nb, and V raw materials and mixed rare earth raw materials mainly composed of Ce, La, Nd, and Pr are selected. The impurity T content in both types of raw materials is about 3at%. Since Ti-Ce, Ti-La, Ti-Nd, Ti-Pr, Nb-Ce, Nb-La, Nb-Nd, Nb-Pr, V-Ce, V-La, V-Nd, and V-Pr are all element pairs that do not form intermetallic compounds, and the melting points of Ti, Nb, and V are higher than those of Ce, La, Nd, and Pr, Ti-Nb-V alloy powder can be prepared based on these element pairs.

[0185] (2) Low-purity Ti, Nb, and V raw materials are alloyed with a mixed rare earth element consisting primarily of Ce, La, Nd, and Pr in a volume ratio of 1:2, wherein Ti, Nb, and V are in equal molar ratios. The alloy raw materials are induction melted to obtain an initial (Ti-Nb-V)-(Ce-La-Nd-Pr)-T alloy melt, wherein the T content is approximately 3 at%.

[0186] (3) The initial alloy melt is rapidly solidified into a strip with a thickness of about 100 μm by means of a copper roller spinning strip. During the solidification process, a dispersed particle phase composed mainly of Ti-Nb-V is embedded in a matrix phase composed mainly of Ce-La-Nd-Pr, thereby obtaining a metal strip composed of endogenous nano-Ti-Nb-V alloy powder and Ce-La-Nd-Pr coating. The atomic percentage composition of the endogenous Ti-Nb-V alloy powder is approximately (Ti-Nb-V) 99.2 (Ce-La-Nd-Pr) 0.5 T 0.3 It is primarily composed of infinitely miscible Ti-Nb-V single crystal particles with particle sizes ranging from 3nm to 300nm. Ce-La-Nd-Pr is dissolved in the endogenous Ti-Nb-V alloy powder, and the T impurity content is significantly reduced compared to the Ti, Nb, and V raw materials, while the remaining T impurities are concentrated in the Ce-La-Nd-Pr cladding. In the resulting metal ribbon composed of endogenous nano-Ti-Nb-V alloy powder and Ce-La-Nd-Pr cladding, the volume percentage of the endogenous Ti-Nb-V alloy powder is comparable to the volume percentage of the Ti, Nb, and V raw materials during the raw material formulation, remaining at approximately 33 vol%, ensuring the dispersed distribution of the Ti-Nb-V alloy powder in the Ce-La-Nd-Pr-dominated matrix phase.

[0187] (4) The Ce-La-Nd-Pr coating in the metal strip composed of endogenous nano-Ti-Nb-V alloy powder and Ce-La-Nd-Pr coating is removed by dilute hydrochloric acid solution. Since the Ti-Nb-V alloy powder does not react with the dilute hydrochloric acid solution, after separation, cleaning and drying, a Ti-Nb-V alloy powder mainly composed of (Ti-Nb-V)-(Ce-La-Nd-Pr)-T can be obtained. Due to the absorption of impurities such as O by the surface layer and surface of the exposed Ti-Nb-V alloy powder, the T impurity content in the obtained Ti-Nb-V alloy powder is slightly higher than that in the endogenous Ti-Nb-V alloy powder.

[0188] Example 5

[0189] This embodiment provides a metal strip composed of endogenous submicron Ti-Co alloy powder and a Ce-La-Nd-Pr coating, a submicron Ti-Co alloy powder, and a preparation method thereof, comprising the following steps:

[0190] (1) Low-purity Ti and Co raw materials and mixed rare earth raw materials mainly composed of Ce, La, Nd, and Pr are selected, wherein the molar ratio of Ti to Co raw materials is 1:1, and the impurity T content in both types of raw materials is about 3at%. Since Ti-Ce, Ti-La, Ti-Nd, and Ti-Pr are all element combinations that do not form intermetallic compounds, and Ti accounts for 50% of the Ti-Co raw materials and is the main element; and the melting point of CoTi intermetallic compound is as high as 1700℃, which is much higher than the melting point of intermetallic compounds that can be formed by Co and elements such as Ce, La, Nd, and Pr. When Co:Ti is 1:1, Co mainly combines with Ti to form a high-melting-point CoTi intermetallic compound. Therefore, based on these element combinations, intermetallic compound CoTi alloy powder can be prepared.

[0191] (2) Low-purity Ti and Co raw materials are alloyed with a mixed rare earth element consisting primarily of Ce, La, Nd, and Pr in a volume ratio of 1:2, with Ti and Co in an equimolar ratio. The alloy raw materials are induction melted to obtain an initial (Ti-Co)-(Ce-La-Nd-Pr)-T alloy melt, in which the T content is approximately 3 at%.

[0192] (3) The initial alloy melt is rapidly solidified into a strip with a thickness of about 300 μm by a copper roller spinning method. During the solidification process, a dispersed particle phase composed mainly of Ti-Co is embedded in a matrix phase composed mainly of Ce-La-Nd-Pr, thereby obtaining a metal strip composed of endogenous submicron Ti-Co alloy powder and Ce-La-Nd-Pr coating. The atomic percentage composition of the endogenous Ti-Co alloy powder is approximately (Ti-Co) 99 (Ce-La-Nd-Pr)0.6 T 0.4 The resulting metal strip, composed primarily of Ti-Co intermetallic compound single crystal particles, ranges in size from 20 nm to 1 μm. Ce-La-Nd-Pr is dissolved in the endogenous Ti-Co alloy powder, and the T impurity content is significantly reduced compared to the Ti and Co raw materials, while the remaining T impurities are concentrated in the Ce-La-Nd-Pr cladding. The volume percentage of the endogenous Ti-Co alloy powder in the resulting metal strip, composed of endogenous submicron Ti-Co alloy powder and Ce-La-Nd-Pr cladding, remains approximately 33 vol%, comparable to the volume percentage of the Ti and Co raw materials during raw material preparation. This ensures the dispersed distribution of the Ti-Co alloy powder within the Ce-La-Nd-Pr-based matrix phase.

[0193] (4) The Ce-La-Nd-Pr coating in the metal strip composed of endogenous submicron Ti-Co alloy powder and Ce-La-Nd-Pr coating is removed by dilute hydrochloric acid solution. Since Ti-Co alloy powder does not easily react with dilute hydrochloric acid solution, Ti-Co alloy powder mainly composed of (Ti-Co)-(Ce-La-Nd-Pr)-T can be obtained after separation, cleaning and drying. Due to the absorption of impurities such as O by the surface layer and surface of the exposed Ti-Co alloy powder, the content of T impurities in the obtained Ti-Co alloy powder is slightly higher than that in the endogenous Ti-Co alloy powder.

[0194] Example 6

[0195] This embodiment provides a metal sheet composed of endogenous micron Ti-Co alloy powder and a Gd coating, a micron Ti-Co alloy powder, and a preparation method thereof, including the following steps:

[0196] (1) Low-purity Ti and Co raw materials and rare earth raw materials mainly composed of Gd are selected, wherein the molar ratio of Ti to Co raw materials is 1:1, and the impurity T content in both types of raw materials is about 3at%. Since Ti-Gd is an element combination pair that does not form intermetallic compounds, and Ti accounts for 50% of the Ti-Co raw materials and is the main element; and the melting point of CoTi intermetallic compound is as high as 1700℃, which is much higher than the melting point of intermetallic compounds that can be formed by elements such as Co and Gd. When Co:Ti is 1:1, Co mainly combines with Ti to form a high-melting-point CoTi intermetallic compound. Therefore, based on these element combinations, intermetallic compound CoTi alloy powder can be prepared.

[0197] (2) Low-purity Ti and Co raw materials are alloyed with a rare earth raw material primarily composed of Gd in a volume ratio of 30:70, with Ti and Co in an equimolar ratio. The alloy raw materials are induction melted to obtain a TiCo-Gd-T initial alloy melt, in which the Ti content is approximately 3 at%.

[0198] (3) The initial alloy melt is solidified into a thin plate with a thickness of about 2 mm. During the solidification process, the dendrite particles composed mainly of Ti-Co are embedded in the matrix phase composed mainly of Gd, and a metal thin plate composed of endogenous micron Ti-Co alloy powder and Gd coating is obtained. The solidification microstructure is shown in Figure 3. The atomic percentage composition of the endogenous Ti-Co alloy powder is approximately (TiCo) 99.5 Gd 0.3 T 0.2 , which is primarily composed of Ti-Co single crystal particles of the intermetallic compound, with particle sizes ranging from 1μm to 60μm. A small amount of Gd is dissolved in the endogenous Ti-Co alloy powder, and the T impurity content is greatly reduced compared to the Ti and Co raw materials, while other large amounts of T impurities are enriched in the Gd coating. The volume percentage of the endogenous Ti-Co alloy powder in the resulting endogenous Ti-Co alloy powder and its Gd-coated thin plate is equivalent to the volume percentage of the Ti and Co raw materials during raw material preparation, still approximately 30 vol%, ensuring the dispersed distribution of the Ti-Co alloy powder in the Gd-based matrix phase.

[0199] (4) The Gd coating in the metal sheet composed of endogenous micron Ti-Co alloy powder and Gd coating is removed by dilute hydrochloric acid solution. Since Ti-Co alloy powder does not easily react with dilute hydrochloric acid solution, after separation, cleaning and drying, a Ti-Co alloy powder mainly composed of (Ti-Co)-Gd-T can be obtained. Its single crystal dendrite morphology is shown in Figure 4. Due to the absorption of impurities such as O by the surface layer and surface of the exposed Ti-Co alloy powder, the content of T impurities in the obtained Ti-Co alloy powder is slightly higher than that in the endogenous Ti-Co alloy powder.

[0200] Example 7

[0201] This embodiment provides a metal strip composed of endogenous micron Fe alloy powder and La coating, a micron Fe alloy powder, and a preparation method thereof, including the following steps:

[0202] (1) A low-purity Fe raw material and a rare earth raw material mainly composed of La are selected, and the impurity T content in both types of raw materials is about 2.5at%. Since Fe-La is an element combination pair that does not form intermetallic compounds, and both are main elements, Fe alloy powder can be prepared based on the Fe-La combination pair.

[0203] (2) Low-purity Fe raw material and rare earth raw material mainly composed of La are alloyed in a volume ratio of 1:2, and the alloy raw materials are induction melted to obtain an Fe-La-T initial alloy melt, wherein the T content is about 2.5at%.

[0204] (3) The initial alloy melt is rapidly solidified into a strip with a thickness of about 500 μm by a copper roller spinning method. During the solidification process, the dispersed particle phase composed mainly of Fe is embedded in the matrix phase composed mainly of La, and a metal strip composed of endogenous micron Fe alloy powder and La coating is obtained. Among them, the atomic percentage composition of the endogenous Fe alloy powder is approximately Fe 99.4 La 0.3 T 0.3 , primarily composed of single-crystal Fe particles with particle sizes ranging from 500nm to 5μm. La is dissolved in the endogenous Fe alloy powder, and the T impurity content is significantly reduced compared to the Fe raw material, while a large amount of other T impurities are concentrated in the La coating. In the resulting metal strip composed of endogenous micronized Fe alloy powder and La coating, the volume percentage of endogenous Fe alloy powder is comparable to the volume percentage of the raw material formulation, still approximately 33 vol%, ensuring the dispersed distribution of the Fe alloy powder in the La-dominant matrix phase.

[0205] (4) The endogenous Fe alloy powder is pre-separated from the La oxide powder in the matrix by natural oxidation and pulverization of the La coating. The Fe alloy powder is then separated from the La oxide in the matrix by a magnetic field, utilizing the magnetic properties of the Fe alloy powder. A small amount of dilute acid solution is then used to completely remove the residual La oxide adsorbed on the surface of the Fe alloy powder. The concentration and amount of acid are controlled to ensure that the Fe alloy powder is retained. After washing, separation, and drying, the Fe alloy powder is finally obtained.

[0206] Example 8

[0207] This embodiment provides a metal strip composed of endogenous nano Cu alloy powder and a Li coating, a nano Cu alloy powder, and a preparation method thereof, including the following steps:

[0208] (1) Low-purity Cu and Li raw materials are selected, and the impurity T content in both types of raw materials is about 1 at%. Since Cu-Li is an element pair that does not form intermetallic compounds, and both are main elements, Cu alloy powder can be prepared based on the Cu-Li pair.

[0209] (2) Low-purity Cu raw material and low-purity Li raw material are alloyed in a volume ratio of 1:3, and the alloy raw materials are induction melted to obtain a Cu-Li-T initial alloy melt, wherein the T content is about 1at%.

[0210] (3) The initial alloy melt is rapidly solidified into a strip with a thickness of about 30 μm by a copper roller. During the solidification process, the dispersed particles composed mainly of Cu are embedded in the matrix phase composed mainly of Li, and a metal strip composed of endogenous nano Cu alloy powder and Li coating is obtained. Among them, the atomic percentage composition of the endogenous Cu alloy powder is approximately Cu 84.8 Li 15 T 0.2 The material is primarily composed of Cu single crystal particles with a large amount of Li dissolved therein, with particle sizes ranging from 3nm to 150nm. The T impurity content is significantly reduced compared to the Cu raw material, while a large amount of other T impurities are concentrated in the Li coating.

[0211] (4) The Li coating in the metal strip composed of endogenous nano-Cu alloy powder and Li coating is removed by using an extremely dilute hydrochloric acid solution. Since the Cu alloy powder does not easily react with the extremely dilute hydrochloric acid solution, nano-scale Cu alloy powder with the main composition of Cu-Li-T can be obtained after separation, cleaning and drying.

[0212] Example 9

[0213] This embodiment provides a metal strip composed of endogenous nano Cu alloy powder and a Pb coating, a nano Cu alloy powder, and a preparation method thereof, comprising the following steps:

[0214] (1) Low-purity Cu and Pb raw materials are selected, and the impurity T content in the two raw materials is approximately 2 at% and 0.5 at%, respectively. Since Cu-Pb is an element pair that does not form intermetallic compounds, and both are main elements, Cu alloy powder can be prepared based on the Cu-Pb pair.

[0215] (2) Low-purity Cu raw material and Pb raw material are alloyed in a volume ratio of 1:3, and the alloy raw materials are induction melted to obtain a Cu-Pb-T initial alloy melt, wherein the T content is about 1at%.

[0216] (3) The initial alloy melt is rapidly solidified into a strip with a thickness of about 30 μm by a copper roller. During the solidification process, the dispersed particles composed mainly of Cu are embedded in the matrix phase composed mainly of Pb, and a metal strip composed of endogenous nano Cu alloy powder and Pb coating is obtained. Among them, the atomic percentage composition of the endogenous Cu alloy powder is approximately Cu 99.5 Pb 0.3 T 0.2The resulting metal strip, composed primarily of Cu single crystal particles containing a small amount of lead dissolved therein, has a particle size range of 3 nm to 150 nm. The T impurity content is significantly reduced compared to the Cu raw material, while the remaining large amounts of T impurities are concentrated in the lead coating. The volume percentage of the endogenous Cu alloy powder in the resulting metal strip, composed of endogenous nano-Cu alloy powder and lead coating, remains approximately 25 vol%, comparable to the volume percentage of the raw material formulation, ensuring a well-dispersed distribution of the Cu alloy powder within the lead-based matrix phase.

[0217] (4) The Pb coating in the metal strip composed of endogenous nano Cu alloy powder and Pb coating is removed by a mixed solution of acetic acid and dilute hydrochloric acid. Since the Cu alloy powder does not easily react with the mixed solution of acetic acid and dilute hydrochloric acid, nano-scale Cu alloy powder mainly composed of Cu-Pb-T can be obtained after separation, cleaning and drying.

[0218] Example 10

[0219] This embodiment provides a metal strip composed of endogenous nano-Nb-V-Mo-W alloy powder and a Cu coating, a nano-Nb-V-Mo-W alloy powder, and a preparation method thereof, including the following steps:

[0220] (1) Low-purity Nb, V, Mo, W raw materials and Cu raw materials are selected, and the impurity T content in both types of raw materials is about 1 at%. Since Cu-Nb, Cu-V, Cu-Mo, and Cu-W are element pairs that do not form intermetallic compounds, and Nb, V, Mo, and W are mutually soluble main elements, Nb-V-Mo-W alloy powder can be prepared based on these pairs.

[0221] (2) Low-purity Nb, V, Mo, and W raw materials are mixed with Cu raw materials in a volume ratio of 1:2, wherein the molar ratio of Nb:V:Mo:W is 2:1:1:1. The alloy raw materials are induction melted to obtain an initial (Nb2VMoW)-Cu-T alloy melt, wherein the T content is approximately 1 at%.

[0222] (3) The initial alloy melt is slowly solidified into a strip with a thickness of about 30 μm by a copper roller spinning method. During the solidification process, the dispersed particle phase composed mainly of Nb2VMoW is embedded in the matrix phase composed mainly of Cu, and a metal strip composed of endogenous nano-Nb-V-Mo-W alloy powder and Cu coating is obtained. Among them, the atomic percentage composition of the endogenous Nb2VMoW alloy powder is approximately (Nb2VMoW) 99.3 Cu 0.5 T 0.2, which is primarily composed of high-entropy Nb2VMoW single crystal particles with a small amount of Cu dissolved therein, with particle sizes ranging from 3nm to 200nm. The T impurity content is significantly reduced compared to the Cu raw material, while the remaining large amount of T impurities is enriched in the Cu coating. In the resulting metal strip composed of endogenous nano-Nb-V-Mo-W alloy powder and Cu coating, the volume percentage of endogenous Nb2VMoW alloy powder is comparable to the volume percentage of the raw material formulation, still approximately 33vol%, ensuring the dispersed distribution of the Nb2VMoW alloy powder in the Cu-dominant matrix phase.

[0223] (4) The Cu coating in the metal strip composed of endogenous nano-Nb-V-Mo-W alloy powder and Cu coating is removed by using a medium-concentration hydrochloric acid solution. Since the Nb2VMoW alloy powder is not easy to react with the medium-concentration hydrochloric acid solution, the nano-scale alloy powder mainly composed of Nb2VMoW can be obtained after separation, cleaning and drying.

[0224] Example 11

[0225] This embodiment provides a metal sheet composed of endogenous micron Nb-V-Mo-W alloy powder and a Cu coating, a micron Nb-V-Mo-W alloy powder, and a preparation method thereof, including the following steps:

[0226] (1) Low-purity Nb, V, Mo, W and Cu raw materials are selected, and the impurity T content in the two raw materials is about 1at%. Since Cu-Nb, Cu-V, Cu-Mo and Cu-W are element pairs that do not form intermetallic compounds, and Nb, V, Mo and W are mutually soluble main elements, Nb-V-Mo-W alloy powder can be prepared based on these pairs.

[0227] (2) Low-purity Nb, V, Mo, and W raw materials are mixed with Cu raw materials in a volume ratio of 1:2, wherein the molar ratio of Nb:V:Mo:W is 1:1:1:1. The alloy raw materials are induction melted to obtain an initial (NbVMoW)-Cu-T alloy melt, wherein the T content is approximately 1 at%.

[0228] (3) The initial alloy melt is solidified into a thin plate with a thickness of about 4 mm. During the solidification process, a dispersed dendrite phase composed mainly of NbVMoW is embedded in the matrix phase composed mainly of Cu, thus obtaining a metal thin plate composed of endogenous micron Nb-V-Mo-W alloy powder and Cu coating. The atomic percentage composition of the endogenous NbVMoW dendrite alloy powder is approximately (NbVMoW) 99.6 Cu 0.3 T 0.1, which is mainly composed of high-entropy NbVMoW single crystal particles with a small amount of Cu dissolved therein, with particle sizes ranging from 1μm to 150μm. The T impurity content is also greatly reduced compared to the Cu raw material, while other large amounts of T impurities are enriched in the Cu coating. In the resulting metal sheet composed of endogenous micron Nb-V-Mo-W alloy powder and Cu coating, the volume percentage of endogenous NbVMoW dendritic alloy powder is equivalent to the volume percentage of the raw material formulation, still approximately 33vol%, ensuring the dispersed distribution of NbVMoW dendritic alloy powder in the Cu-dominant matrix phase.

[0229] (4) The Cu cladding in the metal sheet composed of endogenous micron Nb-V-Mo-W alloy powder and Cu cladding is removed by using a medium-concentration hot hydrochloric acid solution. Since the NbVMoW dendritic alloy powder does not easily react with the medium-concentration hot hydrochloric acid solution, after separation, cleaning and drying, a micron-sized dendritic alloy powder mainly composed of NbVMoW can be obtained.

[0230] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0231] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. A method for preparing a metal material consisting of endogenous alloy powder and a coating, characterized in that: Prepared by the following steps: Step 1: Smelting main element composition is M a0 A b0 T c0 The initial alloy melt, a0, b0, c0 represent the atomic percentage content of the corresponding constituent elements, a0+b0+c0=100%, 0 <c0≤15%; Step 2: Solidify the M a0 A b0 T c0 The initial alloy melt into a solid state, obtaining the M precipitated endogenously from the melt a1 A b1 T c1 Dispersed particle phase and the A coating the dispersed particles b2 T c2 Matrix phase, which is the metal material composed of endogeneous alloy powder and coating; where 0 < c1 < c0 < c2, that is, M a0 A b0 T c0 The content of element T in the initial alloy melt is higher than that in M a1 A b1 T c1 The content of element T in the dispersed particle phase, and at the same time lower than that in A b2 T c2 The content of element T in the matrix phase; The metal material composed of endogenous alloy powder and coating is prepared by solidification of alloy melt, and its composition includes dispersed particles precipitated endogenously during the initial alloy solidification process and a matrix phase coating the dispersed particles, which correspond to the endogenous alloy powder and the coating respectively; the element composition of the endogenous alloy powder is mainly M a1 A b1 T c1 The element composition of the coating is mainly A b2 T c2 ; The M and A each contain one or more metal elements, T is an impurity element including oxygen, a1, b1, c1, b2, c2 represent the atomic percentage content of the corresponding element composition, and a1+b1+c1=100%, b2+c2=100%, c2>c1>0, b1>0; the melting point of the endogenous alloy powder is higher than the melting point of the coating; the endogenous alloy powder M a1 A b1 T c1 A element is solid-dissolved therein; between the M and the A, one or more groups of M that do not form intermetallic compounds are included. 1 -A 1 element combination, where M 1 Represents any element in M, A 1 represents any element in A, and the main elements in M ​​are those that satisfy M 1 -A 1 Each M of the element combination condition 1 Elements, the main elements in A are composed of 1 -A 1 Each A of the element combination conditions 1 The metal material composed of the endogenous alloy powder and the coating is completely melted and then re-solidified, but does not generate an intermetallic compound composed of the main element in M ​​and the main element in A, but generates the endogenous alloy powder M a1 A b1 T c1 With the coating A b2 T c2 .

2. The method for preparing a metal material composed of endogenous alloy powder and a coating according to claim 1, characterized in that: The shape of the metal material composed of endogenous alloy powder and coating is related to the solidification method: when the solidification method is continuous casting, its shape is generally mainly lamellar; when the solidification method is melt stripping, its shape is generally mainly strip or thin plate; when the solidification method is melt drawing, its shape is generally mainly wire-like.

3. The method for preparing a metal material composed of endogenous alloy powder and a coating according to claim 1, characterized in that: The T is O, H, N, P, S, F, Cl element including O, and 0 <c1≤1.5%。 4. The method for preparing a metal material composed of endogenous alloy powder and a coating according to claim 1, characterized in that: The M includes at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti, Fe, Co, Ni, Mn, Cu, and Ag, and A includes at least one of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mg, Ca, Li, Na, K, In, Pb, and Zn.

5. The method for preparing a metal material composed of endogenous alloy powder and a coating according to claim 1, characterized in that: The M includes at least one of Ir, Ru, Re, Os, Tc, W, Cr, Mo, V, Ta, and Nb, and A includes Cu.

6. The method for preparing a metal material composed of endogenous alloy powder and a coating according to claim 5, characterized in that: The metal material composed of the endogenous alloy powder and the coating is a metal material strip composed of the endogenous alloy powder and the coating with a thickness of 10 μm to 5 mm, and the particle size of the endogenous alloy powder contained therein ranges from 3 nm to 200 μm.

7. The method for preparing a metal material composed of endogenous alloy powder and a coating according to claim 1, characterized in that: 0<b1≤15％。 8. The method for preparing a metal material composed of endogenous alloy powder and a coating according to claim 1, characterized in that: The number of single crystal particles in the endogenous alloy powder accounts for no less than 60% of the total number of particles.

9. The method for preparing a metal material composed of endogenous alloy powder and a coating according to claim 1, characterized in that: The M a0 A b0 T c0 The initial alloy melt is formed by melting an alloy raw material comprising a first raw material and a second raw material; wherein the main element composition of the first raw material is M d1 T e1 The main element composition of the second raw material is A d2 T e2 , d1, e1, d2, e2 represent the atomic percentage content of the corresponding elements, and 0 <e1≤10%,0<e2≤10%,d1+e1=100%,d2+e2=100%。 10. The method for preparing a metal material composed of endogenous alloy powder and a coating according to claim 9, characterized in that: The endogenous M a1 A b1 T c1 The content of T impurities in alloy powder is higher than that of M d1 T e1 The raw material is greatly reduced, that is, c1 is less than e1.

11. The method for preparing a metal material composed of endogenous alloy powder and a coating according to claim 9, characterized in that: In the metal material composed of the endogenous alloy powder and the coating, the endogenous M a1 A b1 T c1 The volume percentage of alloy powder and the raw material preparation M d1 T e1 The volume percentages of the raw materials are comparable.

12. The method for preparing a metal material composed of endogenous alloy powder and a coating according to claim 1, characterized in that: The lower limit of the volume percentage content of the endogenous alloy powder in the metal material composed of the endogenous alloy powder and the coating is 1%, and the upper limit is the volume percentage content corresponding to the dispersion distribution of the endogenous alloy powder in the coating.

13. The method for preparing a metal material composed of endogenous alloy powder and a coating according to claim 1, characterized in that: The volume percentage content of the endogenous alloy powder in the metal material composed of the endogenous alloy powder and the coating body is in the range of 1% to 50%.

14. A method for preparing alloy powder, characterized in that: The method is prepared by removing the coating part of the metal material composed of endogenous alloy powder and the coating prepared by the method according to any one of claims 1 to 13, while retaining the endogenous alloy powder that cannot be removed at the same time.

15. The method for preparing alloy powder according to claim 14, characterized in that: The method of removing the coating and retaining the endogenous alloy powder includes at least one of acid solution dissolution reaction removal, alkaline solution dissolution reaction removal, vacuum volatilization removal, and coating natural oxidation-powdering removal.

16. The method for preparing alloy powder according to claim 14, characterized in that: The M contains Fe, the A contains La, and the metal material composed of the endogenous alloy powder and the coating is a metal strip composed of endogenous Fe alloy powder and a La coating, and La is solid-dissolved in the endogenous Fe alloy powder; the endogenous Fe alloy powder and the oxide powder of the matrix La are pre-separated by natural oxidation-pulverization of the La coating, and the Fe alloy powder and the oxide of the matrix La are separated by a magnetic field due to the magnetic properties of the Fe alloy powder.

17. The method for preparing alloy powder according to claim 14, characterized in that: The particle size of the alloy powder ranges from 3 nm to 10 mm.

18. A method for preparing spherical or nearly spherical alloy powder, characterized in that: The alloy powder according to claim 14 is subjected to plasma spheroidization treatment to obtain spherical or nearly spherical alloy powder.

19. The method for preparing spherical or nearly spherical alloy powder according to claim 18, characterized in that: The selected particles are subjected to a jet mill pre-crushing treatment or (and) screening treatment before the plasma spheroidization treatment.

20. A metal material composed of endogenous alloy powder and a coating, characterized in that: The metal material is prepared by the method for preparing a metal material composed of endogenous alloy powder and a coating according to any one of claims 1 to 13.

21. An alloy powder, characterized in that: The alloy powder is prepared by the method for preparing the alloy powder according to claim 14.

22. A spherical or nearly spherical alloy powder, characterized in that: The spherical or nearly spherical alloy powder is prepared by the preparation method of claim 18.

23. An application of a metal material consisting of endogenous alloy powder and a coating in coatings and composite materials, characterized in that: The metal material composed of endogenous alloy powder and a cladding is prepared by the method for preparing a metal material composed of endogenous alloy powder and a cladding according to any one of claims 1 to 13.

24. The use of a metal material consisting of endogenous alloy powder and a coating in coatings and composite materials according to claim 23, characterized in that: After preparing the metal material composed of endogenous alloy powder and the coating, there is no rush to remove the coating and then find other ways to protect the endogenous alloy powder from contamination by impurities such as oxygen. Instead, the coating is directly used to protect the endogenous alloy powder. This metal material composed of endogenous alloy powder and the coating can be directly used as raw material for downstream production. When downstream production requires the use of endogenous alloy powder, the endogenous alloy powder can be released at the right time and under the right environment according to the characteristics of the next process, and then the released endogenous alloy powder can enter the next production process in the shortest possible time, thereby greatly reducing the chance of the alloy powder being contaminated.

25. The use of a metal material consisting of endogenous alloy powder and a coating in coatings and composite materials according to claim 23, characterized in that: A metal material consisting of endogenous alloy powder and a coating having an average particle size of less than 1000 nm is selected, and the coating is removed; while removing the coating or immediately after the coating is removed, the obtained alloy powder is mixed with other components of a coating or a composite material to reduce the content of impurities, including O, newly introduced to the surface or surface layer of the powder after the alloy powder surface is exposed, thereby obtaining an alloy powder with high surface activity and allowing other components of the coating or composite material to be well combined with the surface of the alloy powder at the atomic scale, thereby obtaining a coating or composite material added with high-purity, ultrafine, and high-activity alloy powder, which can be applied to various fields including antibacterial coatings, weather-resistant coatings, stealth coatings, absorbing coatings, wear-resistant coatings, anti-corrosion coatings, and resin-based composite materials.

26. Application of alloy powder in powder metallurgy, metal injection molding, magnetic materials, and coatings, characterized in that: The alloy powder is prepared by the alloy powder preparation method according to claim 14.

27. Application of alloy powder in catalysis, sterilization, metal powder 3D printing, and composite materials, characterized in that: The alloy powder is prepared by the alloy powder preparation method according to claim 14.

28. Application of spherical or nearly spherical alloy powder in powder metallurgy, metal injection molding, and metal powder 3D printing, characterized in that: The spherical or nearly spherical alloy powder is prepared by the method for preparing spherical or nearly spherical alloy powder according to claim 18.

29. A metal material composed of endogenous alloy powder and a coating, characterized in that: The alloy is prepared by solidification of the alloy melt, and its composition includes a dispersed particle phase precipitated endogenously during the initial alloy solidification process and a matrix phase coating the dispersed particles, which correspond to the endogenous alloy powder and the coating respectively; the element composition of the endogenous alloy powder is mainly M a1 A b1 T c1 The element composition of the coating is mainly A b2 T c2 , wherein M and A each contain one or more metal elements, T is an impurity element including oxygen, a1, b1, c1, b2, c2 represent the atomic percentage content of the corresponding element composition, and a1+b1+c1=100%,b2+c2=100%,c2>c1>0,b1>0; the melting point of the endogenous alloy powder is higher than the melting point of the coating; the endogenous alloy powder M a1 A b1 T c1 A element is solid-dissolved therein; between the M and the A, one or more groups of M that do not form intermetallic compounds are included. 1 -A 1 element combination, where M 1 Represents any element in M, A 1 represents any element in A, and the main elements in M ​​are those that satisfy M 1 -A 1 Each M of the element combination condition 1 Elements, the main elements in A are composed of elements that satisfy M 1 -A 1 Each A of the element combination conditions 1 The metal material composed of the endogenous alloy powder and the coating is completely melted and then re-solidified, but does not generate an intermetallic compound composed of the main element in M ​​and the main element in A, but generates the endogenous alloy powder M a1 A b1 T c1 With the coating A b2 T c2 .

30. The metal material composed of endogenous alloy powder and a coating according to claim 29, characterized in that: The M comprises at least one of W, Cr, Mo, V, Ta, Nb, Zr, Hf, Ti, Fe, Co, Ni, Mn, Cu, and Ag; A comprises at least one of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mg, Ca, Li, Na, K, In, Pb, and Zn; T is an impurity element including O, H, N, P, S, F, and Cl; and 0 <c1≤1.5%,0<b1≤15%。 31. An alloy powder prepared by removing the coating from the metal material consisting of endogenous alloy powder and the coating according to any one of claims 29 to 30, characterized in that: Its elemental composition is mainly M a3 A b3 T c3 , a3, b3, c3 respectively represent the atomic percentage content of the corresponding element composition, b3>0, a3+b3+c3=100%, and the T element content in the alloy powder is higher than the T element content in the endogenous alloy powder described in any one of claims 29-30, that is, c3>c1>0.

32. A spherical or nearly spherical alloy powder, characterized in that: The alloy powder of claim 31 is subjected to plasma spheroidization treatment to obtain spherical or nearly spherical alloy powder. It is characterized in that its elemental composition is mainly M a4 A b4 T c4 , a4, b4, c4 respectively represent the atomic percentage content of the corresponding element composition, b4>0, a4+b4+c4=100%, and the T element content in the spherical or nearly spherical alloy powder is higher than the T element content in the alloy powder that has not been plasma spheroidized, that is, c4>c3>c1>0.

33. A method for preparing a metal material composed of endogenous alloy powder and a coating, characterized in that: Prepared by the following steps: (1) The main elements of the smelting are composed of M a0 A b0 T c0 in the initial alloy melt, where both M and A contain one or more metal elements, T is an impurity element including oxygen element, a0, b0, c0 represent the atomic percentage contents of the corresponding constituent elements, a0 + b0 + c0 = 100%, 0 < c0; there is one or more groups of M 1 -A 1 element combinations that do not form intermetallic compounds between the M 1 represents any one element in M, A 1 represents any one element in A; and the main element in M is composed of each M 1 -A 1 element that satisfies the element combination condition, and the main element in A is composed of each A 1 element that satisfies the M 1 -A 1 element combination condition; 1 ​ (2) The M a0 A b0 T c0 The initial alloy melt solidifies into a solid state, and M is endogenously precipitated from the melt. a1 A b1 T c1 A of dispersed particles and coating dispersed particles b2 T c2 The matrix phase is the metal material composed of endogenous alloy powder and coating according to any one of claims 29 to 30, wherein 0 <c1<c0<c2。 34. The method for preparing a metal material composed of endogenous alloy powder and a coating according to claim 33, characterized in that: The M a0 A b0 T c0 The initial alloy melt is formed by melting an alloy raw material comprising a first raw material and a second raw material; wherein the main element composition of the first raw material is M d1 T e1 The main element composition of the second raw material is A d2 T e2 , d1, e1, d2, e2 represent the atomic percentage content of the corresponding elements, and 0 <e1≤10%,0<e2≤10%,d1+e1=100%,d2+e2=100%。 35. A method for preparing alloy powder, characterized in that: The method is prepared by removing the coating portion of the metal material composed of endogenous alloy powder and the coating as claimed in any one of claims 29 to 30, while retaining the endogenous alloy powder that cannot be removed at the same time.

36. Use of the alloy powder according to claim 31, or the alloy powder prepared by the preparation method according to claim 35 in powder metallurgy, metal injection molding, magnetic materials, and coatings.

37. Use of the spherical or nearly spherical alloy powder according to claim 32 in powder metallurgy, metal injection molding, and metal powder 3D printing.

38. Use of the metal material consisting of endogenous alloy powder and a coating according to any one of claims 29-30, or the metal material consisting of endogenous alloy powder and a coating obtained by the preparation method according to any one of claims 33-34 in coatings and composite materials.

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