WO2021179677A1 - 粉体材料的制备方法及其应用 - Google Patents
粉体材料的制备方法及其应用 Download PDFInfo
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- WO2021179677A1 WO2021179677A1 PCT/CN2020/130961 CN2020130961W WO2021179677A1 WO 2021179677 A1 WO2021179677 A1 WO 2021179677A1 CN 2020130961 W CN2020130961 W CN 2020130961W WO 2021179677 A1 WO2021179677 A1 WO 2021179677A1
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- Prior art keywords
- powder material
- phase
- initial alloy
- alloy
- powder
- Prior art date
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Classifications
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Definitions
- the invention relates to the technical field of micro-nano materials, in particular to a method for preparing a powder material and its application.
- the preparation methods of micron, sub-micron, and nanometer particle size ultrafine powder materials can be divided into solid phase method, liquid phase method and gas phase method from the state of matter.
- the solid phase method mainly includes mechanical crushing method, ultrasonic crushing method, thermal decomposition method, explosion method, etc.
- the liquid phase method mainly includes precipitation method, alkoxide method, carbonyl method, spray thermal drying method, freeze drying method, electrolysis method, etc.
- gas phase method mainly includes gas phase reaction method, plasma method, high temperature plasma method, evaporation method, chemical vapor deposition method, etc.
- the impurity content of the powder material especially the oxygen content, has a great influence on its performance.
- the impurity content of metals or alloys is controlled mainly by controlling the purity and vacuum degree of raw materials, which is costly. Therefore, it is of great significance to develop new preparation methods for high-purity powder materials.
- a preparation method of powder material including:
- Step S1 selecting initial alloy raw materials, and melting the initial alloy raw materials according to the initial alloy composition ratio to obtain a uniform initial alloy melt containing the impurity element T, where T contains O, H, N, P, S, F, Cl, At least one of I and Br, and the average composition of the initial alloy melt is A a M b T d , where A contains Zn, Mg, Sn, Pb, Ga, In, Al, La, Ge, Cu At least one of, K, Na, and Li, M contains at least one of B, Bi, Fe, Ni, Cu, Ag, Cr, V, Si, Ge, where a, b, and d represent the corresponding constituent elements Atomic percentage content, and 60% ⁇ a ⁇ 99.5%, 0.5% ⁇ b ⁇ 40%, 0 ⁇ d ⁇ 10%;
- Step S2 solidifying the initial alloy melt into an initial alloy strip;
- the solidification structure of the initial alloy strip includes a matrix phase and a dispersed particle phase; the melting point of the matrix phase is lower than that of the dispersed particle phase, The dispersed particle phase is coated in the matrix phase; during the solidification of the initial alloy melt, the impurity element T in the initial alloy melt is redistributed in the dispersed particle phase and the matrix phase, and is enriched in the matrix Phase, so that the dispersed particle phase is purified;
- the composition of the dispersed particle phase in the initial alloy strip is mainly M x1 T z1 , and the average composition of the matrix phase is mainly A x2 T z2 ; and 98.5% ⁇ x1 ⁇ 100%, 0 ⁇ z1 ⁇ 1.5%; 80% ⁇ x2 ⁇ 100%, 0 ⁇ z2 ⁇ 20%; z1 ⁇ d ⁇ z2, 2z1 ⁇ z2; x1, z1, x2, and z2 respectively represent the atomic percentage content of the corresponding constituent elements;
- Step S3 Remove the matrix phase in the initial alloy strip, and retain the dispersed particle phase that cannot be removed at the same time during the matrix phase removal process, and collect the scattered dispersed particle phase to obtain a high purity composed of the original dispersed particles.
- Target powder material Remove the matrix phase in the initial alloy strip, and retain the dispersed particle phase that cannot be removed at the same time during the matrix phase removal process, and collect the scattered dispersed particle phase to obtain a high purity composed of the original dispersed particles.
- A includes at least one of Sn, Pb, Ga, In, Al, La, Ge, Cu, K, Na, and Li
- M includes at least one of B, Bi, Fe, Ni, Cu, and Ag ;
- M contains B A contains at least one of Sn, Ge, and Cu; when M contains Bi, A contains at least one of Sn, Ga, and Al; when M contains Fe, A contains La At least one of, In, Na, K, and Li; when M contains Ni, A contains at least one of Na, K, and Li; when M contains Cu, A contains Pb, Na, K, and Li At least one; when M contains Ag, A contains at least one of Pb, Na, and K.
- M contains at least one of Si and Ge
- A contains at least one of Zn, Sn, Pb, Ga, In, Ag, Bi, and Al
- M contains at least one of B, Cr, and V In one type
- A contains Zn
- M contains Fe
- A contains Mg
- the source of the T impurity element in the initial alloy melt includes the introduction of impurities into the initial alloy raw materials, and the introduction of impurities into the atmosphere or the crucible during the smelting process.
- the introduction of impurities in the atmosphere refers to impurities such as O, N, and H in the ambient atmosphere absorbed by the alloy melt.
- T is an impurity element and contains at least one of O, H, N, P, S, F, Cl, I, and Br; and the total content of these impurity elements is the content of the T impurity element;
- the raw materials are elemental or intermediate alloys containing impurity elements, they can be melted according to the ratio to prepare the initial alloy melt. If the raw material provided is directly the initial alloy melt composition corresponding to the alloy raw material, it can be remelted to obtain the initial alloy melt.
- the initial alloy raw materials include M-T raw materials containing T as an impurity element.
- M-T raw materials when M is Fe and T contains O, the M-T raw material includes Fe-O raw material containing O impurity.
- the combination of A and M in the average composition of the initial alloy melt in the step S1 is extremely important, and the selection principle is to ensure that no intermetallic compound is formed between A and M during the solidification of the alloy melt. In this way, the two-phase separation of the A-based matrix phase and the M-based particle phase during the initial alloy melt solidification process can be realized, which is beneficial to the subsequent preparation of M-based powder materials.
- the initial alloy strip does not contain intermetallic compounds composed of A and M;
- the method of solidification of the alloy melt includes the stripping method and the continuous casting method; generally speaking, a thinner initial alloy strip can be obtained by the stripping method; a thicker alloy strip can be obtained by the continuous casting method .
- Both the thin alloy strip obtained by the stripping method or the thick alloy strip obtained by the continuous casting method are completely different from the alloy ingots obtained by the ordinary casting method.
- the alloy ingots obtained by the ordinary casting method are generally in terms of size. There is no obvious difference in length, width, or thickness.
- the thickness of the initial alloy strip is in the range of 5 ⁇ m to 10 mm; further, the thickness of the initial alloy strip is in the range of 5 ⁇ m to 5 mm; preferably, the thickness of the initial alloy strip is in the range of 5 ⁇ m to 1 mm. As a further preference, the thickness of the initial alloy strip is in the range of 5 ⁇ m to 200 ⁇ m; as a further preference, the thickness of the initial alloy strip is in the range of 5 ⁇ m to 20 ⁇ m.
- the thickness of the initial alloy strip is millimeter-level, it can also be referred to as an alloy sheet.
- the width of the cross section of the initial alloy strip is more than 2 times its thickness; further, the length of the initial alloy strip is more than 10 times its thickness; preferably, the width of the initial alloy strip The length is more than 50 times its thickness; preferably, the length of the initial alloy strip is more than 100 times its thickness;
- the solidification rate of the initial alloy melt is 1K/s ⁇ 10 7 K/s;
- the particle size of the dispersed particle phase is related to the solidification rate of the initial alloy melt; in general, the particle size of the dispersed particle phase has a negative correlation with the solidification rate of the initial alloy melt, that is, the initial alloy The greater the solidification rate of the melt, the smaller the particle size of the dispersed particle phase.
- the particle size of the dispersed particle phase is in the range of 2nm to 3mm; further, the particle size of the dispersed particle phase is in the range of 2nm to 500 ⁇ m; preferably, the particle size of the dispersed particle phase is in the range of 2nm to 3mm. 99 ⁇ m; as a further preferred, the particle size of the dispersed particle phase ranges from 2nm to 5 ⁇ m; as a further preferred, the particle size of the dispersed particle phase ranges from 2nm to 200nm; as a further preferred, the particle size of the dispersed particle phase The range is from 2nm to 100nm.
- the dispersed particles whose particle size is mainly sub-micron scale can be obtained.
- the dispersed particles whose particle size is mainly on the micron scale can be obtained.
- the particle shape of the dispersed particle phase is not limited, and may include at least one of dendritic shape, spherical shape, nearly spherical shape, square shape, pie shape, and rod shape; when the particle shape is rod shape, the particle shape
- the size specifically refers to the diameter of the cross-section of the bar.
- dispersed particles are of nanometer or submicron scale, spherical or nearly spherical particles are likely to be obtained; when the dispersed particles are of micrometer or above, dendritic particles are likely to be obtained.
- the dispersed particle phase is solidified and precipitated from the initial alloy melt.
- the crystal grains have a fixed orientation relationship for their crystal growth, so that the individual grains precipitated are mainly composed of a single crystal.
- the number of single crystal particles in the dispersed particles in the initial alloy strip accounts for not less than 60% of the total number of dispersed particles.
- the number of single crystal particles in the dispersed particles accounts for not less than 90% of the total number of dispersed particles.
- the volume percentage of the dispersed particle phase in the initial alloy strip can be determined by corresponding to the initial alloy melt composition, the dispersed particle phase composition, and the matrix phase composition, Combining element atomic weight, density parameters and other calculations to determine.
- volume percentage of the dispersed particle phase in its corresponding initial alloy strip is not higher than 50%.
- the atomic percentage content z1 of T impurity elements in the dispersed particles is less than the atomic percentage content of T impurity elements in the M-T raw material.
- z1 ⁇ d ⁇ z2, and 3z1 ⁇ z2 that is, the T impurity content in the dispersed particle phase is lower than the T impurity content in the initial alloy melt, and the T impurity content in the dispersed particle phase is 3% Times is still lower than the T impurity content in the matrix phase;
- the present invention uses the atomic percentage content to express the T impurity content.
- the composition of each element is characterized by the atomic percentage content of the element, and the increase or decrease of the element content, such as the increase or decrease and change of impurity elements, can be accurately expressed through the concept of the amount of matter. If the mass percentage content (or ppm concept) of an element is used to characterize the content of each element, it is easy to produce wrong conclusions due to the difference in the atomic weight of each element. For example, if an alloy with an atomic percentage content of Ti 45 Gd 45 O 10 contains 100 atoms, the atomic percentage content of O is 10 at%.
- the mass percentage content of O in Ti 45 Gd 45 O 10 is 1.70 wt%
- the mass percentage content of O in Ti 45 O 4 and Gd 45 O 6 is 2.9 wt.% and 1.34wt.%
- the dispersed grain phase whose composition is mainly M x1 T z1 in the initial alloy strip does not contain A element;
- composition of the dispersed particle phase in the initial alloy strip is M x1 T z1 .
- the method for removing the matrix phase in the alloy strip includes at least one of acid reaction removal, alkali reaction removal, and vacuum volatilization removal.
- composition and concentration of the acid solution and the alkali solution are not specifically limited, as long as the matrix phase can be removed while retaining the dispersed particle phase.
- the temperature and vacuum degree of the vacuum treatment are not specifically limited, as long as the matrix phase can be removed while retaining the dispersed particle phase.
- the method for removing the matrix phase in the initial alloy strip includes natural oxidation-pulverization and peeling removal of the matrix phase.
- the matrix phase is an element that is easy to be naturally oxidized with oxygen, such as La
- the matrix phase can be separated from the dispersed particle phase through the natural oxidation-pulverization process of the matrix phase, and other technical means, such as magnetic
- the target powder material is the dispersed particle phase shed from the initial alloy strip
- the composition and particle size of the target powder material are all equivalent to the corresponding dispersed particle phase.
- the particle size of the target powder material is in the range of 2nm to 3mm; preferably, the particle size of the target powder material is in the range of 2nm to 500 ⁇ m; preferably, the particle size of the target powder material is The diameter range is 2nm ⁇ 99 ⁇ m; as a further preference, the particle size range of the target powder material is 2nm ⁇ 5 ⁇ m; as a further preference, the particle size range of the target powder material is 2nm ⁇ 200nm; as a further preference , The particle size of the target powder material ranges from 2 nm to 100 nm.
- the dispersed particles are separated from the initial alloy strip, cleaned and dried, and the target powder material is obtained.
- the target powder material whose main component is M x1 T z1 does not contain A element
- composition of the target powder material is mainly M x1 T z1 ; preferably, the composition of the target powder material is M x1 T z1 ;
- the atomic percentage content of the T impurity element in the target powder material does not exceed 1.5%
- step S3 after the powder material is sieved, a powder material with a particle size range of 5 ⁇ m to 200 ⁇ m is selected for plasma spheroidization to obtain a spherical powder material ;
- the invention also relates to the application of the powder material or spherical powder material obtained by the above preparation method in catalytic materials, powder metallurgy, composite materials, wave absorbing materials, sterilization materials, metal injection molding, 3D printing, and coatings.
- the application of the spherical powder material obtained by the above preparation method in the field of metal powder 3D printing is characterized in that the particle size of the spherical powder material ranges from 10 ⁇ m to 200 ⁇ m.
- the application of the powder material obtained by the above preparation method in metal injection molding and powder metallurgy is characterized in that the particle size of the powder material ranges from 0.1 ⁇ m to 200 ⁇ m.
- the application of the powder material obtained by the above preparation method in the coating is characterized in that the particle size of the powder material ranges from 2 nm to 5 ⁇ m.
- the present invention also relates to an alloy strip, which is characterized in that it contains endogenous powder and a coating; the solidification structure of the alloy strip includes a matrix phase and a dispersed particle phase.
- the matrix phase is the coating and the dispersed particles
- the phase is the endogenous powder; the melting point of the coating body is lower than that of the endogenous powder, and the endogenous powder is coated in the coating body;
- the composition of the ingrown powder in the alloy strip is mainly M x1 T z1 , and the average composition of the coating body is mainly A x2 T z2 ; and 98.5% ⁇ x1 ⁇ 100%, 0 ⁇ z1 ⁇ 1.5%; 80% ⁇ x2 ⁇ 100%, 0 ⁇ z2 ⁇ 20%; z1 ⁇ d ⁇ z2, 2z1 ⁇ z2; x1, z1, x2, and z2 respectively represent the atomic percentage content of the corresponding constituent elements; where A contains Sn, Pb, Ga, In , At least one of Al, La, Ge, Cu, K, Na, and Li, and M contains at least one of B, Bi, Fe, Ni, Cu, and Ag;
- M contains B A contains at least one of Sn, Ge, and Cu
- M contains Bi A contains at least one of Sn, Ga, and Al
- M contains Fe A contains La At least one of, In, Na, K, and Li
- M contains Ni A contains at least one of Na, K, and Li
- M contains Cu A contains Pb, Na, K, and Li At least one
- M contains Ag A contains at least one of Pb, Na, and K;
- M contains at least one of Si and Ge
- A contains at least one of Zn, Sn, Pb, Ga, In, Ag, Bi, and Al
- M contains at least one of B, Cr, and V In one type
- A contains Zn
- M contains Fe
- A contains Mg
- the endogenous powder whose main component is M x1 T z1 in the alloy strip does not contain A element
- the composition of the endogenous powder in the alloy strip is M x1 T z1 , and the average composition of the coating body is A x2 T z2 ;
- the thickness of the alloy strip is in the range of 5 ⁇ m to 10 mm; preferably, the thickness of the alloy strip is in the range of 5 ⁇ m to 5 mm; preferably, the thickness of the alloy strip is in the range of 5 ⁇ m to 1 mm; as a further step
- the thickness of the alloy strip is in the range of 5 ⁇ m to 200 ⁇ m; as a further preference, the thickness of the alloy strip is in the range of 5 ⁇ m to 20 ⁇ m.
- the width of the cross section of the alloy strip is more than 2 times its thickness; further, the length of the initial alloy strip is more than 10 times its thickness; preferably, the length of the initial alloy strip It is more than 50 times its thickness; preferably, the length of the initial alloy strip is more than 100 times its thickness.
- the particle size of the endogenous powder ranges from 2 nm to 3 mm; preferably, the particle size range of the endogenous powder is 2 nm to 500 ⁇ m; preferably, the particle size range of the endogenous powder is 2 nm to 99 ⁇ m.
- the particle size range of the endogenous powder is 2nm-10 ⁇ m; as a further preference, the particle size range of the endogenous powder is 2nm-1 ⁇ m; as a further preference, the particle size range of the endogenous powder It is 2 nm to 200 nm; as a further preference, the particle size of the endogenous powder ranges from 2 nm to 100 nm.
- the shape of the endogenous powder includes at least one of a dendritic shape, a spherical shape, a near spherical shape, a square shape, a pie shape, and a rod shape.
- the number of single crystal particles in the endogenous powder in the alloy strip accounts for not less than 60% of the total number of endogenous powders.
- volume percentage content of the endogenous powder in the alloy strip does not exceed 50%.
- the A, M, or T in the solution of the present invention may also contain other elements or impurity elements other than those listed above. As long as the introduction of these elements or the change in content does not cause the initial alloy solidification process and regularity to cause "qualitative change", it will not affect the realization of the above technical solution of the present invention.
- the initial alloy strip does not contain intermetallic compounds mainly composed of A and M;
- the solidification structure of the initial alloy strip includes a matrix phase and a dispersed particle phase; the melting point of the matrix phase is lower than the dispersed particle phase, and the dispersed particle phase is coated in the matrix phase;
- the T impurity content in the initial alloy melt is not 0, the T impurity content in the dispersed particle phase is lower than the T impurity content in the initial alloy melt, and the T impurity content in the dispersed particle phase is less than 2 times is still lower than the T impurity content in the matrix phase.
- phase separation occurs when the initial alloy melt is solidified, so that endogenous particles with a certain particle size and target composition can be formed during the initial alloy melt solidification and can be separated by subsequent processes.
- bottom-up chemical methods such as chemical reduction
- nano metal particles can be prepared relatively easily, but when the size of the particles increases to hundreds of nanometers or even micrometers, it is difficult to prepare.
- top-down physical methods such as atomization, ball milling, etc.
- metal particles of tens of microns or hundreds of microns can be prepared relatively easily, but when the size of the particles is reduced to hundreds of nanometers to several microns, It is also difficult to prepare.
- the technical scheme of the present invention can easily prepare nanometer, submicron, micron, or even millimeter-level target metal powder particles according to the different cooling speeds during the solidification of the initial alloy strips, which breaks through the above technical difficulties and has extremely high Land advantage.
- the realization of obtaining high-purity target powder materials from low-purity raw materials, and pointing out a new way for the preparation of high-purity powder materials from low-purity raw materials, is of positive significance.
- the improvement of the purity of the target powder material of the present invention is mainly achieved through the following three mechanisms: 1) The "absorption" effect of high-active matrix main elements (such as La, Mg, etc.) on the impurity elements of the initial alloy melt.
- the matrix element is generally an element with high activity and low melting point, it has a strong affinity with the impurity element T during the melting and solidification of the alloy melt, which can make the impurity element T in the initial alloy melt or more
- the ground enters the matrix phase mainly composed of the main elements of the matrix phase, or forms a slag with the main elements of the matrix in the melt state, and is separated and removed from the alloy melt; 2)
- the endogenous precipitated dispersed particle phase nucleates and grows , The impurity element T will be discharged into the remaining melt.
- the endogenously precipitated dispersed particle phase precipitates no later than the matrix phase during the solidification process, its impurities will be concentrated in the last solidified part of the melt, that is, the part of the melt mainly composed of the main elements of the matrix phase and solidified to form the matrix phase. . 3)
- the crucible-related impurities that enter the melt due to the interaction between the crucible and the melt during the smelting process are generally concentrated in the second phase matrix, which further ensures the target powder material
- the purity of the smelting process further reduces the requirements on the crucible during the smelting process, which greatly reduces the production cost.
- the target metal powder mainly composed of single crystal particles can be obtained.
- single crystal powder can obtain many significant and beneficial effects.
- each endogenous dispersive particle is nucleated from a certain position in the melt and then grows up according to a specific atomic arrangement.
- the volume percentage of the dispersed particle phase in the initial alloy strip to not exceed 50%, it is possible to ensure that each endogenous particle can be dispersedly distributed, and it is difficult for each endogenous particle to merge and grow. Therefore, most of the dispersed particle phases finally obtained are single crystal phases.
- the growth direction of each secondary dendrite maintains a certain phase relationship with the growth direction of the main dendrite, and it is still a single crystal particle.
- the grain boundaries generally easily contain impurity elements discharged from the crystal during solidification, so it is difficult to obtain high-purity polycrystalline powder materials.
- the target metal powder is mainly composed of single crystal particles, its purity must be guaranteed.
- the surface atoms of the single crystal particles have a specific arrangement, such as (111) plane arrangement, etc. These specific arrangements will give the target metal powder special mechanical, physical, and chemical properties, thereby producing beneficial effects.
- the alloy strip composed of the endogenous powder and the coating creatively uses the in-situ generated matrix phase to wrap the endogenous powder, maintaining the high purity and high activity of the endogenous powder.
- metal or alloy powders prepared by traditional chemical or physical methods especially nano-powders with a large specific surface area, are easily oxidized naturally, and are faced with difficulties in powder preservation.
- the technical solution involved in the present invention after preparing an alloy strip composed of endogenous metal powder and a cladding body (matrix phase), does not rush to remove the cladding body, but directly uses the cladding The body protects the endogenous metal powder from natural oxidation.
- This alloy strip composed of endogenous metal powder and cladding can be directly used as a raw material for downstream production, so it has the potential to become a special kind of product.
- high-purity powders are needed for downstream production, you can choose the right time according to the characteristics of the next process and release the endogenous metal powder from the coating in the alloy strip under the right environment. In a short time, the released endogenous powder enters the next production process, thereby greatly reducing the chance of the endogenous metal powder being polluted by impurities such as oxygen.
- the endogenous metal powder when the endogenous metal powder is nano-powder, the endogenous metal powder can be compounded with the resin at the same time or immediately after the endogenous metal powder is released from the coating, thereby preparing a resin-based composite material added with the endogenous metal powder with high activity.
- the solid alloy obtained by solidification in the step S2 is in a strip shape, which ensures the uniformity of the product shape and the feasibility of large-scale production.
- the alloy strip is a thin alloy strip, it can be prepared by the strip spinning method. As long as the flow rate of the alloy melt to the rotating roll is maintained and the rotation speed of the rotating roll is fixed, an alloy thin strip with uniform thickness can be obtained, and the preparation process It can be carried out continuously, which is conducive to large-scale production.
- the alloy strip is a thick alloy strip, it can be prepared by a mature continuous casting method. The principle of continuous casting is similar to that of the stripping method. A continuous thick strip with uniform thickness can also be obtained from the melt. The preparation process can also be used. Continuous operation is conducive to large-scale production.
- the cooling rate is also more uniform, and the obtained dispersed particle size is also more uniform.
- the solid alloy obtained by solidification is in the shape of an ingot, according to common sense, the ingot has no uniform thickness, no obvious length and end points, which will generally cause difficulty in internal melt heat dissipation, and it is easy to obtain an abnormally large inner diameter. Raw particles, this operation is only required when the large endogenous particles need to be collected and purified. Moreover, it is difficult to continuously produce ordinary ingots. Therefore, the present invention obtains alloy strips through solidification, which is suitable for subsequent preparation of powder materials through the "dephasing method".
- the preparation method of the present invention has the characteristics of simple process, easy operation, and low cost, and can prepare a variety of high-purity powder materials including nanometer, submicrometer, and micrometer. , Wave absorbing materials, sterilization materials, magnetic materials, metal injection molding, 3D printing, coatings and other fields have good application prospects.
- the present invention also provides a method for preparing powder material, which includes the following steps:
- a preparation method of powder material including:
- the composition of the initial alloy is A a M b
- the microstructure of the initial alloy is composed of a matrix phase with a composition A and a dispersed particle phase with a composition M
- A is selected from Sn
- Pb At least one of, Ga, In, Al, La, Ge, Cu, K, Na, Li
- M is selected from at least one of B, Bi, Fe, Ni, Cu, Ag, and a and b represent the corresponding composition
- the atomic percentage of the element, and 1% ⁇ b ⁇ 40%, a+b 100%;
- the composition of the initial alloy has a specific element ratio and composition.
- the principle is to ensure that the microstructure of the initial alloy is composed of a matrix phase of composition A and a dispersed particle phase of composition M.
- the chemical activity of metal element A Higher than the chemical activity of element M.
- A is selected from at least one of Sn, Ge, and Cu;
- A is selected from at least one of Sn, Ga, and Al;
- A is selected from at least one of La, In, Na, K, and Li;
- A is selected from at least one of Na, K, and Li;
- A is selected from at least one of Pb, Na, K, and Li;
- A is selected from at least one of Pb, Na, and K.
- the initial alloy is obtained by the following method:
- the initial alloy is obtained by solidifying the alloy melt, wherein the solidification rate is 1 K/s to 10 7 K/s.
- the initial alloy can be prepared by methods such as "alloy melt solidification + mechanical crushing” or "alloy melt rapid solidification stripping".
- the particle size of the dispersed particle phase of the composition M is related to the solidification rate of the alloy melt during the preparation process.
- the particle size of the dispersed particle phase is negatively related to the solidification rate of the alloy melt, that is, the larger the solidification rate of the alloy melt, the smaller the particle size of the dispersed particle phase. Therefore, in the preparation process of the present invention, the alloy melt obtained by smelting the raw materials is preferably solidified into an initial alloy at a rate of 1K/s ⁇ 10 7 K/s, and the particle size of the dispersed particle phase in the obtained initial alloy is 2nm ⁇ 500 ⁇ m .
- the particle shape of the dispersed particle phase is not limited, and may include at least one of a dendritic shape, a spherical shape, a nearly spherical shape, a square shape, a pie shape, and a rod shape. It should be noted that when the particle shape is a rod shape, the size of the particle specifically refers to the diameter size of the cross section of the rod.
- the etching solution is an acid solution, and the acid in the acid solution includes hydrochloric acid, sulfuric acid, At least one of nitric acid, phosphoric acid, acetic acid, and oxalic acid.
- the corrosive liquid is water, and the water is subjected to deoxygenation treatment.
- the concentration of the acid in the acid solution only needs to be able to react with the matrix phase and basically retain the dispersed particle phase, and the temperature and time of the reaction are also not limited.
- the molar concentration of the acid in the acid solution is 0.01 mol/L to 20 mol/L
- the reaction time of the reaction may be 0.1 min to 5 h
- the reaction temperature may be 0°C to 100°C.
- the particle size and morphology of the finally formed powder material with a composition of M are basically the same as the particle size and morphology of the dispersed particle phase in the initial alloy. Its particle size is 2nm ⁇ 500 ⁇ m.
- the initial alloy with the composition A a M b is made by selecting the metal element A with higher chemical activity and the element M with lower chemical activity than the metal element A.
- the microstructure of the initial alloy is The composition is composed of the matrix phase with the component A and the dispersed particle phase with the component M, and this organization structure is conducive to subsequent separation. Specifically, when this kind of initial alloy reacts with the corrosive liquid, the matrix phase of the composition A will react with the corrosive liquid to become ions into the solution, and the dispersed particle phase of the composition M will not react with the corrosive liquid or only slightly react with the corrosive liquid. After reaction, it is separated from the initial alloy, and the powder material with the composition of M is obtained.
- the preparation method of one of the alternatives has the characteristics of simple process, easy operation, and low cost, and can be prepared including nanometer, submicron, and A variety of micron-sized ultra-fine powder materials have good application prospects in the fields of catalysis, powder metallurgy, sterilization, and 3D printing.
- the preparation method of a type of powder material provided by the present invention includes:
- A includes at least one of Zn, Sn, Pb, Ga, In, Ag, Bi, and Al;
- A contains at least one of Mg and Zn;
- the initial alloy is fully melted to obtain an initial alloy melt.
- no intermetallic compound is formed between A and M, but separation of A and M occurs, and a dispersion with an element composition of M is obtained.
- step S1 the composition of the initial alloy has a specific element ratio and composition.
- the principle is to ensure that the solidified alloy of the initial alloy is composed of a matrix phase of composition A and a dispersed particle phase of composition M.
- the particle size of the dispersed particle phase of the composition M is related to the solidification rate of the initial alloy melt during the preparation process.
- the particle size of the dispersed particle phase is negatively related to the solidification rate of the initial alloy melt, that is, the larger the solidification rate of the initial alloy melt, the smaller the particle size of the dispersed particle phase. Therefore, in the preparation process of the present invention, the initial alloy melt obtained by smelting the raw materials is solidified into a solid alloy at a rate of preferably 1K/s ⁇ 10 7 K/s, and the particle size of the dispersed particle phase in the solid alloy obtained is 2nm ⁇ 500 ⁇ m.
- the thickness of the solidified alloy is controlled to be 10 ⁇ m-50mm, and the reaction area of the obtained alloy is increased as much as possible by methods such as "alloy melt solidification + mechanical crushing” or “alloy melt rapid solidification stripping" to ensure the subsequent A matrix phase Removed smoothly.
- the particle shape of the dispersed particle phase is not limited, and may include at least one of a dendritic shape, a spherical shape, a nearly spherical shape, a square shape, a pie shape, and a rod shape. It should be noted that when the particle shape is a rod shape, the size of the particle specifically refers to the diameter size of the cross section of the rod.
- step S2 the method of removing the A matrix phase is one of acid reaction removal, alkali reaction removal, vacuum volatilization removal, and the like.
- the acid in the acid solution includes at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, and oxalic acid.
- the molar concentration of the acid is 0.1 mol/L to 15 mol/L, and the reaction time is It is 1 min to 1 h, and the reaction temperature is 0°C to 100°C.
- the alkali in the alkali solution includes at least one of NaOH and KOH, the molar concentration of the alkali is 0.1 mol/L to 15 mol/L, the reaction time is 1 min to 1 h, and the reaction temperature is 0°C ⁇ 100°C.
- the vacuum degree in the container where the solid alloy is located is less than 10 Pa
- the processing temperature is related to the melting point T m of the A matrix phase
- the processing temperature ranges from T m -1K to T m -200K
- the processing time is more than 0.1h.
- the particle size and morphology of the final powder material with a composition of M are basically the same as the particle size and morphology of the dispersed particle phase in the solid alloy. Its particle size is 2nm ⁇ 500 ⁇ m.
- step S2 the following steps may be performed: the obtained M powder material is sieved, and plasma spheroidization is performed respectively, to finally obtain spherical M powder materials with different particle diameters.
- the powder material after the screening can be spheroidized by plasma spheroidization.
- the particle size of the spherical M powder material ranges from 1 ⁇ m to 500 ⁇ m.
- the microstructure of the A a M b solid state alloy is composed of a matrix phase with a composition of A and a dispersed particle phase with a composition of M, and this structure is conducive to subsequent separation.
- the matrix phase with the composition A will react with the etching solution to become ions into the solution, and the dispersed particle phase with the composition M will not react with the etching solution, thereby removing from the solid alloy
- a powder material with a composition of M is obtained.
- the A matrix phase with a lower melting point has strong volatility when it is close to the melting point, and the M-dispersed particles with a higher melting point can be better retained at this temperature. Therefore, after the A matrix phase is completely volatilized, the M dispersed particles will also be separated to obtain the corresponding powder material.
- the preparation method of the second alternative invention has the characteristics of simple process, easy operation and low cost, and can be prepared including nanometer and submicron As well as a variety of ultra-fine powder materials in the micron level, they have good application prospects in the fields of catalysis, powder metallurgy, sterilization, powder injection molding, and 3D printing.
- This embodiment provides a method for preparing nano B powder, which includes the following steps:
- the microstructure includes a matrix phase composed of Cu and a dispersed particle phase composed of nano-B particles.
- the dispersed particle phase The particle size is 2nm ⁇ 100nm.
- This embodiment provides a method for preparing submicron B powder, which includes the following steps:
- the microstructure includes a matrix phase composed of Sn and a dispersed particle phase composed of submicron B particles. Among them, the particle size of the dispersed particle phase is 100 nm to 2 ⁇ m.
- This embodiment provides a method for preparing nano Bi powder, which includes the following steps:
- the alloy with the formula molecular formula of Al 75 B i25 is selected, the raw materials are weighed according to the formula, and the alloy melt with the composition of Al 75 B i25 is obtained by vacuum induction melting.
- the alloy melt is prepared at a rate of ⁇ 10 6 K/s into Al 75 B i25 alloy ribbon with a thickness of ⁇ 20 ⁇ m.
- the microstructure includes a matrix phase composed of Al and a dispersed particle phase composed of nano-Bi particles. , The particle size of the dispersed particle phase is 2nm ⁇ 150nm.
- This embodiment provides a method for preparing submicron Fe powder, which includes the following steps:
- the alloy with the formula molecular formula of La 75 Fe 25 is selected, the raw materials are weighed according to the formula, and the alloy melt with the composition of La 75 Fe 25 is obtained by vacuum induction melting.
- the alloy melt was prepared into a thin ribbon-like initial alloy fragment of La 75 Fe 25 with a thickness of 150 ⁇ m at a rate of 10 3 K/s ⁇ 10 4 K/s by a copper roller spinning rapid solidification method.
- the microstructure includes A matrix phase composed of La and a dispersed particle phase composed of sub-micron Fe particles, wherein the dispersed particle phase has a particle size of 200 nm to 3 ⁇ m.
- the La 75 Fe 25 initial alloy fragments prepared above were immersed in 50 mL of a hydrochloric acid aqueous solution with a concentration of 0.01 mol/L for reaction.
- the matrix phase composed of the active element La reacts with the acid and enters the solution, while the less active dispersed Fe particles are separated.
- the application of an auxiliary magnetic field during the reaction can ensure that the Fe particles that have just been separated are separated from the acid solution in time.
- the sub-micron Fe particles are gradually collected, washed and dried to obtain sub-micron Fe particle powder, the particle size of the Fe particles is 200 nm to 3 ⁇ m.
- This embodiment provides a method for preparing submicron Fe powder, which includes the following steps:
- the alloy with the formula formula of Li 75 Fe 25 is selected, the raw materials are weighed according to the formula, and the alloy melt with the composition of Li 75 Fe 25 is obtained by vacuum induction melting.
- the alloy melt is prepared into Li 75 Fe 25 thin ribbon-like initial alloy fragments with a thickness of 150 ⁇ m at a rate of 10 3 K/s to 10 4 K/s by a copper roller spinning rapid solidification method.
- the microstructure includes A matrix phase composed of Li and a dispersed particle phase composed of submicron Fe particles, wherein the dispersed particle phase has a particle size of 200 nm to 3 ⁇ m.
- This embodiment provides a method for preparing nano Fe powder, which includes the following steps:
- the alloy with the formula formula of Li 75 Fe 25 is selected, the raw materials are weighed according to the formula, and the alloy melt with the composition of Li 75 Fe 25 is obtained by vacuum induction melting.
- the alloy melt is prepared into Li 75 Fe 25 thin ribbon-shaped initial alloy fragments with a thickness of -15 ⁇ m at a rate of ⁇ 10 6 K/s by a copper roller spinning rapid solidification method.
- the microstructure includes a matrix composed of Li.
- the phase and the dispersed particle phase composed of nano-Fe particles, wherein the particle size of the dispersed particle phase is 2nm-200nm.
- This embodiment provides a method for preparing nano Ni powder, which includes the following steps:
- the alloy with the formula formula of Li 80 Ni 20 is selected, the raw materials are weighed according to the formula, and the alloy melt with the composition of Li 80 Ni 20 is obtained by vacuum induction melting.
- the alloy melt is prepared into Li 80 Ni 20 thin ribbon-shaped initial alloy fragments with a thickness of -15 ⁇ m at a rate of ⁇ 10 6 K/s by a copper roller spinning rapid solidification method.
- the microstructure includes a matrix composed of Li The phase and the dispersed particle phase composed of nano-Ni particles, wherein the particle size of the dispersed particle phase is 2nm-200nm.
- This embodiment provides a method for preparing nano Ag powder, which includes the following steps:
- the microstructure includes a matrix phase composed of Pb and a dispersed particle phase composed of nano-Ag particles. Among them, the particle size of the dispersed particle phase is 2 nm to 200 nm.
- This embodiment provides a method for preparing micron Ag powder, which includes the following steps:
- the alloy melt is prepared by a casting method at a rate of ⁇ 500K/s
- a Pb 75 Ag 25 thin plate with a thickness of ⁇ 2mm is formed, and its microstructure includes a matrix phase composed of Pb and a dispersed particle phase composed of micron Ag dendritic particles.
- the particle size of the dispersed particle phase is 0.5 ⁇ m-30 ⁇ m.
- This embodiment provides a method for preparing nano Ag powder, which includes the following steps:
- the K 75 Ag 25 thin ribbon-shaped initial alloy fragments with a thickness of -20 ⁇ m are prepared at a rate of 6 K/s.
- the microstructure includes a matrix phase composed of K and a dispersed particle phase composed of nano Ag particles. Among them, the particle size of the dispersed particle phase is 2 nm to 200 nm.
- This embodiment provides a method for preparing submicron Ag powder, which includes the following steps:
- Formulation Methods of formula Na 75 Ag 25 alloy the raw materials were weighed according to the formulation, vacuum induction melting component is obtained Na 75 Ag 25 alloy melt of the alloy melt through a melt spinning copper roller quick setting to 103 K/s ⁇ 10 4 K/s are prepared into Na 75 Ag 25 thin ribbon-like initial alloy fragments with a thickness of ⁇ 150 ⁇ m.
- the microstructure includes a matrix phase composed of Na and a dispersed particle phase composed of submicron Ag particles. . Among them, the particle size of the dispersed particle phase is 100 nm to 3 ⁇ m.
- This embodiment provides a method for preparing micron Cu powder, which includes the following steps:
- the alloy melt is prepared to a thickness of 3mm at a rate of ⁇ 200K/s
- the microstructure of Pb 80 Cu 20 flakes includes a matrix phase composed of Pb and a dispersed particle phase composed of micron Cu particles. Among them, the particle size of the dispersed particle phase is 1 ⁇ m-50 ⁇ m.
- 0.5 g of the Pb 80 Cu 20 initial alloy prepared above was immersed in 100 mL of an aqueous hydrochloric acid solution with a concentration of 2 mol/L for reaction.
- the matrix phase composed of the active element Pb reacts with the acid and enters the solution, while the micron Cu particles that are difficult to react with the acid are gradually separated and dispersed.
- the obtained micron Cu particles are separated from the solution, washed and dried to obtain micron Cu particle powder with a particle size of 1 ⁇ m-50 ⁇ m.
- This embodiment provides a method for preparing nano Cu powder, which includes the following steps:
- the microstructure includes a matrix phase composed of Pb and a dispersed particle phase composed of nano-Cu particles. Among them, the particle size of the dispersed particle phase is 2 nm to 200 nm.
- 0.2 g of the Pb 80 Cu 20 initial alloy fragments prepared above were immersed in 200 mL of a 0.5 mol/L hydrochloric acid aqueous solution for reaction.
- the matrix phase composed of the active element Pb reacts with the acid and enters the solution, while the nano Cu particles that are difficult to react with the acid are gradually separated and dispersed.
- the obtained nano Cu particles are separated from the solution, washed and dried to obtain nano Cu particle powder with a particle size of 2 nm to 200 nm.
- This embodiment provides a method for preparing nano B powder, which includes the following steps:
- the initial alloy with the formula molecular formula of Zn 80 B 20 weigh the raw materials according to the formula, and obtain the initial alloy melt with the composition of Zn 80 B 20 by vacuum induction smelting.
- the initial alloy melt is rapidly solidified by the copper roller spin strip.
- the Zn 80 B 20 thin ribbon-shaped initial alloy fragments with a thickness of 25 ⁇ m are prepared at a rate of 10 5 K/s.
- the microstructure includes a matrix phase composed of Zn and a dispersed particle phase composed of nano-B particles. The dispersed particles The particle size of the phase is 2nm-100nm.
- the Zn 80 B 20 initial alloy fragments prepared above were immersed in a hydrochloric acid aqueous solution with a concentration of 2 mol/L for reaction.
- the matrix phase composed of Zn reacts with hydrochloric acid and enters the solution, while the nano-B particles that do not react with the aqueous hydrochloric acid solution are gradually separated and dispersed.
- the obtained nano-B particles are separated from the solution, washed and dried to obtain nano-B particles powder with a particle size of 2nm-100nm.
- This embodiment provides a method for preparing submicron B powder, which includes the following steps:
- the initial alloy with the formula molecular formula of Zn 80 B 20 weigh the raw materials according to the formula, and obtain the initial alloy melt with the composition of Zn 80 B 20 by vacuum induction smelting.
- the initial alloy melt is rapidly solidified by the copper roller spin strip.
- the Zn 80 B 20 thin strip-shaped initial alloy fragments with a thickness of 200 ⁇ m are prepared at a rate of 10 3 K/s to 10 4 K/s.
- the microstructure includes a matrix phase composed of Zn and a dispersion composed of submicron B particles.
- the particle phase, wherein the particle size of the dispersed particle phase is 100 nm to 2 ⁇ m.
- the Zn 80 B 20 initial alloy fragments prepared above were immersed in a NaOH aqueous solution with a concentration of 5 mol/L for reaction.
- the matrix phase composed of the active element Zn reacts with the base and enters the solution, while the submicron B particles that do not react with the base are gradually separated and dispersed.
- the obtained sub-micron B particles are separated from the solution, washed and dried to obtain sub-micron B particle powder, the size of which is 100 nm to 2 ⁇ m.
- This embodiment provides a method for preparing nano B powder, which includes the following steps:
- the initial alloy with the formula molecular formula of Zn 80 B 20 weigh the raw materials according to the formula, and obtain the initial alloy melt with the composition of Zn 80 B 20 by vacuum induction smelting.
- the initial alloy melt is rapidly solidified by the copper roller spin strip.
- the Zn 80 B 20 thin ribbon-shaped initial alloy fragments with a thickness of 25 ⁇ m are prepared at a rate of 10 5 K/s.
- the microstructure includes a matrix phase composed of Zn and a dispersed particle phase composed of nano-B particles. The dispersed particles The particle size of the phase is 2nm-100nm.
- the Zn 80 B 20 initial alloy fragments prepared above are put into a vacuum tube, the vacuum degree in the vacuum tube is kept below 5 Pa, and the vacuum tube is placed in a tube furnace at a temperature of 400°C. During the heating process, the matrix phase composed of Zn in the alloy continues to volatilize and re-condenses in other lower temperature areas in the vacuum tube, while the non-volatile nano-B particles are gradually separated and dispersed. After 30 minutes, the nano-B particle powder is obtained, the particle size of which is 2nm-100nm.
- This embodiment provides a method for preparing nano Cr powder, which includes the following steps:
- the initial alloy with the formula of Zn 85 Cr 15 is selected, the raw materials are weighed according to the formula , and the initial alloy melt with the composition of Zn 85 Cr 15 is obtained by vacuum induction smelting, and the initial alloy melt is rapidly solidified by a copper roller spin strip
- the Zn 85 Cr 15 thin ribbon-shaped initial alloy fragments with a thickness of 25 ⁇ m are prepared at a rate of 10 5 K/s.
- the microstructure includes a matrix phase composed of Zn and a dispersed particle phase composed of nano-Cr particles. Among them, the dispersed particles The particle size of the phase is 2nm-100nm.
- the Zn 85 Cr 15 initial alloy fragments prepared above were immersed in a hydrochloric acid aqueous solution with a concentration of 1 mol/L for reaction.
- the matrix phase composed of Zn reacts with hydrochloric acid and enters the solution, while the nano-Cr particles that do not react with the dilute hydrochloric acid aqueous solution are gradually separated and dispersed.
- the obtained nano-B particles are separated from the solution, washed and dried to obtain nano-B particles powder, the particle size of which is 2nm-100nm.
- This embodiment provides a method for preparing micron Cr powder, which includes the following steps:
- the initial alloy with the formula molecular formula Zn 85 Cr 15 is selected, the raw materials are weighed according to the formula , and the initial alloy melt with the composition of Zn 85 Cr 15 is obtained by vacuum induction melting.
- the initial alloy melt is casted at a rate of 300K/s.
- a Zn 85 Cr 15 thin plate with a thickness of 2 mm was prepared, and its microstructure included a matrix phase composed of Zn and a dispersed particle phase composed of micron Cr dendritic particles. Among them, the particle size of the dispersed particle phase is 0.5 ⁇ m-30 ⁇ m.
- the Zn 85 Cr 15 initial alloy sheet prepared above was immersed in a hydrochloric acid aqueous solution with a concentration of 1 mol/L for reaction.
- the matrix phase composed of Zn reacts with hydrochloric acid and enters the solution, while the micron Cr particles that do not react with the dilute hydrochloric acid aqueous solution are gradually separated and dispersed.
- the obtained micron Cr particles are separated from the solution, washed and dried to obtain micron Cr particle powder, the particle size of which is 0.5 ⁇ m-30 ⁇ m.
- This embodiment provides a method for preparing spherical micron Cr powder, which includes the following steps:
- the initial alloy with the formula molecular formula Zn 85 Cr 15 is selected, the raw materials are weighed according to the formula , and the initial alloy melt with the composition of Zn 85 Cr 15 is obtained by vacuum induction melting.
- the initial alloy melt is casted at a rate of 300K/s.
- a Zn 85 Cr 15 thin plate with a thickness of 2 mm was prepared, and its microstructure included a matrix phase composed of Zn and a dispersed particle phase composed of micron Cr dendritic particles. Among them, the particle size of the dispersed particle phase is 0.5 ⁇ m-30 ⁇ m.
- the Zn 85 Cr 15 initial alloy sheet prepared above was immersed in a hydrochloric acid aqueous solution with a concentration of 1 mol/L for reaction.
- the matrix phase composed of Zn reacts with hydrochloric acid and enters the solution, while the micron Cr particles that do not react with the dilute hydrochloric acid aqueous solution are gradually separated and dispersed.
- the obtained micron Cr particles are separated from the solution, washed and dried to obtain micron Cr particle powder, the particle size of which is 0.5 ⁇ m-30 ⁇ m.
- micron Cr powder After the prepared micron Cr powder is sieved, through mature plasma spheroidization treatment technology, spherical micron Cr powder with a particle size range of 5 ⁇ m to 30 ⁇ m is further prepared.
- This embodiment provides a method for preparing submicron V powder, which includes the following steps:
- the initial alloy with the formula of Zn 85 V 15 is selected, the raw materials are weighed according to the formula , and the initial alloy melt with the composition of Zn 85 V 15 is obtained by vacuum induction smelting, and the initial alloy melt is rapidly solidified by a copper roller spin strip.
- the Zn 85 V 15 thin ribbon-shaped initial alloy fragments with a thickness of 200 ⁇ m are prepared at a rate of 10 3 K/s to 10 4 K/s.
- the microstructure includes a matrix phase composed of Zn and a dispersion composed of submicron V particles.
- the particle phase wherein the particle size of the dispersed particle phase is 100 nm to 2 ⁇ m.
- the Zn 85 V 15 initial alloy fragments prepared above were immersed in a NaOH aqueous solution with a concentration of 5 mol/L for reaction.
- the matrix phase composed of the active element Zn reacts with the base and enters the solution, while the submicron V particles that do not react with the base are gradually separated and dispersed.
- the obtained sub-micron V particles are separated from the solution, washed and dried to obtain sub-micron V particle powder with a size of 100 nm to 2 ⁇ m.
- This embodiment provides a method for preparing nano-Mn powder, which includes the following steps:
- the initial alloy with the formula of Mg 85 Mn 15 is selected, the raw materials are weighed according to the formula , and the initial alloy melt with the composition of Mg 85 Mn 15 is obtained by vacuum induction smelting, and the initial alloy melt is rapidly solidified by a copper roller spin strip
- the Mg 85 Mn 15 thin ribbon-shaped initial alloy fragments with a thickness of 20 ⁇ m are prepared at a rate of 10 6 K/s.
- the microstructure includes a matrix phase composed of Mg and a dispersed particle phase composed of nano-Mn particles. Among them, the dispersed particles The particle size of the phase is 2nm-100nm.
- the Mg 85 Mn 15 initial alloy fragments prepared above are put into a vacuum tube, the vacuum degree in the vacuum tube is kept below 0.1 Pa, and the vacuum tube is placed in a tube furnace at a temperature of 600°C. During the heating process, the matrix phase composed of Mg in the alloy continues to volatilize and re-condenses in other lower temperature areas in the vacuum tube, while the non-volatile nano-Mn particles are gradually separated and dispersed. After 0.5h, the nano-Mn particle powder is obtained, the particle size of which is 2nm-100nm.
- This embodiment provides a method for preparing nano FeMn powder, which includes the following steps:
- the method of coagulation prepares the initial alloy fragments of Mg 80 Fe 10 Mn 10 with a thickness of 20 ⁇ m at a rate of 10 6 K/s into thin ribbon-like initial alloy fragments.
- the microstructure includes a matrix phase composed of Mg and a dispersed particle phase composed of nano-FeMn particles. , Wherein the particle size of the dispersed particle phase is 2nm-100nm.
- the Mg 80 Fe 10 Mn 10 initial alloy fragments prepared above are put into a vacuum tube, the vacuum degree in the vacuum tube is kept below 0.1 Pa, and the vacuum tube is placed in a tube furnace at a temperature of 600°C. During the heating process, the matrix phase composed of Mg in the alloy continues to volatilize and re-condenses in other lower temperature areas in the vacuum tube, while the non-volatile nano FeMn particles are gradually separated and dispersed. After 0.5h, nano-FeMn particle powder is obtained, the particle size of which is 2nm-100nm.
- This embodiment provides a method for preparing nano Si powder, which includes the following steps:
- the initial alloy whose formula is Zn 80 Si 20 is selected, the raw materials are weighed according to the formula, and the initial alloy melt with the composition of Zn 80 Si 20 is obtained by vacuum induction melting.
- the initial alloy melt is prepared by the method of rapid solidification by copper roll spinning at a cooling rate of 10 6 K/s into a thin ribbon-like initial alloy fragment of Zn 80 Si 20 with a thickness of 20 ⁇ m.
- the microstructure includes a matrix composed of Zn.
- the phase and the dispersed particle phase composed of nano Si particles, wherein the particle size of the dispersed particle phase is 5 nm to 300 nm.
- the Zn 80 Si 20 initial alloy fragments prepared above were immersed in a NaOH aqueous solution with a concentration of 10 mol/L for reaction.
- the matrix phase composed of the active element Zn reacts with the alkali and enters the solution, while the nano Si particles that do not react with the alkali solution are gradually separated and dispersed.
- the obtained nearly spherical nano Si particles are separated from the solution, washed and dried to obtain nano Si particle powder, and the particle size of the Si particles is 5 nm to 300 nm.
- This embodiment provides a method for preparing submicron Si powder, which includes the following steps:
- the initial alloy whose formula is Sn 80 Si 20 is selected, the raw materials are weighed according to the formula, and the initial alloy melt with the composition of Sn 80 Si 20 is obtained by vacuum induction melting.
- the initial alloy melt is prepared into Sn 80 Si 20 thin ribbon-like initial alloy fragments with a thickness of 150 ⁇ m by a method of rapid solidification by a copper roll spinning strip at a cooling rate of 10 3 K/s to 10 4 K/s.
- the microstructure is It includes a matrix phase composed of Sn and a dispersed particle phase composed of submicron Si particles, wherein the particle size of the dispersed particle phase is 20nm-2 ⁇ m.
- the Sn 80 Si 20 initial alloy fragments prepared above were immersed in an aqueous solution of nitric acid with a concentration of 0.5 mol/L for reaction.
- the matrix phase composed of the active element Sn reacts with the acid and enters the solution, while the submicron Si particles that do not react with the acid are gradually separated and dispersed.
- the obtained sub-micron Si particles are separated from the solution, washed and dried to obtain sub-micron Si particle powder, the particle size of the Si particles is 20nm-2 ⁇ m.
- This embodiment provides a method for preparing micron Ge powder, which includes the following steps:
- the initial alloy whose formula is Sn 75 Ge 25 is selected, the raw materials are weighed according to the formula, and the initial alloy melt with the composition of Sn 75 Ge 25 is obtained by vacuum induction melting.
- the initial alloy melt is solidified at a solidification rate of 100K/s to obtain an initial alloy of Sn 75 Ge 25.
- Its microstructure includes a matrix phase composed of Sn and a dispersed particle phase composed of micron Ge particles. The particle size is 2 ⁇ m ⁇ 120 ⁇ m.
- the Sn 75 Ge 25 initial alloy prepared above was immersed in a hydrochloric acid aqueous solution with a concentration of 1 mol/L for reaction. During the reaction, the matrix phase composed of the active element Sn reacts with the acid and enters the solution, while the dispersed Ge particles with poor activity break out. After 20 minutes, the obtained Ge particles are separated from the solution, washed and dried to obtain micron Ge particle powder, and the particle size of the Ge particles is 2 ⁇ m to 120 ⁇ m.
- This embodiment provides a method for preparing nano Si-Ge powder, which includes the following steps:
- the initial alloy whose formula is Zn 80 Si 10 Ge 10 is selected, the raw materials are weighed according to the formula, and the initial alloy melt with the composition of Zn 80 Si 10 Ge 10 is obtained by vacuum induction melting.
- the initial copper alloy melt by the method of melt spinning roller quick-setting cold 10 6 K / s speed to prepare a Zn 80 Si 10 Ge 10 alloy ribbon-shaped fragments of the initial thickness of 20 ⁇ m, which comprises a microstructure consisting of Zn
- the Zn 80 Si 10 Ge 10 initial alloy fragments prepared above were immersed in a hydrochloric acid aqueous solution with a concentration of 1 mol/L for reaction.
- the matrix phase composed of the active element Zn reacts with the acid and enters the solution, while the nano Si-Ge particles that do not react with the acid solution are gradually separated and dispersed.
- the obtained nearly spherical nano Si-Ge particles are separated from the solution, washed and dried to obtain nano Si-Ge particle powder, and the Si-Ge particles have a particle size of 5 nm to 300 nm.
- This embodiment provides a method for preparing sub-micron-micron Fe powder.
- the preparation method includes the following steps:
- La raw materials with atomic percentage content of T including O, H, N, P, S, F, Cl, Br, I
- impurity elements 1 at.% and 2.5 at.%
- La:Fe molar ratio of about 2:1 each alloy raw material is melted to obtain a uniform initial alloy melt with the composition of the atomic percentage mainly La 65.3 Fe 32.7 T 2.
- the initial alloy melt is prepared into a La 65.3 Fe 32.7 T 2 alloy strip with a thickness of 100 ⁇ m at a solidification rate of about -10 4 K/s through a copper roll spinning technique.
- the solidified structure of the alloy strip is composed of a matrix phase whose atomic percentage composition is mainly La 97.2 T 2.8 and a large amount of dispersed grain phase whose composition is mainly Fe 99.7 T 0.3.
- the shape of Fe 99.7 T 0.3 dispersed particles is nearly spherical or dendritic, and the particle size ranges from 500 nm to 3 ⁇ m.
- the volume percentage of Fe 99.7 T 0.3 dispersed particles in the alloy strip is about 14%;
- the La 97.2 T 2.8 matrix phase in the alloy strip is removed by the dilute acid solution , and the Fe 99.7 T 0.3 dispersed particles are quickly separated from the dilute acid solution by the magnetism of Fe , and the main component of Fe 99.7 T 0.3 is obtained.
- the submicron-micron powder has a particle size ranging from 500nm to 3 ⁇ m, and the total content of O, H, N, P, S, F, Cl, Br, and I contained in it is 0.3 at.%.
- the prepared sub-micron-micron Fe powder can be used for magnetic materials.
- This embodiment provides a method for preparing nano Fe powder, which includes the following steps:
- La raw materials with atomic percentage content of T including O, H, N, P, S, F, Cl, Br, I
- impurity elements 1 at.% and 2.5 at.%
- La:Fe molar ratio of about 60:40, each alloy raw material is melted to obtain a uniform initial alloy melt with an atomic percentage composition mainly of La 58.5 Fe 39.6 T 1.9.
- the initial alloy melt is prepared into a La 58.5 Fe 39.6 T 1.9 alloy strip with a thickness of -20 ⁇ m at a solidification rate of about -10 6 K/s through the copper roll spinning technique.
- the solidified structure of the alloy strip is composed of a matrix phase whose atomic percentage composition is mainly La 97 T 3 and a large amount of dispersed grain phase whose composition is mainly Fe 99.75 T 0.25.
- the shape of Fe 99.75 T 0.25 dispersed particles is nearly spherical, and the particle size ranges from 20 nm to 200 nm.
- the volume percentage of Fe 99.75 T 0.25 dispersed particles in the alloy strip is about 17.5%;
- the Fe particles are separated from the oxides after La pulverization to obtain nano-Fe particles with a particle size ranging from 20nm to 200nm, and nano-Fe
- the total content of O, H, N, P, S, F, Cl, Br, and I in the powder is 0.25 at.%.
- This embodiment provides a method for preparing nano Fe powder, which includes the following steps:
- La raw materials with atomic percentage content of T including O, H, N, P, S, F, Cl, Br, I
- impurity elements 1 at.% and 2.5 at.%
- the La raw material also contains 1 at.% Ce
- the Fe raw material also contains 0.5 at.% Mn.
- each alloy raw material is melted to obtain a uniform initial alloy melt with an atomic percentage composition mainly of (La 99 Ce 1 ) 58.5 (Fe 99.5 Mn 0.5 ) 39.6 T 1.9.
- the initial alloy melt is prepared into a (La 99 Ce 1 ) 58.5 (Fe 99.5 Mn 0.5 ) 39.6 T 1.9 alloy strip with a thickness of -20 ⁇ m at a solidification rate of about -10 6 K/s through a copper roll spinning technique.
- the solidified structure of the alloy strip is composed of a matrix phase whose main composition is (La 99 Ce 1 ) 97 T 3 in atomic percentage and a large amount of dispersed grain phase whose main composition is (Fe 99.5 Mn 0.5 ) 99.75 T 0.25.
- the (Fe 99.5 Mn 0.5 ) 99.75 T 0.25 dispersive particles are nearly spherical in shape, and their particle size ranges from 20 nm to 200 nm.
- the volume percentage of dispersed particles in the alloy strip is about 17.5%; moreover, the introduction of Mn and Ce in the alloy melt did not result in the formation of La, The intermetallic compound composed of Ce, Fe and Mn; and does not affect the structural characteristics of the matrix phase and the dispersed particle phase in the alloy strip, nor does it affect the rule of reducing the impurity content in the dispersed particle phase.
- the (Fe 99.5 Mn 0.5 ) 99.75 T 0.25 particles are separated from the pulverized oxides of La to obtain nanometer (Fe 99.5 Mn 0.5 ) 99.75 T 0.25 particles, the particle size range is 20nm ⁇ 200nm, and the total content of O, H, N, P, S, F, Cl, Br, I in nanometer (Fe 99.5 Mn 0.5 ) 99.75 T 0.25 powder is 0.25at .%.
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- Processes Of Treating Macromolecular Substances (AREA)
Abstract
一种粉末材料的制备方法及应用，所述制备方法通过合金熔体的凝固获得含有基体相与弥散颗粒相的初始合金条带，再将所述初始合金条带中的基体相去除，并同时保留弥散颗粒相，从而得到由原弥散颗粒相组成的粉末材料，该制备方法工艺简单，可以制备包括纳米级、亚微米级、微米级的多种尺寸的粉末材料，在催化材料、粉末冶金、复合材料、吸波材料、杀菌材料、金属注射成型、3D打印、涂料等领域具有很好的应用前景。
Description
本发明涉及微纳米材料技术领域，特别是涉及一种粉体材料的制备方法及其应用。
微米、亚微米、纳米粒径的超细粉体材料的制备方法从物质的状态分有固相法、液相法和气相法。其中，固相法主要有机械粉碎法、超声波粉碎法、热分解法、爆炸法等，液相法主要有沉淀法、醇盐法、羰基法、喷雾热干燥法、冷冻干燥法、电解法、化学凝聚法等，气相法主要有气相反应法、等离子体法、高温等离子体法、蒸发法、化学气相沉积法等。
虽然超细粉体材料的制备方法有很多种，但每种方法都有一定的局限性。例如，液相法的缺点是产量低、成本高和工艺复杂等；机械法的缺点是在制取粉体材料后存在分级困难的问题，且产品的纯度、细度和形貌均难以保证；旋转电极法和气体雾化法是目前制备高性能金属及合金粉体的主要方法，但生产效率低，收得率不高，且能耗相对较大；气流磨法、氢化脱氢法适合大批量工业化生产，但对原料和合金的选择性较强。
此外，粉体材料的杂质含量，尤其是氧含量，对其性能具有极大的影响。目前，主要通过控制原料纯度与真空度的方法来控制金属或合金的杂质含量，成本高昂。因此，开发新的高纯粉体材料的制备方法，具有重要的意义。
发明内容
基于此，有必要针对上述问题，提供一种工艺简单、易于操作的粉体材料的制备方法。
一种粉体材料的制备方法，包括：
步骤S1，选择初始合金原料，按照初始合金成分配比将初始合金原料熔化，得到含有杂质元素T的均匀初始合金熔体，其中，T包含O、H、N、P、S、F、Cl、I、Br中的至少一种，且所述初始合金熔体的平均成分为A
aM
bT
d，其中，A包含Zn、Mg、Sn、Pb、Ga、In、Al、La、Ge、Cu、K、Na、Li中的至少一种，M包含B、Bi、Fe、Ni、Cu、Ag、Cr、V、Si、Ge中的至少一种，其中a、b、d代表对应组成元素的原子百分比含量，且60％≤a≤99.5％，0.5％≤b≤40％，0≤d≤10％；
步骤S2，将所述初始合金熔体凝固成初始合金条带；所述初始合金条带的凝固组织包括基体相和弥散颗粒相；所述基体相的熔点低于所述弥散颗粒相，所述弥散颗粒相被包覆于所述基体相中；所述初始合金熔体凝固过程中，初始合金熔体中的杂质元素T在弥散颗粒相与基体相中重新分配，并富集于所述基体相中，从而使所述弥散颗粒相得到纯化；
所述初始合金条带中弥散颗粒相的成分主要为M
x1T
z1，基体相的平均成分主要为A
x2T
z2；且98.5％≤x1≤100％,0≤z1≤1.5％；80％≤x2≤100％,0≤z2≤20％；z1≤d≤z2，2z1≤z2；x1、z1、x2、z2分别代表对应组成元素的原子百分比含量；
步骤S3，将所述初始合金条带中的基体相去除，并保留基体相去除过程中不能被同时去除的弥散颗粒相，收集脱落出来的弥散颗粒相，即得到由原弥散颗粒组成的高纯目标粉体材料。
所述步骤S1中，
进一步地，A包含Sn、Pb、Ga、In、Al、La、Ge、Cu、K、Na、Li中的至少一种，M包含B、Bi、Fe、Ni、Cu、Ag中的至少一种；
作为优选，当M包含B时，A包含Sn、Ge、Cu中的至少一种；当M包含Bi时，A包含Sn、Ga、Al中的至少一种；当M包含Fe时，A包含La、In、Na、K、Li中的至少一种；当M包含Ni时，A包含Na、K、Li中的至少一种；当M包含Cu时，A包含Pb、Na、K、Li中的至少一种；当M包含Ag时，A包含Pb、Na、K中的至少一种。
进一步地，当M包含Si、Ge中的至少一种时，A包含Zn、Sn、Pb、Ga、In、Ag、Bi、Al中的至少一种；当M包含B、Cr、V中的至少一种时，A包含Zn；当M包含Fe时，A包含Mg；
进一步地，60％≤a<99.5％，0.5％≤b<40％，0<d≤10％；
进一步地，所述初始合金熔体中的T杂质元素来源包括：初始合金原料引入杂质，熔炼过程中气氛或坩埚引入杂质。其中，气氛引入杂质是指合金熔体吸收的环境气氛中的O、N、H等杂质。
进一步地，T为杂质元素且包含O、H、N、P、S、F、Cl、I、Br中的至少一种；且这些杂质元素的总含量即为T杂质元素的含量；
进一步地，如果原料是含有杂质元素的各单质或中间合金，则可将其按照配比熔化制备所述初始合金熔体。如果提供的原料直接为初始合金熔体成分对应合金原料时，则可以将其重熔得到初始合金熔体。
进一步地，所述初始合金原料包括含有杂质元素T的M-T原料。例如，当M为Fe，且T包含O时，M-T原料即包括含有O杂质的Fe-O原料。
进一步的，所述步骤S1中初始合金熔体平均成分中A与M的组合极为重要，其选择原则是确保合金熔体凝固过程中A与M之间不形成金属间化合物。这样就能实现初始合金熔体凝固过程中以A主的基体相和与M为的颗粒相的两相分离，有利于后续制备以M为主的粉体材料。
所述步骤S2中，
进一步地，所述初始合金条带中不含有包含A与M构成的金属间化合物；
进一步地，所述合金熔体凝固的方式包括甩带法、连铸法；一般来说，通过甩带法可以获得较薄的初始合金条带；通过连铸法可以获得较厚的合金条带。
不论是甩带法获得的薄合金条带，还是连铸法获得的厚合金条带，均与普通铸造法获得的合金铸锭形貌完全不同，普通铸造法获得的合金铸锭在尺度上一般没有明显的长度、宽度、厚度区别。
进一步地，所述初始合金条带的厚度范围为5μm～10mm；进一步地，所述初始合金条带的厚度范围为5μm～5mm；作为优选，所述初始合金条带的厚度范围为5μm～1mm；作为进一步优选，所述初始合金条带的厚度范围为5μm～200μm；作为进一步优选，所述初始合金条带的厚度范围为5μm～20μm。
需要说明的是，当初始合金条带的厚度为毫米级时，其也可以被称为合金薄板。
进一步地，所述初始合金条带横截面的宽度是其厚度的2倍以上；进一步地，所述初始合金条带的长度是其厚度的10倍以上；作为优选，所述初始合金条带的长度是其厚度的50倍以上；作为优选，所述初始合金条带的长度是其厚度的100倍以上；
进一步地，所述初始合金熔体凝固的速率为1K/s～10
7K/s；
进一步地，所述弥散颗粒相的颗粒大小与初始合金熔体的凝固速率有关；一般来说，弥散颗粒相的颗粒粒径大小与初始合金熔体的凝固速率成负相关的关系，即初始合金熔体的凝固速率越大，弥散颗粒相的颗粒粒径就越小。
进一步地，所述弥散颗粒相的颗粒粒径范围为2nm～3mm；进一步地，所述弥散颗粒相的粒径范围为2nm～500μm；作为优选，所述弥散颗粒相的粒径范围为2nm～99μm；作为进一步优选，所述弥散颗粒相的粒径范围为2nm～5μm；作为进一步优选，所述弥散颗粒相的粒径范围为2nm～200nm；作为进一步优选，所述弥散颗粒相的粒径范围为2nm～100nm。
进一步地，所述初始合金熔体凝固的速率为10
5K/s～10
7K/s时，可以获得粒径以纳米级尺度为主的弥散颗粒。
进一步地，所述初始合金熔体凝固的速率为10
4K/s～10
5K/s时，可以获得粒径以亚微米级尺度为主的弥散颗粒。
进一步地，所述初始合金熔体凝固的速率为10
2K/s～10
4K/s时，可以获得粒径以微米级尺度为主的弥散颗粒。
进一步地，所述初始合金熔体凝固的速率为1K/s～10
2K/s时，可以获得粒径以毫米级尺度为主的弥散颗粒。
进一步地，所述弥散颗粒相的颗粒形状不限，可包括枝晶形、球形、近球形、方块形、饼形、棒条形中的至少一种；当颗粒形状为棒条形时，颗粒的大小特指棒条横截面的直径尺寸。
进一步的，当弥散颗粒为纳米级或亚微米级尺度时，大概率获得球形或近球形颗粒；当弥散颗粒为微米级及以上尺度时，大概率获得枝晶形颗粒。
进一步地，所述弥散颗粒相从所述初始合金熔体中凝固析出，根据形核长大理论，无论是刚刚形核长大的近球形纳米颗粒，还是充分长大的微米级、毫米级树枝晶颗粒，其晶体生长都具有固定的取向关系，从而使得析出的单个颗粒均主要由一个单晶构成。
当所述弥散颗粒在整个初始合金条带中体积百分含量较高时，在单晶颗粒的内生析出过程中，不排除有两个或两个以上颗粒合并的情况。如果两个或两个以上单晶颗粒仅仅软团聚、相互吸附、或者仅少许部位接触连接在一起，没有像多晶材料那样通过正常晶界充分结合成一个颗粒，其仍然为两个单晶颗粒。其特点是，在后续过程去除基体相后，这些单晶颗粒可以轻易地通过包括超声分散处理、气流磨碎化等技术等分开。而正常的韧性金属或合金的多晶材料，则难以通过包括超声分散处理、气流磨碎化等技术将晶界分开。
作为优选，所述初始合金条带中弥散颗粒中的单晶颗粒数目在所有弥散颗粒数目中的占比不低于60％。
作为进一步优选，所述弥散颗粒中的单晶颗粒数目在所有弥散颗粒数目中的占比不低于90％。
进一步地，对于某一确定的初始合金条带来说，所述弥散颗粒相在该初始合金条带中的体积百分含量可以通过对应初始合金熔体成分、弥散颗粒相成分、基体相成分，结合元素原子量、密度参数等计算确定。
进一步地，所述弥散颗粒相在其对应的初始合金条带中的体积百分含量不高于50％。
进一步地，98.5％≤x1<100％,0<z1≤1.5％；80％≤x2<100％,0<z2≤20％；z1<d<z2，2z1<z2；
进一步地，所述弥散颗粒中的T杂质元素原子百分比含量z1小于M-T原料中的T杂质元素原子百分比含量。
进一步地，z1≤d≤z2，且2z1≤z2，
作为优选，z1≤d≤z2，且3z1≤z2，即所述弥散颗粒相中T杂质含量低于所述初始合金熔 体中的T杂质含量，且所述弥散颗粒相中T杂质含量的3倍仍然低于所述基体相中的T杂质含量；
本发明采用原子百分比含量来表达T杂质含量。通过元素的原子百分比含量来表征各元素的组成，可以通过物质的量的概念准确地表达元素含量的增减变化，比如杂质元素的增减与变化。如果采用元素的质量百分比含量(或ppm概念)来表征各个元素的含量，由于各元素原子量的不同，则容易产生错误的结论。举例来说，如原子百分比含量为Ti
45Gd
45O
10的合金，包含100个原子，O的原子百分比含量为10at％。将这100个原子分成Ti
45O
4(原子百分比组成为Ti
91.8O
8.2)与Gd
45O
6(原子百分比组成为Gd
88.2O
11.8)两部分，Gd
45O
6中氧的原子百分比含量增为11.8at％，Ti
45O
4中氧的原子百分比含量减为8.2at％，可以很准确地表达Gd中富集了O。但若采用O的质量百分比含量来衡量，Ti
45Gd
45O
10中O的质量百分比含量为1.70wt％，Ti
45O
4与Gd
45O
6中O的质量百分比含量分别为2.9wt.％与1.34wt.％，将会得出Ti
45O
4中O含量相比Gd
45O
6中O含量明显增加的错误结论。
进一步地，所述初始合金条带中成分主要为M
x1T
z1的弥散颗粒相中不含有A元素；
进一步地，所述初始合金条带中弥散颗粒相的成分为M
x1T
z1。
所述步骤S3中，
进一步地，所述将合金条带中基体相去除方法包括：酸反应去除、碱反应去除、真空挥发去除中的至少一种。
所述酸溶液与碱溶液的组成与浓度不做具体限定，只要能够保证去除基体相，同时保留弥散颗粒相即可。
所述真空处理的温度与真空度不做具体限定，只要能够保证去除基体相，同时保留弥散颗粒相即可。
进一步地，所述将初始合金条带中基体相去除方法包括基体相自然氧化-粉化剥落去除。
当基体相为极易与氧发生自然氧化的元素，如La等时，通过基体相的自然氧化-粉化过程，就可以将基体相与弥散颗粒相分开，再辅以其它技术手段，如磁选，就可以将诸如具有磁性的弥散颗粒相与基体相的自然氧化物分开。
进一步地，由于目标粉体材料为初始合金条带中脱落下来的弥散颗粒相，因此所述目标粉体材料的成分、颗粒粒径等均与对应的弥散颗粒相的成分、颗粒粒径相当。
进一步地，所述目标粉体材料的颗粒粒径范围为2nm～3mm；作为优选，所述目标粉体材料的颗粒粒径范围为2nm～500μm；作为优选，所述目标粉体材料的颗粒粒径范围为2nm～99μm；作为进一步优选，所述目标粉体材料的颗粒粒径范围为2nm～5μm；作为进一步优选，所述目标粉体材料的颗粒粒径范围为2nm～200nm；作为进一步优选，所述目标粉体材 料的颗粒粒径范围为2nm～100nm。
进一步地，初始合金条带与酸溶液反应后，弥散颗粒从初始合金条带中脱离出来，对其清洗、干燥，即得到目标粉体材料。
进一步的，所述主要成分为M
x1T
z1的目标粉体材料中不含有A元素；
进一步地，所述目标粉体材料的成分主要为M
x1T
z1；作为优选，所述目标粉体材料的成分为M
x1T
z1；
进一步地，所述目标粉体材料中的T杂质元素的原子百分比含量不超过1.5％；
进一步地，在所述步骤S3之后还进行以下步骤：将所述粉体材料筛分后，选择粒径范围为5μm～200μm的粉体材料进行等离子球化处理，以得到呈球形的粉体材料；
本发明还涉及上述制备方法得到的粉体材料或球形粉体材料在催化材料、粉末冶金、复合材料、吸波材料、杀菌材料、金属注射成型、3D打印、涂料中的应用。
进一步地，如上述制备方法得到的球形粉体材料在金属粉3D打印领域中的应用，其特征在于，球形粉体材料的粒径范围为10μm～200μm。
进一步地，如上述制备方法得到的粉体材料在金属注射成型、粉末冶金中的应用，其特征在于，粉体材料的粒径范围为0.1μm～200μm。
进一步地，如上述制备方法得到的粉体材料在涂料中的应用，其特征在于，粉体材料的粒径范围为2nm～5μm。
本发明还涉及一种合金条带，其特征在于，包含内生粉与包覆体；所述合金条带的凝固组织包括基体相和弥散颗粒相，基体相即为所述包覆体，弥散颗粒相即为所述内生粉；所述包覆体的熔点低于所述内生粉，所述内生粉被包覆于所述包覆体中；
所述合金条带中内生粉的成分主要为M
x1T
z1，包覆体的平均成分主要为A
x2T
z2；且98.5％≤x1≤100％,0≤z1≤1.5％；80％≤x2≤100％,0≤z2≤20％；z1≤d≤z2，2z1≤z2；x1、z1、x2、z2分别代表对应组成元素的原子百分比含量；其中，A包含Sn、Pb、Ga、In、Al、La、Ge、Cu、K、Na、Li中的至少一种，M包含B、Bi、Fe、Ni、Cu、Ag中的至少一种；
作为优选，当M包含B时，A包含Sn、Ge、Cu中的至少一种；当M包含Bi时，A包含Sn、Ga、Al中的至少一种；当M包含Fe时，A包含La、In、Na、K、Li中的至少一种；当M包含Ni时，A包含Na、K、Li中的至少一种；当M包含Cu时，A包含Pb、Na、K、Li中的至少一种；当M包含Ag时，A包含Pb、Na、K中的至少一种；
进一步地，当M包含Si、Ge中的至少一种时，A包含Zn、Sn、Pb、Ga、In、Ag、Bi、Al中的至少一种；当M包含B、Cr、V中的至少一种时，A包含Zn；当M包含Fe时，A 包含Mg；
进一步地，所述合金条带中主要成分为M
x1T
z1的内生粉中不含有A元素；
作为优选，所述合金条带中的内生粉的成分为M
x1T
z1，包覆体的平均成分为A
x2T
z2；
进一步地，所述合金条带的厚度范围为5μm～10mm；作为优选，所述合金条带的厚度范围为5μm～5mm；作为优选，所述合金条带的厚度范围为5μm～1mm；作为进一步优选，所述合金条带的厚度范围为5μm～200μm；作为进一步优选，所述合金条带的厚度范围为5μm～20μm。
进一步地，所述合金条带横截面的宽度是其厚度的2倍以上；进一步地，所述初始合金条带的长度是其厚度的10倍以上；作为优选，所述初始合金条带的长度是其厚度的50倍以上；作为优选，所述初始合金条带的长度是其厚度的100倍以上。
进一步地，所述内生粉的粒径范围为2nm～3mm；作为优选，所述内生粉的粒径范围为2nm～500μm；作为优选，所述内生粉的粒径范围为2nm～99μm；作为进一步优选，所述内生粉的粒径范围为2nm～10μm；作为进一步优选，所述内生粉的粒径范围为2nm～1μm；作为进一步优选，所述内生粉的粒径范围为2nm～200nm；作为进一步优选，所述内生粉的粒径范围为2nm～100nm。
进一步地，所述内生粉的形状包括枝晶形、球形、近球形、方块形、饼形、棒条形中的至少一种。
进一步地，所述合金条带中内生粉中的单晶颗粒数目在所有内生粉数目中的占比不低于60％。
进一步地，所述内生粉在所述合金条带中的体积百分含量不超过50％。
进一步地，98.5％≤x1<100％,0<z1≤1.5％；80％≤x2<100％,0<z2≤20％；z1<d<z2，2z1<z2；
进一步地，2z2≤z1，且0≤z2≤1.5％；
作为优选，3z2<z1，且0<z2≤1.5％；
作为进一步优选，3z2<z1，且0<z2≤0.75％。
需要说明的是，本发明所述方案中所述A、M或者T中还可以含有上述所列元素之外的其它元素或杂质元素。只要这些元素的引入或者含量的变化不引起初始合金凝固过程与规律发生“质变”的结果，都不影响本发明上述技术方案的实现。
具体来说，所述初始合金凝固过程与规律不发生“质变”的结果，是指所述A、M或者T中含有上述所列元素之外的其它元素或杂质元素时，下述1)-3)所列事实过程与规律仍然存在：
1)所述初始合金条带中不含有主要由A与M构成的金属间化合物；
2)所述初始合金条带的凝固组织包括基体相和弥散颗粒相；所述基体相的熔点低于所述弥散颗粒相，所述弥散颗粒相被包覆于所述基体相中；
3)当初始合金熔体中T杂质含量不为0时，所述弥散颗粒相中T杂质含量低于所述初始合金熔体中的T杂质含量，且所述弥散颗粒相中T杂质含量的2倍仍然低于所述基体相中的T杂质含量。
本发明所述技术方案具有以下有益效果：
首先，通过巧妙的合金设计，使得初始合金熔体凝固的时候发生相的分离，使得一定粒径目标成分的内生颗粒可以在初始合金熔体凝固过程中形成，并可以通过后续过程分离。一般来说，通过自下而上的化学方法，如化学还原，可以比较容易地制备纳米金属颗粒，但当颗粒的尺度增加到数百纳米甚至微米级时，则难以制备。通过自上而下的物理方法，如雾化法、球磨法等，可以比较容易地制备数十微米或者数百微米的金属颗粒，但当颗粒的尺度降低到数百纳米到几个微米时，则也很难制备。本发明的技术方案可以根据初始合金条带凝固过程中冷速的不同，非常容易地制备纳米级，亚微米级、微米级、甚至毫米级的目标金属粉颗粒，突破了上述技术难点，具有极大地优势。
其次，实现了通过低纯原料获得高纯目标粉体材料，并为低纯原料制备高纯粉体材料指出了一条新的途径，具有积极意义。本发明目标粉体材料纯度的提高主要通过以下三个机制实现：1)高活性的基体主元素(如La、Mg等元素)对初始合金熔体杂质元素的“吸收”作用。由于基体元素一般为高活性，低熔点的元素，在合金熔体熔化及凝固过程中其与杂质元素T之间具有极强的亲和力，这可以使得初始合金熔体中的杂质元素T要么更多地进入主要由基体相主元素组成的基体相中，要么在熔体状态时与基体主元素形成熔渣，并与合金熔体分离去除；2)内生析出的弥散颗粒相形核长大过程中，杂质元素T会被排入剩余熔体中。只要凝固过程中内生析出的弥散颗粒相不晚于基体相析出，其杂质都会富集于最后凝固的那部分熔体，即主要由基体相主元素组成并凝固形成基体相的那部分熔体。3)由于第二相基体的存在，熔炼过程中由于坩埚与熔体相互作用从而进入熔体的与坩埚相关的杂质也一般集中在第二相基体中，这就进一步地保证了目标粉体材料的纯度，并使得熔炼过程中对坩埚的要求进一步降低，极大地降低了生产成本。
第三，可以获得以单晶颗粒为主的目标金属粉。相比多晶粉体，单晶粉体可以获得诸多显著且有益效果。在所述初始合金熔体凝固过程中，每一个内生弥散颗粒都是从熔体中某个位置形核后按照特定的原子排列方式长大生成。通过控制弥散颗粒相在初始合金条带中的体积百分含量不超过50％，确保每个内生颗粒可以弥散分布的情况下，各个内生颗粒之间难以 发生合并长大。因此，最终获得的各个弥散分布的颗粒相大多都是单晶相。即使尺度大到数十微米或毫米级的枝晶颗粒，其每个次级枝晶的生长方向都与主枝晶的生长方向保持一定的位相关系，其仍然属于单晶颗粒。对于多晶材料来说，其晶界一般容易含有凝固过程中从晶内排出来的杂质元素，因此很难获得高纯的多晶粉体材料。而当目标金属粉主要由单晶颗粒组成时，其纯度必然能得到保障。而且，单晶颗粒表面原子具有特定的排列方式，如(111)面排列等，这些特定的排列方式会赋予目标金属粉特殊的力学、物理、化学性能，从而产生有益的效果。
第四，所述由内生粉与包覆体(基体相)构成的合金条带，创造性地利用原位生成的基体相包裹内生粉，保持了内生粉的高纯度与高活性。具体来说，无论传统化学方法还是物理方法所制备的金属或合金粉，尤其是比表面积极大的纳米粉，极易自然氧化，都面临粉体的保存困难问题。针对这一问题，本发明所涉及技术方案在制备出由内生金属粉与包覆体(基体相)构成的合金条带之后，可以并不急于将包覆体去除，而是直接利用包覆体保护内生金属粉不被自然氧化。这种由内生金属粉与包覆体构成的合金条带可以直接作为下游生产的原料，因此有成为一类特殊产品的潜力。当下游生产需要使用高纯粉体时，可以根据下一工序的特点，选择合适的时机并在合适的环境下将内生金属粉从合金条带中的包覆体中释放，再在尽可能短的时间使释放出来的内生粉进入下一生产流程，从而使内生金属粉受到氧等杂质污染的机会大大减少。例如，当内生金属粉为纳米粉时，可以在内生金属粉从包覆体中释放的同时或者随后马上与树脂复合，从而制备具有高活性的内生金属粉添加的树脂基复合材料。
第五，所述步骤S2中通过凝固获得的固态合金为条带状，其保证了产品形状的均一性与大规模生产的可行性。当合金条带为薄合金条带时，可以通过甩带法制备，只要维持合金熔体流向旋转辊的流量固定，旋转辊的转速固定，就可以获得厚度均一的合金薄带，而且该制备过程可以连续进行，利于大规模生产。当合金条带为厚合金条带时，可以通过成熟的连铸法制备，连铸的原理与甩带法的原理相似，也可以通过熔体获得连续且厚度均一的厚带，制备过程也可以连续进行，利于大规模生产。当合金条带厚度均一时，冷速也较为均匀，获得弥散颗粒粒度也较为均匀。相比而言，如果凝固获得的固态合金为铸锭状时，根据常识，铸锭没有均一的厚度，也没有明显的长度及端点，一般会导致内部熔体散热困难，容易获得异常大的内生颗粒，只有单纯需要对大的内生颗粒进行收集并对其提纯的时候才需要这样操作。而且普通铸锭难以连续生产。因此，本发明通过凝固获得合金条带，适合后续通过“去相法”进行粉体材料的制备。
因此，本发明的制备方法具有工艺简单、易于操作、成本低的特点，可以制备包括纳米级、亚微米级、以及微米级的多种高纯粉体材料，在催化材料、粉末冶金、复合材料、吸波 材料、杀菌材料、磁性材料、金属注射成型、3D打印、涂料等领域具有很好的应用前景。
作为备选方案之一，本发明还提供一种粉末材料的制备方法，其包括以下步骤：
一种粉末材料的制备方法，包括：
S1，提供初始合金，所述初始合金的成分为A
aM
b，所述初始合金的微观组织由成分为A的基体相以及成分为M的弥散颗粒相组成，其中，A选自Sn、Pb、Ga、In、Al、La、Ge、Cu、K、Na、Li中的至少一种，M选自B、Bi、Fe、Ni、Cu、Ag中的至少一种，a、b代表对应组成元素的原子百分含量，且1％≤b≤40％，a+b＝100％；
S2，将所述初始合金与腐蚀液混合，使所述基体相与所述腐蚀液反应变成离子进入溶液，所述弥散颗粒相脱离出来，即得到成分为M的粉末材料。
步骤S1中，初始合金的成分有特定的元素配比及组成，原则是保证初始合金的微观组织由成分为A的基体相以及成分为M的弥散颗粒相组成，其中，金属元素A的化学活性高于元素M的化学活性。
为确保金属元素A和元素M能够更好的形成成分为A的基体相以及成分为M的弥散颗粒相，以进一步确保基体相与弥散颗粒相的分离。
具体地，当M为B时，A选自Sn、Ge、Cu中的至少一种；
具体地，当M为Bi时，A选自Sn、Ga、Al中的至少一种；
具体地，当M为Fe时，A选自La、In、Na、K、Li中的至少一种；
具体地，当M为Ni时，A选自Na、K、Li中的至少一种；
具体地，当M为Cu时，A选自Pb、Na、K、Li中的至少一种；
具体地，当M为Ag时，A选自Pb、Na、K中的至少一种。
在其中一个实施例中，所述初始合金通过以下方法得到：
按照配比称取原料并将所述原料熔化得到合金熔体；
将所述合金熔体凝固得到所述初始合金，其中，所述凝固的速率为1K/s～10
7K/s。
所述初始合金可以通过“合金熔体凝固+机械破碎”或“合金熔体速凝甩带”等方法制备。
具体地，在制备初始合金的过程中，成分为M的弥散颗粒相的颗粒大小与制备过程中合金熔体的凝固速率有关。一般来说，弥散颗粒相的粒径大小与合金熔体的凝固速率成负相关的关系，即：合金熔体的凝固速率越大，弥散颗粒相的粒径越小。所以，本发明在制备过程中，将原料熔炼得到的合金熔体凝固成初始合金的速率优选为1K/s～10
7K/s，获得的初始合金中弥散颗粒相的颗粒大小为2nm～500μm。
所述弥散颗粒相的颗粒形状不限，可包括枝晶形、球形、近球形、方块形、饼形、棒形 中的至少一种。需要说明的是，当颗粒形状为棒状时，颗粒的大小特指棒横截面的直径尺寸。
步骤S2中，当A选自Sn、Pb、Ga、In、Al、La、Ge、Cu中的至少一种时，所述腐蚀液为酸溶液，所述酸溶液中的酸包括盐酸、硫酸、硝酸、磷酸、醋酸、草酸中的至少一种。
当A选自Na、K、Li中的至少一种时，所述腐蚀液为水，且所述水经过除氧处理。
所述酸溶液中酸的浓度只要可与基体相反应并基本保留弥散颗粒相即可，该反应的温度和时间也不做限定。优选地，所述酸溶液中酸的摩尔浓度为0.01mol/L～20mol/L，该反应的反应时间可为0.1min～5h，反应温度可为0℃～100℃。
由于弥散颗粒相不与腐蚀液反应或仅轻微与腐蚀液反应，所以，最终形成的成分为M的粉末材料的颗粒大小与形貌与初始合金中弥散颗粒相的颗粒大小与形貌基本一致，其颗粒大小为2nm～500μm。
备选方案之一的制备方法中，通过选择化学活性较高的金属元素A和化学活性低于金属元素A的元素M制成成分为A
aM
b的初始合金，该初始合金的微观组织由成分为A的基体相和成分为M的弥散颗粒相组成，该组织结构有利于后续分离。具体来说，该种初始合金在与腐蚀液反应时，成分为A的基体相会与腐蚀液反应变成离子进入溶液，成分为M的弥散颗粒相不与腐蚀液反应或仅轻微与腐蚀液反应，从而从初始合金中脱离出来，即得到成分为M的粉末材料。
因此，备选方案之一的制备方法相对于传统的固相法、液相法和气相法而言，具有工艺简单、易于操作、成本低的特点，而且可以制备包括纳米级、亚微米级以及微米级的多种超细尺寸的粉末材料，在催化、粉末冶金、杀菌、3D打印等领域具有很好的应用前景。
作为备选方案之二，提供一类粉体材料的制备方法，其包括以下步骤：
本发明提供的一类粉体材料的制备方法，包括：
S1，选择成分为A
aM
b的初始合金，a、b代表对应组成元素的原子百分比含量，且0.1％≤b≤40％，a+b＝100％；
当M为Si、Ge中的至少一种时，A包含Zn、Sn、Pb、Ga、In、Ag、Bi、Al中的至少一种；
当M为B、Cr、V中的至少一种时，A为Zn；
当M为Fe、Mn中的至少一种时，A为Mg；
当M为C时，A包含Mg、Zn中的至少一种；
将所述初始合金充分熔化，得到初始合金熔体，在随后的冷却及凝固过程中，A与M之间不形成金属间化合物，而是发生A与M的分离，得到元素组成为M的弥散颗粒相分布于 A基体相中的凝固态合金；
S2，去除所述凝固态合金中的A基体相，使得不能被同时去除的弥散颗粒相得到保留并分散脱离出来，即得到成分为M的粉体材料。
步骤S1中，初始合金的成分有特定的元素配比及组成，原则是保证初始合金的凝固态合金由成分为A的基体相以及成分为M的弥散颗粒相组成。
具体地，在制备凝固态合金的过程中，成分为M的弥散颗粒相的颗粒大小与制备过程中初始合金熔体的凝固速率有关。一般来说，弥散颗粒相的粒径大小与初始合金熔体的凝固速率成负相关的关系，即：初始合金熔体的凝固速率越大，弥散颗粒相的粒径越小。所以，本发明在制备过程中，将原料熔炼得到的初始合金熔体凝固成凝固态合金的速率优选为1K/s～10
7K/s，获得凝固态合金中的弥散颗粒相的颗粒大小为2nm～500μm。
所述凝固态合金的厚度控制在10μm～50mm，并通过“合金熔体凝固+机械破碎”或“合金熔体速凝甩带”等方法尽量增加所得合金的反应面积，保证后续A基体相的顺利去除。
所述弥散颗粒相的颗粒形状不限，可包括枝晶形、球形、近球形、方块形、饼形、棒形中的至少一种。需要说明的是，当颗粒形状为棒状时，颗粒的大小特指棒横截面的直径尺寸。
步骤S2中，去除A基体相的方式为酸反应去除、碱反应去除、真空挥发去除等方式中的某一种。
所述酸反应除A基体的过程中，酸溶液中的酸包括盐酸、硫酸、硝酸、磷酸、醋酸、草酸中的至少一种，酸的摩尔浓度为0.1mol/L～15mol/L，反应时间为1min～1h，反应温度为0℃～100℃。
所述碱反应除A基体的过程中，碱溶液中的碱包括NaOH与KOH中的至少一种，碱的摩尔浓度为0.1mol/L～15mol/L，反应时间为1min～1h，反应温度为0℃～100℃。
所述真空挥发去除A基体的过程中，所述凝固态合金所处容器内的真空度小于10Pa，处理温度与A基体相的熔点T
m相关，其处理温度范围为T
m-1K～T
m-200K，处理时间为0.1h以上。
由于弥散颗粒相不与腐蚀液反应或不会被挥发去除，所以最终形成的成分为M的粉体材料的颗粒大小与形貌与凝固态合金中弥散颗粒相的颗粒大小与形貌基本一致，其颗粒大小为2nm～500μm。
进一步的，在步骤S2之后，还可进行以下步骤:将所得的M粉体材料进行筛分，并分别进行等离子球化处理，最终得到具有不同粒径且呈球形的M粉体材料。
该筛选之后的粉体材料通过等离子球化处理，可实现球化。
所述球形M粉体材料的粒径范围为1μm～500μm。
备选方案之二的制备方法中，A
aM
b凝固态合金的微观组织由成分为A的基体相和成分为M的弥散颗粒相组成，该组织结构有利于后续分离。具体来说，采用酸反应去除或碱反应去除时，成分为A的基体相会与腐蚀液反应变成离子进入溶液，成分为M的弥散颗粒相不与腐蚀液反应，从而从凝固态合金中脱离出来，即得到成分为M的粉体材料。采用真空挥发去除时，熔点较低的A基体相在接近熔点的时就具有很强的挥发性，而熔点更高的M弥散颗粒在该温度可以较好地保留。因此，A基体相挥发殆尽后，M弥散颗粒也会脱离出来，得到相应的粉体材料。
因此，备选方案之二发明的制备方法相对于传统的固相法、液相法和气相法而言，具有工艺简单、易于操作、成本低的特点，而且可以制备包括纳米级、亚微米级以及微米级的多种超细尺寸的粉体材料，在催化、粉末冶金、杀菌、粉末注射成型，3D打印等领域具有很好的应用前景。
以下，将通过以下具体实施例对所述粉末材料的制备方法做进一步的说明。
实施例1
本实施例提供一种纳米B粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为Cu
80B
20的合金，按照该配方称取原料，真空感应熔炼得到成分为Cu
80B
20的合金熔体，将该合金熔体通过铜辊甩带速凝的方法以～10
6K/s的速率制备成厚度为～15μm的Cu
80B
20薄带状初始合金碎片，其微观组织包括由Cu组成的基体相与由纳米B颗粒组成的弥散颗粒相，其中，弥散颗粒相的颗粒大小为2nm～100nm。
室温下，将0.25克上述制得的Cu
80B
20初始合金碎片没入50mL浓度为2mol/L，温度为60℃的盐酸水溶液中进行反应。反应过程中，由Cu组成的基体相与热的盐酸反应进入溶液，而不与盐酸水溶液反应的纳米B颗粒则逐步脱离分散出来。25min后，将所得的纳米B颗粒与溶液进行分离，经清洗干燥，即得纳米B颗粒粉末，其颗粒大小为2nm～100nm。
实施例2
本实施例提供一种亚微米B粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为Sn
98B
2的合金，按照该配方称取原料，真空感应熔炼得到成分为Sn
98B
2的合金熔体，将该合金熔体通过铜辊甩带速凝的方法以10
3K/s～10
4K/s的速率制备成厚度为150μm的Sn
98B
2薄带状初始合金碎片，其微观组织包括由Sn组成的基体相与由亚微米B颗粒组成的弥散颗粒相，其中，弥散颗粒相的颗粒大小为100nm～2μm。
室温下，将0.25克上述制得的Sn
98B
2初始合金碎片没入50mL浓度为0.5mol/L的硫酸水溶液中进行反应。反应过程中，由活性元素Sn组成的基体相与酸反应进入溶液，而不与酸反应的亚微米B颗粒则逐步脱离分散出来。20min后，将所得的亚微米B颗粒与溶液进行分离，经清洗干燥，即得亚微米B颗粒粉末，其大小为100nm～2μm。
实施例3
本实施例提供一种纳米Bi粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为Al
75B
i25的合金，按照该配方称取原料，真空感应熔炼得到成分为Al
75B
i25的合金熔体。将该合金熔体～10
6K/s的速率制备成厚度为～20μm的Al
75B
i25合金薄带，其微观组织包括由Al组成的基体相与由纳米Bi颗粒组成的弥散颗粒相，其中，弥散颗粒相的颗粒大小为2nm～150nm。
室温下，将0.5克上述制得的Al
75B
i25初始合金碎片没入50mL浓度为1mol/L的盐酸水溶液中进行反应。反应过程中，由活性元素Al组成的基体相与酸反应进入溶液，而不与酸反应的纳米Bi颗粒则逐步脱离分散出来。20min后，将所得的纳米Bi颗粒与溶液进行分离，经清洗干燥，即得纳米Bi颗粒粉末，其颗粒大小为2nm～150nm。
实施例4
本实施例提供一种亚微米Fe粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为La
75Fe
25的合金，按照该配方称取原料，真空感应熔炼得到成分为La
75Fe
25的合金熔体。将该合金熔体通过铜辊甩带速凝的方法以10
3K/s～10
4K/s的速率制备成厚度为150μm的La
75Fe
25薄带状初始合金碎片，其微观组织包括由La组成的基体相与由亚微米Fe颗粒组成的弥散颗粒相，其中，弥散颗粒相的颗粒大小为200nm～3μm。
室温下，将0.5克上述制得的La
75Fe
25初始合金碎片没入50mL浓度为0.01mol/L的盐酸水溶液中进行反应。反应过程中，由活性元素La组成的基体相与酸反应进入溶液，而活性稍差的弥散Fe颗粒则脱离出来。反应过程施加辅助磁场，可以保证刚刚分离出来的Fe颗粒与酸溶液及时分离。30min后，逐步收集的亚微米Fe颗粒，并清洗干燥，即得亚微米Fe颗粒粉末，Fe颗粒的颗粒大小为200nm～3μm。
实施例5
本实施例提供一种亚微米Fe粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为Li
75Fe
25的合金，按照该配方称取原料，真空感应熔炼得到成分为Li
75Fe
25的合金熔体。将该合金熔体通过铜辊甩带速凝的方法以10
3K/s～10
4K/s的速率制备成厚度为150μm的Li
75Fe
25薄带状初始合金碎片，其微观组织包括由Li组成的基体相与由亚微米Fe颗粒组成的弥散颗粒相，其中，弥散颗粒相的颗粒大小为200nm～3μm。
室温下，将0.5克上述制得的Li
75Fe
25初始合金碎片没入50mL水溶液中进行反应。反应过程中，由活性元素Li组成的基体相与水反应进入溶液，而弥散Fe颗粒则脱离出来。5min后，逐步收集的亚微米Fe颗粒，并清洗干燥，即得亚微米Fe颗粒粉末，其颗粒大小为200nm～3μm。
实施例6
本实施例提供一种纳米Fe粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为Li
75Fe
25的合金，按照该配方称取原料，真空感应熔炼得到成分为Li
75Fe
25的合金熔体。将该合金熔体通过铜辊甩带速凝的方法以～10
6K/s的速率制备成厚度为～15μm的Li
75Fe
25薄带状初始合金碎片，其微观组织包括由Li组成的基体相与由纳米Fe颗粒组成的弥散颗粒相，其中，弥散颗粒相的颗粒大小为2nm～200nm。
室温下，将0.25克上述制得的Li
75Fe
25初始合金碎片没入50mL已通过氩气除氧的水溶液中进行反应。反应过程中，由活性元素Li组成的基体相与水反应进入溶液，而弥散纳米Fe颗粒则脱离出来。5min后，将所得的纳米Fe颗粒与溶液进行分离，即得纳米Fe颗粒粉末，其颗粒大小为2nm～200nm。
实施例7
本实施例提供一种纳米Ni粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为Li
80Ni
20的合金，按照该配方称取原料，真空感应熔炼得到成分为Li
80Ni
20的合金熔体。将该合金熔体通过铜辊甩带速凝的方法以～10
6K/s的速率制备成厚度为～15μm的Li
80Ni
20薄带状初始合金碎片，其微观组织包括由Li组成的基体相与由纳米Ni颗粒组成的弥散颗粒相，其中，弥散颗粒相的颗粒大小为2nm～200nm。
室温下，将0.25克上述制得的Li
80Ni
20初始合金碎片没入50mL已通过氩气除氧的水溶液中进行反应。反应过程中，由活性元素Li组成的基体相与水反应进入溶液，而弥散纳米Ni颗粒则脱离出来。5min后，将所得的纳米Ni颗粒与溶液进行分离，即得纳米Ni颗粒粉末，其颗粒大小为2nm～200nm。
实施例8
本实施例提供一种纳米Ag粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为Pb
75Ag
25的合金，按照该配方称取原料，真空感应熔炼得到成分为Pb
75Ag
25的合金熔体，将该合金熔体通过铜辊甩带速凝的方法以～10
6K/s的速率制备成厚度为～20μm的Pb
75Ag
25薄带状初始合金碎片，其微观组织包括由Pb组成的基体相与由纳米Ag颗粒组成的弥散颗粒相。其中，弥散颗粒相的颗粒大小为2nm～200nm。
室温下，将0.5克上述制得的Pb
75Ag
25初始合金碎片没入50mL浓度为2mol/L的盐酸水 溶液中进行反应。反应过程中，由活性元素Pb组成的基体相与酸反应进入溶液，而不与酸反应的纳米Ag颗粒则逐步脱离分散出来。10min后，将所得的近球形的纳米Ag颗粒与溶液进行分离，经清洗干燥，即得纳米Ag颗粒粉末，颗粒大小为2nm～200nm。
实施例9
本实施例提供一种微米Ag粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为Pb
75Ag
25的合金，按照该配方称取原料，真空感应熔炼得到成分为Pb
75Ag
25的合金熔体，将该合金熔体通过铸造的方法以～500K/s的速率制备成厚度为～2mm的Pb
75Ag
25薄板，其微观组织包括由Pb组成的基体相与由微米Ag枝晶颗粒组成的弥散颗粒相。其中，弥散颗粒相的颗粒大小为0.5μm～30μm。
室温下，将0.5克上述制得的Pb
75Ag
25初始合金碎片没入50mL浓度为3mol/L的盐酸水溶液中进行反应。反应过程中，由活性元素Pb组成的基体相与酸反应进入溶液，而不与酸反应的微米Ag颗粒则逐步脱离分散出来。20min后，将所得的枝晶微米Ag颗粒与溶液进行分离，经清洗干燥，即得微米Ag颗粒粉末，其颗粒大小为0.5μm～30μm。
实施例10
本实施例提供一种纳米Ag粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为K
75Ag
25的合金，按照该配方称取原料，真空感应熔炼得到成分为K
75Ag
25的合金熔体，将该合金熔体通过铜辊甩带速凝的方法以～10
6K/s的速率制备成厚度为～20μm的K
75Ag
25薄带状初始合金碎片，其微观组织包括由K组成的基体相与由纳米Ag颗粒组成的弥散颗粒相。其中，弥散颗粒相的颗粒大小为2nm～200nm。
室温下，将0.5克上述制得的K
75Ag
25初始合金碎片没入50mL水溶液中进行反应。反应过程中，由K组成的基体相与水反应进入溶液，而不与水反应的纳米Ag颗粒则逐步脱离分散出来。5min后，将所得的纳米Ag颗粒与溶液进行分离，经清洗干燥，即得纳米Ag颗粒粉末，其大小为2nm～200nm。
实施例11
本实施例提供一种亚微米Ag粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为Na
75Ag
25的合金，按照该配方称取原料，真空感应熔炼得到成分为Na
75Ag
25的合金熔体，将该合金熔体通过铜辊甩带速凝的方法以10
3K/s～10
4K/s的速率制备成厚度为～150μm的Na
75Ag
25薄带状初始合金碎片，其微观组织包括由Na组成的基体相与由亚微米Ag颗粒组成的弥散颗粒相。其中，弥散颗粒相的颗粒大小为100nm～3μm。
室温下，将0.5克上述制得的Na
75Ag
25初始合金碎片没入50mL水溶液中进行反应。反应过程中，由Na组成的基体相与水反应进入溶液，而不与水反应的亚微米Ag颗粒则逐步脱 离分散出来。5min后，将所得的亚微米Ag颗粒与溶液进行分离，经清洗干燥，即得亚微米Ag颗粒粉末，其大小为100nm～3μm。
实施例12
本实施例提供一种微米Cu粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为Pb
80Cu
20的合金，按照该配方称取原料，真空感应熔炼得到成分为Pb
80Cu
20的合金熔体，将该合金熔体以～200K/s的速率制备成厚度为3mm的Pb
80Cu
20薄片，其微观组织包括由Pb组成的基体相与由微米Cu颗粒组成的弥散颗粒相。其中，弥散颗粒相的颗粒大小为1μm～50μm。
室温下，将0.5克上述制得的Pb
80Cu
20初始合金没入100mL浓度为2mol/L的盐酸水溶液中进行反应。反应过程中，由活性元素Pb组成的基体相与酸反应进入溶液，而难与酸反应的微米Cu颗粒则逐步脱离分散出来。20min后，将所得的微米Cu颗粒与溶液进行分离，经清洗干燥，即得微米Cu颗粒粉末，颗粒大小为1μm～50μm。
实施例13
本实施例提供一种纳米Cu粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为Pb
80Cu
20的合金，按照该配方称取原料，真空感应熔炼得到成分为Pb
80Cu
20的合金熔体，将该合金熔体通过铜辊甩带速凝的方法以～10
6K/s的速率制备成厚度为～15μm的Pb
80Cu
20薄带状初始合金碎片，其微观组织包括由Pb组成的基体相与由纳米Cu颗粒组成的弥散颗粒相。其中，弥散颗粒相的颗粒大小为2nm～200nm。
室温下，将0.2克上述制得的Pb
80Cu
20初始合金碎片没入200mL浓度为0.5mol/L的盐酸水溶液中进行反应。反应过程中，由活性元素Pb组成的基体相与酸反应进入溶液，而难与酸反应的纳米Cu颗粒则逐步脱离分散出来。5min后，将所得的纳米Cu颗粒与溶液进行分离，经清洗干燥，即得纳米Cu颗粒粉末，颗粒大小为2nm～200nm。
实施例14
本实施例提供一种纳米B粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为Zn
80B
20的初始合金，按照该配方称取原料，真空感应熔炼得到成分为Zn
80B
20的初始合金熔体，将该初始合金熔体通过铜辊甩带速凝的方法以10
5K/s的速率制备成厚度为25μm的Zn
80B
20薄带状初始合金碎片，其微观组织包括由Zn组成的基体相与由纳米B颗粒组成的弥散颗粒相，其中，弥散颗粒相的颗粒大小为2nm～100nm。
室温下，将上述制得的Zn
80B
20初始合金碎片没入浓度为2mol/L的盐酸水溶液中进行反应。反应过程中，由Zn组成的基体相与盐酸反应进入溶液，而不与盐酸水溶液反应的纳米B颗粒则逐步脱离分散出来。10min后，将所得的纳米B颗粒与溶液进行分离，经清洗干燥， 即得纳米B颗粒粉末，其颗粒大小为2nm～100nm。
实施例15
本实施例提供一种亚微米B粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为Zn
80B
20的初始合金，按照该配方称取原料，真空感应熔炼得到成分为Zn
80B
20的初始合金熔体，将该初始合金熔体通过铜辊甩带速凝的方法以10
3K/s～10
4K/s的速率制备成厚度为200μm的Zn
80B
20薄带状初始合金碎片，其微观组织包括由Zn组成的基体相与由亚微米B颗粒组成的弥散颗粒相，其中，弥散颗粒相的颗粒大小为100nm～2μm。
室温下，将上述制得的Zn
80B
20初始合金碎片没入浓度为5mol/L的NaOH水溶液中进行反应。反应过程中，由活性元素Zn组成的基体相与碱反应进入溶液，而不与碱反应的亚微米B颗粒则逐步脱离分散出来。20min后，将所得的亚微米B颗粒与溶液进行分离，经清洗干燥，即得亚微米B颗粒粉末，其大小为100nm～2μm。
实施例16
本实施例提供一种纳米B粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为Zn
80B
20的初始合金，按照该配方称取原料，真空感应熔炼得到成分为Zn
80B
20的初始合金熔体，将该初始合金熔体通过铜辊甩带速凝的方法以10
5K/s的速率制备成厚度为25μm的Zn
80B
20薄带状初始合金碎片，其微观组织包括由Zn组成的基体相与由纳米B颗粒组成的弥散颗粒相，其中，弥散颗粒相的颗粒大小为2nm～100nm。
室温下，将上述制得的Zn
80B
20初始合金碎片放入真空管中，真空管内真空度保持在5Pa以下，真空管置于温度为400℃的管式炉中。加热过程中，合金中由Zn组成的基体相持续挥发并重新冷凝在真空管内其它温度较低的区域，而不挥发的纳米B颗粒则逐步脱离分散出来。30min后，即得纳米B颗粒粉末，其颗粒大小为2nm～100nm。
实施例17
本实施例提供一种纳米Cr粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为Zn
85Cr
15的初始合金，按照该配方称取原料，真空感应熔炼得到成分为Zn
85Cr
15的初始合金熔体，将该初始合金熔体通过铜辊甩带速凝的方法以10
5K/s的速率制备成厚度为25μm的Zn
85Cr
15薄带状初始合金碎片，其微观组织包括由Zn组成的基体相与由纳米Cr颗粒组成的弥散颗粒相，其中，弥散颗粒相的颗粒大小为2nm～100nm。
室温下，将上述制得的Zn
85Cr
15初始合金碎片没入浓度为1mol/L的盐酸水溶液中进行反应。反应过程中，由Zn组成的基体相与盐酸反应进入溶液，而不与稀盐酸水溶液反应的纳米Cr颗粒则逐步脱离分散出来。10min后，将所得的纳米B颗粒与溶液进行分离，经清洗干燥，即得纳米B颗粒粉末，其颗粒大小为2nm～100nm。
实施例18
本实施例提供一种微米Cr粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为Zn
85Cr
15的初始合金，按照该配方称取原料，真空感应熔炼得到成分为Zn
85Cr
15的初始合金熔体，将该初始合金熔体通过铸造方法以300K/s的速率制备成厚度为2mm的Zn
85Cr
15薄板，其微观组织包括由Zn组成的基体相与由微米Cr枝晶颗粒组成的弥散颗粒相。其中，弥散颗粒相的颗粒大小为0.5μm～30μm。
室温下，将上述制得的Zn
85Cr
15初始合金薄板没入浓度为1mol/L的盐酸水溶液中进行反应。反应过程中，由Zn组成的基体相与盐酸反应进入溶液，而不与稀盐酸水溶液反应的微米Cr颗粒则逐步脱离分散出来。30min后，将所得的微米Cr颗粒与溶液进行分离，经清洗干燥，即得微米Cr颗粒粉末，其颗粒大小为0.5μm～30μm。
实施例19
本实施例提供一种球形微米Cr粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为Zn
85Cr
15的初始合金，按照该配方称取原料，真空感应熔炼得到成分为Zn
85Cr
15的初始合金熔体，将该初始合金熔体通过铸造方法以300K/s的速率制备成厚度为2mm的Zn
85Cr
15薄板，其微观组织包括由Zn组成的基体相与由微米Cr枝晶颗粒组成的弥散颗粒相。其中，弥散颗粒相的颗粒大小为0.5μm～30μm。
室温下，将上述制得的Zn
85Cr
15初始合金薄板没入浓度为1mol/L的盐酸水溶液中进行反应。反应过程中，由Zn组成的基体相与盐酸反应进入溶液，而不与稀盐酸水溶液反应的微米Cr颗粒则逐步脱离分散出来。30min后，将所得的微米Cr颗粒与溶液进行分离，经清洗干燥，即得微米Cr颗粒粉末，其颗粒大小为0.5μm～30μm。
将所制得的微米Cr粉经过筛分后，通过成熟的等离子球化处理技术，进一步制得粒径范围为5μm～30μm的球形微米Cr粉。
实施例20
本实施例提供一种亚微米V粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为Zn
85V
15的初始合金，按照该配方称取原料，真空感应熔炼得到成分为Zn
85V
15的初始合金熔体，将该初始合金熔体通过铜辊甩带速凝的方法以10
3K/s～10
4K/s的速率制备成厚度为200μm的Zn
85V
15薄带状初始合金碎片，其微观组织包括由Zn组成的基体相与由亚微米V颗粒组成的弥散颗粒相，其中，弥散颗粒相的颗粒大小为100nm～2μm。
室温下，将上述制得的Zn
85V
15初始合金碎片没入浓度为5mol/L的NaOH水溶液中进行反应。反应过程中，由活性元素Zn组成的基体相与碱反应进入溶液，而不与碱反应的亚微米V颗粒则逐步脱离分散出来。20min后，将所得的亚微米V颗粒与溶液进行分离，经清洗干 燥，即得亚微米V颗粒粉末，其大小为100nm～2μm。
实施例21
本实施例提供一种纳米Mn粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为Mg
85Mn
15的初始合金，按照该配方称取原料，真空感应熔炼得到成分为Mg
85Mn
15的初始合金熔体，将该初始合金熔体通过铜辊甩带速凝的方法以10
6K/s的速率制备成厚度为20μm的Mg
85Mn
15薄带状初始合金碎片，其微观组织包括由Mg组成的基体相与由纳米Mn颗粒组成的弥散颗粒相，其中，弥散颗粒相的颗粒大小为2nm～100nm。
室温下，将上述制得的Mg
85Mn
15初始合金碎片放入真空管中，真空管内真空度保持在0.1Pa以下，真空管置于温度为600℃的管式炉中。加热过程中，合金中由Mg组成的基体相持续挥发并重新冷凝在真空管内其它温度较低的区域，而不易挥发的纳米Mn颗粒则逐步脱离分散出来。0.5h后，即得纳米Mn颗粒粉末，其颗粒大小为2nm～100nm。
实施例22
本实施例提供一种纳米FeMn粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为Mg
80Fe
10Mn
10的合金，按照该配方称取原料，真空感应熔炼得到成分为Mg
80Fe
10Mn
10的初始合金熔体，将该初始合金熔体通过铜辊甩带速凝的方法以10
6K/s的速率制备成厚度为20μm的Mg
80Fe
10Mn
10薄带状初始合金碎片，其微观组织包括由Mg组成的基体相与由纳米FeMn颗粒组成的弥散颗粒相，其中，弥散颗粒相的颗粒大小为2nm～100nm。
室温下，将上述制得的Mg
80Fe
10Mn
10初始合金碎片放入真空管中，真空管内真空度保持在0.1Pa以下，真空管置于温度为600℃的管式炉中。加热过程中，合金中由Mg组成的基体相持续挥发并重新冷凝在真空管内其它温度较低的区域，而不易挥发的纳米FeMn颗粒则逐步脱离分散出来。0.5h后，即得纳米FeMn颗粒粉末，其颗粒大小为2nm～100nm。
实施例23
本实施例提供一种纳米Si粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为Zn
80Si
20的初始合金，按照该配方称取原料，真空感应熔炼得到成分为Zn
80Si
20的初始合金熔体。将该初始合金熔体通过铜辊甩带速凝的方法以10
6K/s的冷速制备成厚度为20μm的Zn
80Si
20薄带状初始合金碎片，其微观组织包括由Zn组成的基体相与由纳米Si颗粒组成的弥散颗粒相，其中，弥散颗粒相的颗粒大小为5nm～300nm。
室温下，将上述制得的Zn
80Si
20初始合金碎片没入浓度为10mol/L的NaOH水溶液中进行反应。反应过程中，由活性元素Zn组成的基体相与碱反应进入溶液，而不与碱溶液反应的纳米Si颗粒则逐步脱离分散出来。10min后，将所得的近球形的纳米Si颗粒与溶液进行分离，经清洗干燥，即得纳米Si颗粒粉末，Si颗粒的颗粒大小为5nm～300nm。
实施例24
本实施例提供一种亚微米Si粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为Sn
80Si
20的初始合金，按照该配方称取原料，真空感应熔炼得到成分为Sn
80Si
20的初始合金熔体。将该初始合金熔体通过铜辊甩带速凝的方法以10
3K/s～10
4K/s的冷速制备成厚度为150μm的Sn
80Si
20薄带状初始合金碎片，其微观组织包括由Sn组成的基体相与由亚微米Si颗粒组成的弥散颗粒相，其中，弥散颗粒相的颗粒大小为20nm～2μm。
室温下，将上述制得的Sn
80Si
20初始合金碎片没入浓度为0.5mol/L的硝酸水溶液中进行反应。反应过程中，由活性元素Sn组成的基体相与酸反应进入溶液，而不与酸反应的亚微米Si颗粒则逐步脱离分散出来。20min后，将所得的亚微米Si颗粒与溶液进行分离，经清洗干燥，即得亚微米Si颗粒粉末，Si颗粒的颗粒大小为20nm～2μm。
实施例25
本实施例提供一种微米Ge粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为Sn
75Ge
25的初始合金，按照该配方称取原料，真空感应熔炼得到成分为Sn
75Ge
25的初始合金熔体。将该初始合金熔体以100K/s的凝固速率凝固得到Sn
75Ge
25的初始合金，其微观组织包括由Sn组成的基体相与由微米Ge颗粒组成的弥散颗粒相，其中，弥散颗粒相的颗粒大小为2μm～120μm。
室温下，将上述制得的Sn
75Ge
25初始合金没入浓度为1mol/L的盐酸水溶液中进行反应。反应过程中，由活性元素Sn组成的基体相与酸反应进入溶液，而活性差的弥散Ge颗粒则脱离出来。20min后，将所得的Ge颗粒与溶液进行分离，经清洗干燥，即得微米Ge颗粒粉末，Ge颗粒的颗粒大小为2μm～120μm。
实施例26
本实施例提供一种纳米Si-Ge粉的制备方法，该制备方法包括如下步骤：
选用配方分子式为Zn
80Si
10Ge
10的初始合金，按照该配方称取原料，真空感应熔炼得到成分为Zn
80Si
10Ge
10的初始合金熔体。将该初始合金熔体通过铜辊甩带速凝的方法以10
6K/s的冷速制备成厚度为20μm的Zn
80Si
10Ge
10薄带状初始合金碎片，其微观组织包括由Zn组成的基体相与由纳米Si-Ge颗粒组成的弥散颗粒相，其中，弥散颗粒相的颗粒大小为5nm～300nm。
室温下，将上述制得的Zn
80Si
10Ge
10初始合金碎片没入浓度为1mol/L的盐酸水溶液中进行反应。反应过程中，由活性元素Zn组成的基体相与酸反应进入溶液，而不与酸溶液反应的纳米Si-Ge颗粒则逐步脱离分散出来。10min后，将所得的近球形的纳米Si-Ge颗粒与溶液进行分离，经清洗干燥，即得纳米Si-Ge颗粒粉末，Si-Ge颗粒的颗粒大小为5nm～300nm。
实施例27
本实施例提供一种亚微米-微米Fe粉的制备方法，该制备方法包括如下步骤：
选用T(包含O、H、N、P、S、F、Cl、Br、I)杂质元素的原子百分比含量分别为1at.％与2.5at.％的Fe片与稀土La原料。按照La:Fe的摩尔比约为2:1将各合金原料熔化，得到原子百分比成分主要为La
65.3Fe
32.7T
2的均匀初始合金熔体。
通过铜辊甩带技术以约～10
4K/s的凝固速率将初始合金熔体制备成厚度为～100μm的La
65.3Fe
32.7T
2合金条带。该合金条带的凝固组织由原子百分比成分主要为La
97.2T
2.8的基体相与大量成分主要为Fe
99.7T
0.3的弥散颗粒相组成。其中Fe
99.7T
0.3弥散颗粒的形状为近球形或枝晶形，其粒径大小范围为500nm～3μm。Fe
99.7T
0.3弥散颗粒在合金条带中的体积百分含量约为14％；
通过稀酸溶液将合金条带中的La
97.2T
2.8基体相去除，同时利用Fe的磁性将脱离出来的Fe
99.7T
0.3弥散颗粒与稀酸溶液迅速分离，即得到主要成分为Fe
99.7T
0.3的亚微米-微米粉，其粒径大小范围为500nm～3μm，且其含有的O、H、N、P、S、F、Cl、Br、I的总含量为0.3at.％。
所制备得到的亚微米-微米Fe粉可用于磁性材料。
实施例28
本实施例提供一种纳米Fe粉的制备方法，该制备方法包括如下步骤：
选用T(包含O、H、N、P、S、F、Cl、Br、I)杂质元素的原子百分比含量分别为1at.％与2.5at.％的Fe片与稀土La原料。按照La:Fe的摩尔比约为60:40将各合金原料熔化，得到原子百分比成分主要为La
58.5Fe
39.6T
1.9的均匀初始合金熔体。
通过铜辊甩带技术以约～10
6K/s的凝固速率将初始合金熔体制备成厚度为～20μm的La
58.5Fe
39.6T
1.9合金条带。该合金条带的凝固组织由原子百分比成分主要为La
97T
3的基体相与大量成分主要为Fe
99.75T
0.25的弥散颗粒相组成。其中Fe
99.75T
0.25弥散颗粒的形状为近球形，其粒径大小范围为20nm～200nm。Fe
99.75T
0.25弥散颗粒在合金条带中的体积百分含量约为17.5％；
通过La在空气中的自然氧化-粉化过程以及Fe颗粒的磁性特性将Fe颗粒与La粉化后的氧化物分离，即得到纳米Fe颗粒，其粒径大小范围为20nm～200nm，且纳米Fe粉中的O、H、N、P、S、F、Cl、Br、I的总含量为0.25at.％。
实施例29
本实施例提供一种纳米Fe粉的制备方法，该制备方法包括如下步骤：
选用T(包含O、H、N、P、S、F、Cl、Br、I)杂质元素的原子百分比含量分别为1at.％与2.5at.％的Fe片与稀土La原料。其中，La原料中还含有1at.％的Ce，Fe原料中还含有0.5at.％的Mn。按照La:Fe的摩尔比约为60:40将各合金原料熔化，得到原子百分比成分主要为 (La
99Ce
1)
58.5(Fe
99.5Mn
0.5)
39.6T
1.9的均匀初始合金熔体。
通过铜辊甩带技术以约～10
6K/s的凝固速率将初始合金熔体制备成厚度为～20μm的(La
99Ce
1)
58.5(Fe
99.5Mn
0.5)
39.6T
1.9合金条带。该合金条带的凝固组织由原子百分比成分主要为(La
99Ce
1)
97T
3的基体相与大量成分主要为(Fe
99.5Mn
0.5)
99.75T
0.25的弥散颗粒相组成。其中(Fe
99.5Mn
0.5)
99.75T
0.25弥散颗粒的形状为近球形，其粒径大小范围为20nm～200nm。(Fe
99.5Mn
0.5)
99.75T
0.25弥散颗粒在合金条带中的体积百分含量约为17.5％；而且，合金熔体中Mn与Ce的引入，并没有导致初始合金条带中生成由La、Ce与Fe、Mn构成的金属间化合物；且不影响合金条带中基体相与弥散颗粒相的结构特征，也不影响弥散颗粒相中杂质含量的降低的规律。
通过La在空气中的自然氧化-粉化过程以及Fe颗粒的磁性特性将(Fe
99.5Mn
0.5)
99.75T
0.25颗粒与La粉化后的氧化物分离，即得到纳米(Fe
99.5Mn
0.5)
99.75T
0.25颗粒，其粒径大小范围为20nm～200nm，且纳米(Fe
99.5Mn
0.5)
99.75T
0.25粉中的O、H、N、P、S、F、Cl、Br、I的总含量为0.25at.％。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。
Claims (29)
- 一种粉体材料的制备方法，其特征在于，包括以下步骤：步骤一，选择初始合金原料，按照初始合金成分配比将初始合金原料熔化，得到含有杂质元素T的均匀初始合金熔体，其中，T包含O、H、N、P、S、F、Cl、I、Br中的至少一种，且所述初始合金熔体的平均成分为A aM bT d，其中，A包含Zn、Mg、Sn、Pb、Ga、In、Al、La、Ge、Cu、K、Na、Li中的至少一种，M包含B、Bi、Fe、Ni、Cu、Ag、Cr、V、Si、Ge中的至少一种，其中a、b、d代表对应组成元素的原子百分比含量，且60％≤a≤99.5％，0.5％≤b≤40％，0≤d≤10％；步骤二，将所述初始合金熔体凝固成初始合金条带；所述初始合金条带的凝固组织包括基体相和弥散颗粒相；所述基体相的熔点低于所述弥散颗粒相，所述弥散颗粒相被包覆于所述基体相中；所述初始合金熔体凝固过程中，初始合金熔体中的杂质元素T在弥散颗粒相与基体相中重新分配，并富集于所述基体相中，从而使所述弥散颗粒相得到纯化；所述初始合金条带中弥散颗粒相的成分主要为M x1T z1，基体相的平均成分主要为A x2T z2；且98.5％≤x1≤100％,0≤z1≤1.5％；80％≤x2≤100％,0≤z2≤20％；z1≤d≤z2，2z1≤z2；x1、z1、x2、z2分别代表对应组成元素的原子百分比含量；步骤三，将所述初始合金条带中的基体相去除，并保留基体相去除过程中不能被同时去除的弥散颗粒相；收集脱落出来的弥散颗粒相，即得到由原弥散颗粒组成的高纯目标粉体材料。
- 根据权利要求1所述的粉体材料的制备方法，其特征在于，所述初始合金熔体中的T杂质元素来源包括：初始合金原料引入杂质，熔炼过程中气氛或坩埚引入杂质。
- 根据权利要求1所述的粉体材料的制备方法，其特征在于，所述初始合金条带中不含有包含A与M构成的金属间化合物。
- 根据权利要求1所述的粉体材料的制备方法，其特征在于，所述初始合金条带中弥散颗粒的单晶颗粒数目在所有弥散颗粒数目中的占比不低于60％。
- 根据权利要求1所述的粉体材料的制备方法，其特征在于，所述初始合金条带中弥散颗粒的粒径范围为2nm～3mm。
- 根据权利要求1所述的粉体材料的制备方法，其特征在于，所述将合金条带中基体相去除方法包括：酸反应去除、碱反应去除、真空挥发去除、基体相自然氧化-粉化剥落去除中的至少一种。
- 根据权利要求1所述的粉体材料的制备方法，其特征在于，所述目标粉体材料的颗粒粒径 范围为2nm～3mm。
- 根据权利要求1所述的粉体材料的制备方法，其特征在于，在所述步骤三之后还进行以下步骤：将所述粉体材料筛分后，选择粒径范围为5μm～200μm的高纯粉体材料进行等离子球化处理，得到呈球形的粉体材料。
- 根据权利要求1-8任一项所述的粉体材料或球形粉体材料在催化材料、粉末冶金、复合材料、吸波材料、杀菌材料、磁性材料、金属注射成型、3D打印、涂料中的应用。
- 一种合金条带，其特征在于，包含内生粉与包覆体；所述合金条带的凝固组织包括基体相和弥散颗粒相，基体相即为所述包覆体，弥散颗粒相即为所述内生粉；所述包覆体的熔点低于所述内生粉的熔点，所述内生粉被包覆于所述包覆体中；所述合金条带中内生粉的成分主要为M x1T z1，包覆体的平均成分主要为A x2T z2；且98.5％≤x1≤100％,0≤z1≤1.5％；80％≤x2≤100％,0≤z2≤20％；z1≤d≤z2，2z1≤z2；x1、z1、x2、z2分别代表对应组成元素的原子百分比含量；其中，A包含Zn、Mg、Sn、Pb、Ga、In、Al、La、Ge、Cu、K、Na、Li中的至少一种，M包含B、Bi、Fe、Ni、Cu、Ag、Si、Ge、Cr、V中的至少一种；T包含O、H、N、P、S、F、Cl、I、Br中的至少一种。
- 一种粉末材料的制备方法，其特征在于，包括：提供初始合金，所述初始合金的成分为A aM b，所述初始合金的微观组织由成分为A的基体相以及成分为M的弥散颗粒相组成，其中，A选自Sn、Pb、Ga、In、Al、La、Ge、Cu、K、Na、Li中的至少一种，M选自B、Bi、Fe、Ni、Cu、Ag中的至少一种，a、b代表对应组成元素的原子百分含量，且1％≤b≤40％，a+b＝100％；将所述初始合金与腐蚀液混合，使所述基体相与所述腐蚀液反应变成离子进入溶液，所述弥散颗粒相脱离出来，即得到成分为M的粉末材料。
- 根据权利要求11所述的粉末材料的制备方法，其特征在于，当M为B时，A选自Sn、Ge、Cu中的至少一种；当M为Bi时，A选自Sn、Ga、Al中的至少一种；当M为Fe时，A选自La、In、Na、K、Li中的至少一种；当M为Ni时，A选自Na、K、Li中的至少一种；当M为Cu时，A选自Pb、Na、K、Li中的至少一种；当M为Ag时，A选自Pb、Na、K中的至少一种。
- 根据权利要求11所述的粉末材料的制备方法，其特征在于，所述初始合金通过以下方法得到：按照配比称取原料并将所述原料熔化得到合金熔体；将所述合金熔体凝固得到所述初始合金，其中，所述凝固的速率为1K/s～10 7K/s。
- 根据权利要求11所述的粉末材料的制备方法，其特征在于，所述弥散颗粒相的颗粒大小为2nm～500μm。
- 根据权利要求11所述的粉末材料的制备方法，其特征在于，当A选自Sn、Pb、Ga、In、Al、La、Ge、Cu中的至少一种时，所述腐蚀液为酸溶液。
- 根据权利要求11所述的粉末材料的制备方法，其特征在于，所述酸溶液中的酸包括盐酸、硫酸、硝酸、磷酸、醋酸、草酸中的至少一种。
- 根据权利要求16所述的粉末材料的制备方法，其特征在于，所述酸溶液中酸的摩尔浓度为0.01mol/L～20mol/L。
- 根据权利要求11所述的粉末材料的制备方法，其特征在于，当A选自Na、K、Li中的至少一种时，所述腐蚀液为水。
- 根据权利要求11所述的粉末材料的制备方法，其特征在于，所述初始合金与所述腐蚀液反应的步骤中，反应时间为1min～5h，反应温度为0℃～100℃。
- 根据权利要求11所述的粉末材料的制备方法，其特征在于，所述粉末材料的颗粒大小为2nm～500μm。
- 一类粉体材料的制备方法，其特征在于，包括：选择成分为A aM b的初始合金，a、b代表对应组成元素的原子百分比含量，且0.1％≤b≤40％，a+b＝100％；当M为Si、Ge中的至少一种时，A包含Zn、Sn、Pb、Ga、In、Ag、Bi、Al中的至少一种；当M为B、Cr、V中的至少一种时，A为Zn；当M为Fe、Mn中的至少一种时，A为Mg；当M为C时，A包含Mg、Zn中的至少一种；将所述初始合金充分熔化，得到初始合金熔体，在随后的冷却及凝固过程中，A与M之间不形成金属间化合物，而是发生A与M的分离，得到元素组成为M的弥散颗粒相分布于A基体相中的凝固态合金；去除所述凝固态合金中的A基体相，使得不能被同时去除的弥散颗粒相得到保留并分散脱离出来，即得到成分为M的粉体材料。
- 根据权利要求21所述的粉体材料的制备方法，其特征在于，去除A基体相的方式为酸反应去除、碱反应去除、真空挥发去除中的一种。
- 根据权利要求21所述的粉体材料的制备方法，其特征在于，所述初始合金熔体的冷却凝 固速率为1K/s～10 7K/s，所述凝固态合金的厚度为10μm～50mm，所述凝固态合金中弥散颗粒相的颗粒大小为2nm～500μm。
- 根据权利要求22所述的粉体材料的制备方法，其特征在于，所述酸反应去除中的酸包括盐酸、硫酸、硝酸、磷酸、醋酸、草酸中的至少一种，酸的摩尔浓度为0.1mol/L～15mol/L，反应时间为1min～1h，反应温度为0℃～100℃。
- 根据权利要求22所述的粉体材料的制备方法，其特征在于，所述碱反应去除中的碱包括NaOH与KOH中的至少一种，碱的摩尔浓度为0.1mol/L～15mol/L，反应时间为1min～1h，反应温度为0℃～100℃。
- 根据权利要求22所述的粉体材料的制备方法，其特征在于，所述真空挥发去除的过程中，所述凝固态合金所处容器内的真空度小于10Pa，处理温度与A基体相的熔点T m相关，其处理温度范围为T m-1K～T m-200K，处理时间为0.1h以上。
- 根据权利要求21所述的粉体材料的制备方法，其特征在于，所述粉体材料的颗粒大小为2nm～500μm。
- 根据权利要求21至27中任一项所述的粉体材料的制备方法，其特征在于，在将所述合金去除基体A之后还进行以下步骤:将所得的M粉体材料进行筛分，并分别进行等离子球化处理，最终得到具有不同粒径且呈球形的M粉体材料。
- 根据权利要求28所述的金属粉体材料的制备方法，其特征在于，所述球形的M粉体材料的粒径范围为1μm～500μm。
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| AU2020435277A1 (en) | 2022-11-10 |
| EP4119265A4 (en) | 2023-09-27 |
| EP4119265A1 (en) | 2023-01-18 |
| JP2023510987A (ja) | 2023-03-15 |
| CA3171452A1 (en) | 2021-09-16 |
| KR20220151645A (ko) | 2022-11-15 |
| US20230158568A1 (en) | 2023-05-25 |
| AU2020435277B2 (en) | 2024-05-16 |
| JP7550475B2 (ja) | 2024-09-13 |
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| CN112207285A (zh) | 2021-01-12 |
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