WO2019227664A1 - 一种提高烧结钕铁硼磁体耐蚀性能的激光冲击强化方法 - Google Patents

一种提高烧结钕铁硼磁体耐蚀性能的激光冲击强化方法 Download PDF

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WO2019227664A1
WO2019227664A1 PCT/CN2018/098901 CN2018098901W WO2019227664A1 WO 2019227664 A1 WO2019227664 A1 WO 2019227664A1 CN 2018098901 W CN2018098901 W CN 2018098901W WO 2019227664 A1 WO2019227664 A1 WO 2019227664A1
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sintered
magnet
laser
corrosion resistance
neodymium iron
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罗开玉
王长雨
王芳
尹叶芳
许小红
鲁金忠
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Jiangsu University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D10/00—Modifying the physical properties by methods other than heat treatment or deformation
    • C21D10/005—Modifying the physical properties by methods other than heat treatment or deformation by laser shock processing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
    • H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/026—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets protecting methods against environmental influences, e.g. oxygen, by surface treatment

Definitions

  • the invention relates to the technical field of surface modification of neodymium-iron-boron magnets, in particular to a laser shock strengthening method for improving the corrosion resistance of sintered neodymium-iron-boron magnets.
  • NdFeB magnets are the permanent magnets with the strongest magnetic force so far.
  • they have high performance. They are widely used in energy, transportation, machinery, medical, IT, home appliances and other industries.
  • new applications have been continuously brought to the rare earth permanent magnet NdFeB industry and other functional materials, which has brought a wider market prospect for the NdFeB industry.
  • the presence of the Nd-rich phase makes the magnet prone to intergranular corrosion, and its corrosion resistance is poor, which severely limits its application.
  • Sintered neodymium iron boron magnets are mainly composed of Nd-Fe-B main phase and Nd-rich grain boundary phase.
  • the Nd-rich phase has high activity and low potential. It is easy to corrode in environments containing corrosive media, damp heat, etc., because of the Nd-rich phase and Nd- There is a large potential difference between the main phases of Fe-B, and the sintered NdFeB magnet has the behavior of intergranular corrosion. Low corrosion resistance is a disadvantage of NdFeB magnets and one of the factors restricting its wide application. Corrosion of sintered NdFeB magnets not only destroys the integrity of the magnet, but also reduces its magnetic properties, which seriously affects its practical application. Therefore, since the sintered neodymium iron boron magnet was successfully prepared in 1983, it is of great practical significance to study its corrosion mechanism and improve the corrosion resistance of the magnet from the root according to the corrosion mechanism of the magnet.
  • the surface protection methods of sintered neodymium iron boron magnets are mainly electroplated zinc, electroplated nickel, electrophoretic coating, etc.
  • surface protection has so far limited the sintered neodymium iron.
  • One of the key issues in the application of boron magnets Obtaining amorphous nickel-phosphorus alloy by electroless plating is a simple and easy method, and has achieved a good anti-corrosion effect as an anti-corrosion protective layer for many corrosive materials.
  • the preparation process of the sintered NdFeB magnet material its surface is rough and has many pores. People have discovered through a lot of experiments. The traditional electroless plating process still cannot fully meet the protection requirements of magnets. Therefore, it is necessary to develop a new surface modification method to improve the corrosion resistance of sintered NdFeB magnets.
  • Laser shock strengthening also known as laser shot peening
  • Laser shot peening is a new type of material surface strengthening technology. It uses high-power laser-induced shock wave mechanical effects to process materials. It has the characteristics of high pressure, high energy, ultra-fast and ultra-high strain rate.
  • the plastic surface of the material undergoes plastic deformation, which changes the microstructure of the surface material and achieves the effect of grain refinement.
  • the depth of the induced residual stress layer can reach 1 to 2 mm, which can significantly improve the strength, hardness, wear resistance and corrosion resistance of the material. performance.
  • the invention proposes a new surface modification method for improving the corrosion resistance of sintered neodymium iron boron magnets, that is, first immersing the sintered neodymium iron boron magnets in a chlorine-containing solution for a period of time, so that The surface is slightly corroded, and atomic vacancies or gaps are generated at the surface grain boundaries of the sintered neodymium iron boron magnet after corrosion, and then the laser nano-powder compound nano-powder coated on the surface of the sintered neodymium iron boron magnet is implanted into the grain boundary by laser impact strengthening.
  • the compound nano-powder is implanted into the surface layer of the sintered NdFeB magnet under the action of the super strong shock wave generated by the impact strengthening to obtain a high-performance gradient nano-material.
  • This technology effectively implants compound nano-powder into the surface layer of sintered NdFeB magnets under the action of super-shock waves generated by laser shock strengthening, changes the composition and structure of the grain boundary phase, and improves the physical and chemical properties of the grain boundary phase.
  • the surface of the neodymium-iron-boron magnet is nano-sized, which induces a deeper layer of high residual residual compressive stress layer, which significantly improves the corrosion resistance of the sintered neodymium-iron-boron magnet.
  • the laser uses a single-pulse Nd: YAG laser.
  • the operating parameters are: wavelength 1064nm, pulse width 8-16ns, and single pulse energy 5-7.6J.
  • the spot radius is 2-3mm, and the overlap rate between the rows and columns is set to 50%.
  • the center of the laser beam spot and the upper left corner of the surface of the magnet to be impacted are used as the starting position of the laser impact strengthening, and the area to be impacted X
  • the axis and Y axis directions are consistent with the X and Y axis directions of the loading platform;
  • the compound nano powder is evenly coated on the etched surface of the sintered NdFeB magnet sample, and the laser is turned on at the same time, and the sintered NdFeB magnet sample is controlled to move to the focal point of the laser beam by a robot by using a progressive processing method.
  • the laser lap smashed the sintered neodymium iron boron magnet to corrode the surface.
  • the compound nano powder was implanted into the surface of the sintered neodymium iron boron magnet sample under the action of the super strong shock wave generated by the laser shock strengthening. High-thickness residual compressive stress layer with deeper thickness to obtain high-performance gradient nanomaterials.
  • the atomic percentage of the sintered neodymium-iron-boron magnet is Nd a R b Fe 100-abcd B c M d , where 8 ⁇ a ⁇ 18, 0.5 ⁇ b ⁇ 5, 3.5 ⁇ c ⁇ 8, 0.1 ⁇ d ⁇ 5, R is one or more of Pr, Dy, Tb, Ho, Gd, Ce, Co, Ni, Al, Cu, Ga, and M is Al, Cu, Ga, Mg, Zn, Sn , Si, Co, Ni, Nb, Zr, Ti, W, and V elements.
  • the chlorine-containing solution is a 3.5% by mass NaCl solution or a 14% by mass MgCl 2 solution, and the soaking time is 30-120 minutes.
  • the thickness of the compound nano powder layer applied in the step (5) is 0.5-1 mm, and the average particle size of the compound nano powder is 30-150 nm.
  • the compound nanopowder is a high melting point AlN nanopowder, which belongs to a covalent bond compound, has good thermal stability, and can stably exist in grain boundaries.
  • the sintered neodymium iron boron magnet is first immersed in a chlorine-containing solution for a period of time to slightly corrode the surface. After the corrosion, atomic vacancies or gaps are generated at the surface grain boundaries of the sintered neodymium iron boron magnet, and then the Laser shock strengthening implants compound nano powder coated on the surface of sintered neodymium iron boron magnets into the grain boundaries, and compound nano powders are implanted into the surface layer of sintered neodymium iron boron magnets under the action of super strong shock waves generated by laser shock strengthening to obtain high performance
  • the gradient nanomaterials change the composition and structure of the grain boundary phase, and improve the physical and chemical properties of the grain boundary phase.
  • the surface of the sintered neodymium iron boron magnet is nanometered by laser shock strengthening, which induces a deeper high-pressure residual compressive stress layer, which significantly improves Corrosion resistance of sintered NdFeB magnets.
  • Figure 1 shows the corrosion morphology on the surface of a sintered NdFeB magnet.
  • FIG. 2 is a schematic diagram of a comparison of kinetic potential polarization curves of a sintered neodymium-iron-boron magnet Nd 8 Pr 4 Fe 81 Co 2 B 3.5 Cu 1.5 with and without AlN nanopowder in a 14% NaCl solution.
  • FIG. 3 is a comparison diagram of the kinetic potential polarization curves of sintered Nd 10 Dy 2 Fe 79 B 8 Al 0.5 Mg 0.5 sintered Nd 10 Dy 2 Fe 79 B 8 Al 0.5 Mg 0.5 with and without added AlN nano powder.
  • FIG. 4 is a schematic diagram of a comparison of kinetic potential polarization curves of sintered neodymium iron boron magnets Nd 15 Gd 0.5 Fe 80 B 4 Ni 0.5 with and without AlN nano powder added in a 3.5% NaCl solution.
  • the sintered NdFeB magnet is immersed in a 14% MgCl 2 solution and left for 30 minutes. At this time, atomic vacancies or gaps are generated at the grain boundaries after the surface of the sintered NdFeB magnet is corroded.
  • the laser uses a single-pulse Nd: YAG laser.
  • the operating parameters are: wavelength 1064nm, pulse width 16ns, single pulse energy 5.6J, and spot radius 3mm.
  • the compound AlN nano powder with an average particle size of 50 nm is uniformly coated on the etched surface of the sintered neodymium iron boron magnet sample, the coating thickness is 0.5 mm, the laser is turned on, and the process is controlled by a robot using a progressive processing method
  • the sintered NdFeB magnet sample was moved to the focal point of the laser beam, and large-area laser lap impact strengthening was performed on the magnet's corroded surface.
  • the compound AlN nano-powder was implanted into the sintered neodymium under the action of the super strong shock wave generated by the laser impact strengthening.
  • the surface layer of the iron-boron magnet is strengthened by laser shock to induce a high-thickness residual compressive stress layer with a deep thickness, thereby obtaining a high-performance gradient nanomaterial.
  • an electrochemical corrosion test is performed on the sintered neodymium-iron-boron magnet Nd 8 Tb 3 Fe 83 Co 2 B 3.5 Cu 1.5 , and it is compared with that before treatment. It can be seen from FIG. 2 that after the compound AlN nano-powder is added, the corrosion potential of the sample increases and the corrosion current density decreases.
  • the experimental results show that the addition of AlN nano-powder at the grain boundary reduces the number of Nd-rich phases in the grain boundary region, increases the corrosion potential of the grain boundary phase, and increases the stability of the grain boundary. According to the mechanism of the electrode reaction, the potential of the grain boundary phase increases. High will increase the corrosion potential of the entire sintered NdFeB magnet. It was further illustrated that the addition of AlN nano-powder at the grain boundary can significantly improve the corrosion resistance of sintered sintered NdFeB magnets Nd 8 Pr 4 Fe 83 Co 2 B 3.5 Cu 1.5 .
  • the sintered NdFeB magnet is immersed in a 3.5% NaCl solution and left for 60 minutes. At this time, atomic vacancies or gaps are generated at the grain boundaries after the surface of the sintered NdFeB magnet is corroded.
  • the laser uses a single-pulse Nd: YAG laser.
  • the operating parameters are: wavelength 1064nm, pulse width 8ns, single pulse energy 7.6J, and spot radius 3mm.
  • the compound AlN nano powder with an average particle size of 150 nm is uniformly coated on the etched surface of the sintered NdFeB magnet sample, the coating thickness is 1 mm, the laser is turned on, and the sintering is controlled by a robot using a progressive processing method
  • the NdFeB magnet sample is moved to the focal point of the laser beam, and the surface of the magnet after corrosion is strengthened by laser lap impact strengthening.
  • the compound AlN nano powder is implanted into the sintered NdFe under the action of the super strong shock wave generated by the laser impact strengthening.
  • the surface of the boron magnet is strengthened by laser shock to induce a high-thickness residual compressive stress layer with a deep thickness, thereby obtaining a high-performance gradient nanomaterial.
  • an electrochemical corrosion test is performed on a sintered neodymium iron boron magnet Nd 8 Pr 4 Fe 83 Co 2 B 3.5 Cu 1.5 , and it is compared with that before treatment. It can also be seen from FIG. 3 that after the compound AlN nano-powder is added, the corrosion potential of the sample increases and the corrosion current density decreases.
  • the laser uses a single-pulse Nd: YAG laser.
  • the operating parameters are: wavelength 1064nm, pulse width 10ns, single pulse energy 6J, spot radius 3mm.
  • the overlap rate of the spot between rows and columns is 50%.
  • the center of the laser beam spot and the upper left corner of the surface of the magnet to be impacted are used as the starting position of the laser impact strengthening, and the X and Y directions of the area to be impacted are loaded.
  • the X-axis and Y-axis directions of the platform are the same;
  • the compound AlN nano powder with an average particle size of 100 nm was uniformly coated on the etched surface of the sintered neodymium iron boron magnet sample, the coating thickness was 0.7 mm, the laser was turned on, and the process was controlled by a robot using a progressive processing method.
  • the sintered NdFeB magnet sample was moved to the focal point of the laser beam, and large-area laser lap impact strengthening was performed on the magnet's corroded surface.
  • the compound AlN nano-powder was implanted into the sintered neodymium under the action of the super strong shock wave generated by the laser impact strengthening.
  • the surface layer of the iron-boron magnet is strengthened by laser shock to induce a high-thickness residual compressive stress layer with a deep thickness, thereby obtaining a high-performance gradient nanomaterial.
  • an electrochemical corrosion test is performed on a sintered neodymium iron boron magnet Nd 8 Pr 4 Fe 83 Co 2 B 3.5 Cu 1.5 , and it is compared with that before treatment. It can also be seen from FIG. 4 that after the compound AlN nano-powder is added, the corrosion potential of the sample increases and the corrosion current density decreases.

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Abstract

一种提高烧结钕铁硼磁体耐蚀性能的激光冲击强化方法。先将烧结钕铁硼磁体浸泡在含氯溶液中使其表面轻微腐蚀，腐蚀后烧结钕铁硼磁体表层晶界处有原子空位或者缝隙产生，然后采用激光冲击强化将涂敷在烧结钕铁硼磁体表面的化合物纳米粉末植入晶界，在激光冲击强化产生的超强冲击波作用下将化合物纳米粉末植入到烧结钕铁硼磁体表层，获得高性能的梯度纳米材料，同时激光冲击强化使烧结钕铁硼磁体表面纳米化，诱导较深厚度的高幅残余压应力层，显著提高烧结钕铁硼磁体的耐腐蚀性能。

Description

一种提高烧结钕铁硼磁体耐蚀性能的激光冲击强化方法 技术领域
本发明涉及钕铁硼磁铁表面改性技术领域，特指一种提高烧结钕铁硼磁体耐蚀性能的激光冲击强化方法。
背景技术
钕铁硼磁铁为至目前为止具有最强磁力的永久磁铁，作为第三代稀土永磁材料，具有很高的性能，其广泛应用于能源、交通、机械、医疗、IT、家电等行业，特别是随着信息技术为代表的知识经济的发展，给稀土永磁钕铁硼产业等功能材料不断带来新的用途，这为钕铁硼产业带来更为广阔的市场前景。然而在潮湿的环境中，由于富Nd相的存在，使得磁体容易产生晶间腐蚀，其耐腐蚀性差，严重限制了其应用范围。烧结钕铁硼磁铁主要由Nd-Fe-B主相和富Nd晶界相组成，富Nd相活性大，电位低，在含有腐蚀介质、湿热等环境中容易腐蚀，由于富Nd相和Nd-Fe-B主相之间具有较大的电位差，烧结钕铁硼磁铁具有晶间腐蚀的行为。低的抗腐蚀性是钕铁硼磁铁的缺点，是制约其广泛应用的因素之一。烧结钕铁硼磁体的腐蚀不仅破坏了磁体的完整性，而且降低了其磁性能，从而严重影响其实际应用。因此，从烧结钕铁硼磁铁在1983年成功制备以来，研究其腐蚀机理，根据磁体的腐蚀机理从根源上提高磁体的抗腐蚀性能，具有非常重大的实际意义
目前，烧结钕铁硼磁体表面防护处理的方法主要有电镀锌、电镀镍、电泳涂覆等，但由于存在镀层结合力弱、抗腐蚀能力不足等缺点，表面防护迄今为止仍是限制烧结钕铁硼磁体应用的关键问题之一。化学镀获得非晶态镍磷合金是一种简单易行的方法，作为许多易腐蚀材料的抗腐蚀保护层取得了很好的抗腐蚀效果。但是由于烧结钕铁硼磁体材料制备工艺的限制，其表面粗糙、孔隙多。人们经过大量的实验发现。传统的化学镀工艺仍然不能充分的满足磁体的防护要求。因此，发展一种新型的提高烧结钕铁硼磁体耐腐蚀性能的表面改性方法成为必然。
激光冲击强化(又叫激光喷丸)是一种新型的材料表面强化技术，利用强激光诱导的冲击波力学效应对材料进行加工，具有高压、高能、超快和超高应变率等特点，同时在材料表层发生塑性变形，使得表层材料微观组织发生变化，达到细化晶粒的效果，同时诱导的残余应力层深度可达1～2mm，能够明显提高材料的强度、硬度、耐磨性和耐腐蚀性能。
发明内容
本发明基于烧结钕铁硼磁体的腐蚀机理，提出一种新型的提高烧结钕铁硼磁体耐蚀性能的表面改性方法，即先将烧结钕铁硼磁体浸泡在含氯溶液中一段时间，使其表面轻微腐蚀，腐蚀后的烧结钕铁硼磁体表层晶界处有原子空位或者缝隙产生，然后采用激光冲击强化将涂敷在烧结钕铁硼磁体表面的化合物纳米粉末植入晶界，在激光冲击强化产生的超强冲击波作用下将化合物纳米粉末植入到烧结钕铁硼磁体表层，获得高性能的梯度纳米材料。该技术通过在激光冲击强化产生的超强冲击波作用下将化合物纳米粉末有效植入到烧结钕铁硼磁体表层，改变晶界相成分和结构，改善晶界相物化性质，同时激光冲击强化使烧结钕铁硼磁体表面纳米化，诱导较深厚度的高副残余压应力层，显著提高烧结钕铁硼磁体的耐腐蚀性能。
具体步骤如下：
(1)将烧结钕铁硼磁体表面进行打磨、抛光处理后，放在酒精溶液中用超声波清洗机清除表面的灰尘与油渍；
(2)将烧结钕铁硼磁体浸泡在含氯溶液中使得烧结钕铁硼磁体表面腐蚀后晶界处有原子空位或者缝隙产生；
(3)将预处理的烧结钕铁硼磁体取出并用冷风吹干，安装在机械手专用夹具上；
(4)通过激光器控制装置设定激光器的输出功率和光斑参数，激光器采用的是单脉冲Nd：YAG激光器，工作参数为：波长1064nm，脉冲宽度8-16ns，单次脉冲能量5-7.6J，光斑半径2-3mm，设定行间和列间光斑搭接率为50％，同时将激光束光斑中心与磁体待冲击表面左上角重合，作为激光冲击强化起始位置，并使待冲击区域X轴和Y轴方向与加载平台的X轴和Y轴方向一致；
(5)将化合物纳米粉末均匀涂敷在烧结钕铁硼磁体试样腐蚀后的表面，同时打开激光器，采用逐行加工的方法通过机械手控制烧结钕铁硼磁体试样移动到激光束聚焦点上，对烧结钕铁硼磁体腐蚀后的表面进行激光搭接冲击强化，在激光冲击强化产生的超强冲击波作用下将化合物纳米粉末植入到烧结钕铁硼磁体试样表层，同时激光冲击强化诱导较深厚度的高幅残余压应力层，从而获得高性能的梯度纳米材料。
所述步骤(1)中，烧结钕铁硼磁体的原子百分比为Nd aR bFe 100-a-b-c-dB cM d，其中8≤a≤18，0.5≤b≤5，3.5≤c≤8，0.1≤d≤5，R为Pr、Dy、Tb、Ho、Gd、Ce、Co、Ni、Al、Cu、Ga元素中的一种或几种，M为Al、Cu、Ga、Mg、Zn、Sn、Si、Co、Ni、Nb、Zr、Ti、W、V元素中一种或几种。
所述步骤(2)中，含氯溶液为质量分数3.5％的NaCl溶液或者质量分数14％的MgCl 2 溶液，浸泡时间为30-120分钟。
所述步骤(5)中，所述步骤(5)中涂敷的化合物纳米粉末层厚度为0.5-1mm，化合物纳米粉末的平均颗粒尺度为30-150nm。
所述步骤(5)中，化合物纳米粉末为高熔点的AlN纳米粉末，属于共价键化合物，具有良好的热稳定性，能够稳定存在于晶界中。
本发明的技术效果：本发明先将烧结钕铁硼磁体浸泡在含氯溶液中一段时间，使其表面轻微腐蚀，腐蚀后烧结钕铁硼磁体表层晶界处有原子空位或者缝隙产生，然后采用激光冲击强化将涂敷在烧结钕铁硼磁体表面的化合物纳米粉末植入晶界，在激光冲击强化产生的超强冲击波作用下将化合物纳米粉末植入到烧结钕铁硼磁体表层，获得高性能的梯度纳米材料，改变了晶界相成分和结构，改善了晶界相物化性质，同时激光冲击强化使烧结钕铁硼磁体表面纳米化，诱导较深厚度的高幅残余压应力层，显著提高了烧结钕铁硼磁体的耐腐蚀性能。
附图说明
图1为烧结钕铁硼磁体表面的腐蚀形貌。
图2为添加与未添加AlN纳米粉末的烧结钕铁硼磁体Nd 8Pr 4Fe 81Co 2B 3.5Cu 1.5在质量分数14％的NaCl溶液中的动电位极化曲线对比示意图。
图3为添加与未添加AlN纳米粉末的烧结钕铁硼磁体Nd 10Dy 2Fe 79B 8Al 0.5Mg 0.5在质量分数3.5％的NaCl溶液中的动电位极化曲线对比示意图。
图4为添加与未添加AlN纳米粉末的烧结钕铁硼磁体Nd 15Gd 0.5Fe 80B 4Ni 0.5在质量分数3.5％的NaCl溶液中的动电位极化曲线对比示意图。
具体实施方式
下面结合附图和具体实施例，对本发明的技术方案做进一步详细说明。
一种使用上述强化方法加工烧结钕铁硼磁体的实例，其步骤为:
实施例1：
(1)将烧结钕铁硼磁体Nd 8Pr 4Fe 81Co 2B 3.5Cu 1.5表面用500#到2400#的SiC砂纸进行打磨、抛光处理后，放在酒精溶液中用超声波清洗机清除表面的灰尘与油渍；
(2)将烧结钕铁硼磁体浸泡在质量分数为14％的MgCl 2溶液中，静置30分钟，这时烧结钕铁硼磁体表面腐蚀后晶界处有原子空位或者缝隙产生。
(3)将预处理的烧结钕铁硼磁体取出并用冷风吹干，安装在机械手专用夹具上；
(4)通过激光器控制装置设定激光器的输出功率和光斑参数，激光器采用的是单脉 冲Nd：YAG激光器，工作参数为：波长1064nm，脉冲宽度16ns，单次脉冲能量5.6J，光斑半径3mm，设定行间和列间光斑搭接率为50％，同时将激光束光斑中心与磁体待冲击表面左上角重合，作为激光冲击强化起始位置，并使待冲击区域X轴和Y轴方向与加载平台的X轴和Y轴方向一致；
(5)将平均颗粒尺度为50nm的化合物AlN纳米粉末均匀涂敷在烧结钕铁硼磁体试样的腐蚀后的表面，涂层厚度为0.5mm，打开激光器，采用逐行加工的方法通过机械手控制烧结钕铁硼磁体试样移动到激光束聚焦点上，对磁体腐蚀后的表面进行大面积激光搭接冲击强化，在激光冲击强化产生的超强冲击波作用下化合物AlN纳米粉末植入到烧结钕铁硼磁体表层，同时激光冲击强化诱导较深厚度的高幅残余压应力层，从而获得高性能的梯度纳米材料。
本实施例对烧结钕铁硼磁体Nd 8Tb 3Fe 83Co 2B 3.5Cu 1.5进行电化学腐蚀测试，并与处理前对比。从图2中可以看出，添加化合物AlN纳米粉末后，试样的腐蚀电位升高，腐蚀电流密度降低。实验结果说明，晶界添加AlN纳米粉使晶界区域富Nd相数量减少，增加了晶界相的腐蚀电位，使晶界的稳定性升高，根据电极反应的机理，晶界相电位的升高会使整个烧结钕铁硼磁体的腐蚀电位升高。进一步说明了晶界添加AlN纳米粉末能够显著提高烧结烧结钕铁硼磁体Nd 8Pr 4Fe 83Co 2B 3.5Cu 1.5的抗腐蚀性能。
实施例2：
(1)将烧结钕铁硼磁体Nd 10Dy 2Fe 79B 8Al 0.5Mg 0.5表面用500#到2400#的SiC砂纸进行打磨、抛光处理后，放在酒精溶液中用超声波清洗机清除表面的灰尘与油渍；
(2)将烧结钕铁硼磁体浸泡在质量分数为3.5％的NaCl溶液中，静置60分钟，这时烧结钕铁硼磁体表面腐蚀后晶界处有原子空位或者缝隙产生。
(3)将预处理的烧结钕铁硼磁体取出并用冷风吹干，安装在机械手专用夹具上；
(4)通过激光器控制装置设定激光器的输出功率和光斑参数，激光器采用的是单脉冲Nd：YAG激光器，工作参数为：波长1064nm，脉冲宽度8ns，单次脉冲能量7.6J，光斑半径3mm，设定行间和列间光斑搭接率为50％，同时将激光束光斑中心与磁体待冲击表面左上角重合，作为激光冲击强化起始位置，并使待冲击区域X轴和Y轴方向与加载平台的X轴和Y轴方向一致；
(5)将平均颗粒尺度为150nm的化合物AlN纳米粉末均匀涂敷在烧结钕铁硼磁体试样的腐蚀后的表面，涂层厚度为1mm，打开激光器，采用逐行加工的方法通过机械手控制烧结钕铁硼磁体试样移动到激光束聚焦点上，对磁体腐蚀后的表面进行大面积激光搭 接冲击强化，在激光冲击强化产生的超强冲击波作用下化合物AlN纳米粉末植入到烧结钕铁硼磁体表层，同时激光冲击强化诱导较深厚度的高幅残余压应力层，从而获得高性能的梯度纳米材料。
本实施例对烧结钕铁硼磁体Nd 8Pr 4Fe 83Co 2B 3.5Cu 1.5进行电化学腐蚀测试，并与处理前对比。从图3中同样可以看出，添加化合物AlN纳米粉末后，试样的腐蚀电位升高，腐蚀电流密度降低。
实施例3：
(1)将烧结钕铁硼磁体Nd 15Gd 0.5Fe 80B 4Ni 0.5表面用500#到2400#的SiC砂纸进行打磨、抛光处理后，放在酒精溶液中用超声波清洗机清除表面的灰尘与油渍；
(2)将烧结钕铁硼磁体浸泡在质量分数为3.5％的NaCl溶液中，静置90分钟，这时烧结钕铁硼磁体表面腐蚀后晶界处有原子空位或者缝隙产生。
(3)将预处理的烧结钕铁硼磁体取出并用冷风吹干，安装在机械手专用夹具上；
(4)通过激光器控制装置设定激光器的输出功率和光斑参数，激光器采用的是单脉冲Nd：YAG激光器，工作参数为：波长1064nm，脉冲宽度10ns，单次脉冲能量6J，光斑半径3mm，设定行间和列间光斑搭接率为50％，同时将激光束光斑中心与磁体待冲击表面左上角重合，作为激光冲击强化起始位置，并使待冲击区域X轴和Y轴方向与加载平台的X轴和Y轴方向一致；
(5)将平均颗粒尺度为100nm的化合物AlN纳米粉末均匀涂敷在烧结钕铁硼磁体试样的腐蚀后的表面，涂层厚度为0.7mm，打开激光器，采用逐行加工的方法通过机械手控制烧结钕铁硼磁体试样移动到激光束聚焦点上，对磁体腐蚀后的表面进行大面积激光搭接冲击强化，在激光冲击强化产生的超强冲击波作用下化合物AlN纳米粉末植入到烧结钕铁硼磁体表层，同时激光冲击强化诱导较深厚度的高幅残余压应力层，从而获得高性能的梯度纳米材料。
本实施例对烧结钕铁硼磁体Nd 8Pr 4Fe 83Co 2B 3.5Cu 1.5进行电化学腐蚀测试，并与处理前对比。从图4中同样可以看出，添加化合物AlN纳米粉末后，试样的腐蚀电位升高，腐蚀电流密度降低。

Claims (8)

  1. 一种提高烧结钕铁硼磁体耐蚀性能的激光冲击强化方法，其特征在于：先将打磨、抛光、清洗后的烧结钕铁硼磁体浸在含氯溶液中使其表面腐蚀，腐蚀后烧结钕铁硼磁体原始晶界处有原子空位或者缝隙产生，然后采用激光冲击强化将涂敷在烧结钕铁硼磁体表面的化合物纳米粉末植入晶界，在激光冲击强化产生的超强冲击波作用下将化合物纳米粉末植入到烧结钕铁硼磁体表层，获得梯度纳米材料，同时激光冲击强化使烧结钕铁硼磁体表面纳米化，诱导形成残余压应力层，改变了晶界相成分和结构，改善了晶界相物化性质，达到抑制磁体表面晶界腐蚀的效果，从而显著提高烧结钕铁硼磁体的耐腐蚀性能。
  2. 如权利要求1所述的一种提高烧结钕铁硼磁体耐蚀性能的激光冲击强化方法，其特征在于，具体步骤如下：
    (1)将烧结钕铁硼磁体表面进行打磨、抛光处理后，放在酒精溶液中用超声波清洗机清除表面的灰尘与油渍；
    (2)将烧结钕铁硼磁体浸泡在含氯溶液中使得烧结钕铁硼磁体表面腐蚀后晶界处有原子空位或者缝隙产生；
    (3)将预处理的烧结钕铁硼磁体取出并用冷风吹干，安装在机械手专用夹具上；
    (4)通过激光器控制装置设定激光器的输出功率和光斑参数，同时将激光束光斑中心与磁体待冲击表面左上角重合，作为激光冲击强化起始位置，并使待冲击区域X轴和Y轴方向与加载平台的X轴和Y轴方向一致；
    (5)将化合物纳米粉末均匀涂敷在烧结钕铁硼磁体试样腐蚀后的表面，同时打开激光器，采用逐行加工的方法通过机械手控制烧结钕铁硼磁体试样移动到激光束聚焦点上，对烧结钕铁硼磁体腐蚀后的表面进行激光搭接冲击强化，在激光冲击强化产生的超强冲击波作用下将化合物纳米粉末植入到烧结钕铁硼磁体试样表层，同时激光冲击强化诱导形成残余压应力层，从而获得高性能的梯度纳米材料。
  3. 如权利要求2所述的一种提高烧结钕铁硼磁体耐蚀性能的激光冲击强化方法，其特征在于，所述步骤(1)中，烧结钕铁硼磁体的原子百分比为Nd aR bFe 100-a-b-c-dB cM d，其中8≤a≤18，0.5≤b≤5，3.5≤c≤8，0.1≤d≤5，R为Pr、Dy、Tb、Ho、Gd、Ce、Co、Ni、Al、Cu、Ga元素中的一种或几种，M为Al、Cu、Ga、Mg、Zn、Sn、Si、Co、Ni、Nb、Zr、Ti、W、V元素中一种或几种。
  4. 如权利要求2所述的一种提高烧结钕铁硼磁体耐蚀性能的激光冲击强化方法，其特征在于，所述步骤(2)中，含氯溶液为质量分数3.5％的NaCl溶液或者质量分数14％的 MgCl 2溶液，浸泡时间为30-120分钟。
  5. 如权利要求2所述的一种提高烧结钕铁硼磁体耐蚀性能的激光冲击强化方法，其特征在于，步骤(4)中，激光器采用的是单脉冲Nd：YAG激光器，工作参数为：波长1064nm，脉冲宽度8-16ns，单次脉冲能量5-7.6J，光斑半径2-3mm。
  6. 如权利要求2所述的一种提高烧结钕铁硼磁体耐蚀性能的激光冲击强化方法，其特征在于，步骤(4)中，设定行间和列间光斑搭接率为50％。
  7. 如权利要求2所述的一种提高烧结钕铁硼磁体耐蚀性能的激光冲击强化方法，其特征在于，所述步骤(5)中，所述步骤(5)中涂敷的化合物纳米粉末层厚度为0.5-1mm，化合物纳米粉末的平均颗粒尺度为30-150nm。
  8. 如权利要求2所述的一种提高烧结钕铁硼磁体耐蚀性能的激光冲击强化方法，其特征在于，所述步骤(5)中，化合物纳米粉末为高熔点的AlN纳米粉末，属于共价键化合物，具有良好的热稳定性，能够稳定存在于晶界中。
PCT/CN2018/098901 2018-05-28 2018-08-06 一种提高烧结钕铁硼磁体耐蚀性能的激光冲击强化方法 Ceased WO2019227664A1 (zh)

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