WO2020248644A1 - 一种金属材料及其表面原位溶出改性方法 - Google Patents

一种金属材料及其表面原位溶出改性方法 Download PDF

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WO2020248644A1
WO2020248644A1 PCT/CN2020/080643 CN2020080643W WO2020248644A1 WO 2020248644 A1 WO2020248644 A1 WO 2020248644A1 CN 2020080643 W CN2020080643 W CN 2020080643W WO 2020248644 A1 WO2020248644 A1 WO 2020248644A1
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metal material
metal
modification
powder
heat treatment
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PCT/CN2020/080643
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English (en)
French (fr)
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张亚鹏
刘太楷
邓春明
谢迎春
邓子谦
刘敏
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广东省新材料研究所
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Priority to US16/982,042 priority Critical patent/US20210146438A1/en
Publication of WO2020248644A1 publication Critical patent/WO2020248644A1/zh

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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
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    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134—Plasma spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8906—Iron and noble metals
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
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    • 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
    • C23C24/085—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
    • C23C24/087—Coating with metal alloys or metal elements only
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    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
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    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
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    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
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    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
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Definitions

  • the invention relates to the field of material preparation and modification, in particular to a method for in-situ dissolution modification on the surface of metal materials to enhance electrochemical performance.
  • noble metal catalysts show excellent electrochemical catalytic performance, but due to cost issues, they are not suitable for large-scale applications.
  • Traditional catalysts such as Fe, Co, Ni, Cu, etc. also have certain catalytic activity, and because of their large reserves and low cost, they are widely used in the catalytic industry.
  • technologies such as fuel cells, electrolysis of water, organic catalysis, etc. have increasingly demanded catalyst activity.
  • a single traditional catalyst can no longer meet the requirements of its catalytic performance.
  • Material modification is needed to improve performance.
  • material modification methods such as electrodeposition, magnetron sputtering, heteroatom substitution, etc.
  • the interaction between the prepared modified particles and the base material is not strong. Although it will improve the initial performance, it often leads to stability. decline.
  • some modification methods are only applicable to the laboratory stage and are not suitable for large-scale production applications. Therefore, it is urgent to develop a new and stable method for surface modification of metal materials.
  • In-situ dissolution is an emerging material modification method. It is a very stable and efficient material modification method. Using this method to modify traditional metal catalysts requires less precious metals and can significantly improve performance while maintaining the original stability. Therefore, it can be foreseen its good application prospects in the field of material preparation and modification. At present, there are no reports on surface modification of metal materials by in-situ stripping method in China.
  • the purpose of the present invention is to overcome the above shortcomings of the prior art and provide a method for in-situ stripping modification of the surface of metal materials to enhance electrochemical performance.
  • the method is aimed at the modification of traditional metal catalysts, can be applied to multiple material processing and preparation technical fields, and can be completed with only a small amount of precious metal doping, is convenient to operate, low in cost, and has obvious experimental value and application prospects.
  • the technical solution adopted by the present invention is: an in-situ dissolution modification method on the surface of a metal material, which includes the following steps:
  • step (1) The raw material powder obtained in step (1) is prepared by a preparation method under non-equilibrium conditions to obtain a metal material
  • step (3) The metal material prepared in step (2) is heat-treated to bring it to an equilibrium state, and the doped phase is dissolved out to the surface of the metal material to obtain a modified metal material.
  • in-situ dissolution is an emerging material modification method. It refers to the mixing of doped particles with the substrate under certain non-equilibrium conditions to prepare a metal material, and then changing the conditions to make the metal material reach a stable state, and use the difference in performance of the doped metal to dissolve from the bulk phase to the surface and form nano islands Shaped pinning structure.
  • the dissolved nanoparticles are tightly combined with the substrate, have strong interaction, and the structure formed by the modification has high stability.
  • island-shaped nanoparticles can increase the roughness of the substrate surface and increase the specific surface area, thereby increasing the catalytic active sites of the metal material and improving the catalytic performance of the metal material.
  • the base metal is at least one of Mn, Fe, Co, Ni, Cu, and Zn.
  • the modified metal is at least one of Mo, Ru, Rh, Pd, Ag, Ir, Pt, and Au.
  • the mass percentage of the modified metal in the raw material powder is 0.1-15%.
  • the content is less than 0.1%, the surface dissolution of the modified metal cannot be guaranteed to ensure the realization of the modification; when the content is greater than 15%, it is easy to cause the enrichment of surface particles, thereby reducing the modification effect and increasing the cost.
  • the preparation methods under non-equilibrium conditions are supersonic flame spraying, explosive spraying, atmospheric plasma spraying, supersonic plasma spraying, (ultra) low pressure plasma spraying, plasma spraying-physical vapor deposition, At least one of electron beam deposition, cold spraying, and laser 3D printing.
  • the temperature of the heat treatment is 500-900° C., and the duration of the heat treatment is 1 to 24 h.
  • the mixing method is mechanical mixing or spray granulation.
  • the heat treatment is a heat treatment under a vacuum condition, a protective atmosphere or a reducing atmosphere.
  • the present invention also provides a metal material prepared by the modification method.
  • the in-situ stripping modified metal material of the present invention has a wide range of applications, and can be applied to the catalytic performance of metal catalysts in various aspects, such as the modification of hydrogen and oxygen evolution, the modification of oxygen reduction, the modification of hydrogenation performance, and the modification of catalytic cracking of organic compounds. Improved, and has a unique structural stability, significant commercial value.
  • the doped metal is pinned to the surface of the base metal in a nanostructure.
  • the dissolved nanoparticles are tightly combined with the substrate, have strong interaction, and the structure formed by the modification has high stability.
  • island-shaped nanoparticles can increase the roughness of the substrate surface and increase the specific surface area, thereby increasing the catalytic active sites of the metal material and improving the catalytic performance of the metal material.
  • the modification method of the present invention is simple to operate, and only needs to be mixed with a small amount of modified metal to be used as a raw material for preparation, and subsequently supplemented with heat treatment to obtain a modified metal catalyst.
  • the modification method of the present invention has a wide range of applications, including supersonic flame spraying, explosive spraying, atmospheric plasma spraying, supersonic plasma spraying, (ultra) low pressure plasma spraying, plasma spraying-physical vapor deposition, electron beam deposition, cold spraying , Laser 3D printing and other preparation technologies are applicable, with high application value.
  • the in-situ stripping-modified metal material of the present invention has a wide range of uses, and can be applied to various metal catalysts such as the modification of hydrogen and oxygen evolution, the modification of oxygen reduction, the modification of hydrogenation, the modification of catalytic cracking of organic compounds, etc.
  • the catalytic performance is improved, and it has unique structural stability, and its commercial value is significant.
  • Figure 1 is an SEM image of the surface of the untreated coated catalyst obtained in Example 1 of the present invention.
  • Example 2 is a SEM image of the surface of the coated catalyst obtained in Example 1 of the present invention after heat treatment for 4 hours;
  • Example 3 is a SEM image of the surface of the coated catalyst obtained in Example 1 of the present invention after 8 hours of heat treatment;
  • Example 4 is a graph showing the EDX result of the surface of the untreated coated catalyst obtained in Example 1 of the present invention.
  • Figure 5 is a graph showing the EDX result of the coated catalyst surface obtained in Example 1 of the present invention after 8 hours of heat treatment;
  • Figure 6 is an SEM image of the surface of the untreated coated catalyst obtained in Example 2 of the present invention.
  • Figure 7 is an SEM image of the surface of the coated catalyst obtained in Example 2 of the present invention after heat treatment for 4 hours;
  • Figure 8 is an SEM image of the surface of the coated catalyst obtained in Example 2 of the present invention after heat treatment for 8 hours;
  • Example 9 is a graph showing the EDX result of the cross-sectional surface layer of the coated catalyst obtained in Example 2 of the present invention after 8 hours of heat treatment;
  • Example 10 is a graph showing the EDX result of the cross-section bulk phase of the coated catalyst obtained in Example 2 of the present invention after 8 hours of heat treatment.
  • metal material of the present invention is prepared by the following method:
  • metal material of the present invention is prepared by the following method:
  • metal material of the present invention is prepared by the following method:
  • modified metal Fe powder weigh 499.5g of metal Fe powder as base metal powder, and weigh 0.5g of metal Au powder as modified metal powder.
  • the mass fraction of modified metal powder is 0.1%; move the weighed powder into a ball mill tank and use water as a dispersant , Mixed for 6 hours at a speed of 400r min -1 to make it fully mixed, and then dried in an oven as the raw material powder for use; the above raw material powder will be used to prepare the coating catalyst by atmospheric plasma spraying; the prepared coating catalyst Enclosed in a quartz tube, evacuated to vacuum at room temperature and backfilled with 300mbar argon; heat the sealed quartz tube in a muffle furnace to 500°C and keep it for 8h and 12h respectively. After the sintering process, open the quartz tube and take out the sample.
  • the modified metal material can be dissolved out in situ.
  • the surface morphology analysis of the prepared in-situ leaching modified metal material is the same as that of Example 1 and Example 2, and will not be repeated here.
  • metal material of the present invention is prepared by the following method:
  • the surface morphology analysis of the prepared in-situ leaching modified metal material is the same as that of Example 1 and Example 2, and will not be repeated here.

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Abstract

一种金属材料表面原位溶出改性方法，包括如下步骤：（1）将基底金属与改性金属粉末充分混合，得到原料粉末；（2）将步骤（1）得到的原料粉末通过非平衡条件下的制备手段制备得到金属材料；（3）对步骤（2）制备得到的金属材料进行热处理，使之达到平衡状态，降至室温后，掺杂相即溶出到金属材料表面，得到改性后的金属材料。

Description

一种金属材料及其表面原位溶出改性方法 技术领域
本发明涉及材料制备及改性领域，具体是涉及一种金属材料表面原位溶出改性以增强电化学性能的方法。
背景技术
目前，贵金属催化剂表现出了优异的电化学催化性能，但由于成本问题，并不适宜规模化应用。传统的催化剂如Fe、Co、Ni、Cu等也具有一定的催化活性，且由于其储量大、成本低，因此被广泛用于催化行业。随着现今催化行业的发展，诸如燃料电池、电解水、有机催化等技术对催化剂的活性需求日益增高，现阶段单一的传统催化剂已经不能够满足其催化性能的要求，需要进行材料改性以提高性能。然而，一般的材料改性方法如电沉积、磁控溅射、杂原子取代等，制备的改性粒子与基底材料间的相互作用不强，尽管会提升初期性能，但往往会导致稳定性的下降。其中，部分改性方法仅适用于实验室阶段，并不适合大规模生产应用。因此，开发一种新的稳定的金属材料表面改性方法迫在眉睫。
原位溶出是一种新兴的材料改性方法。它是一种非常稳定、高效的材料改性方法。采用该方法对传统金属催化剂进行改性，仅需要较少的贵金属，便可以在维持原有稳定性的条件下显著提高性能。因此，可以预见其在材料制备及改性领域良好的应用前景。目前，国内尚未见采用原位溶出法对金属材料表面改性的相关报道。
发明内容
基于此，本发明的目的在于克服上述现有技术的不足之处而提供一种金属材料表面原位溶出改性以增强电化学性能的方法。该方法针对传统金属催化剂的改性，可应用在多个材料加工及制备技术领域，仅需少量贵金属掺杂便可完成，操作方便，成本低廉，具有明显的实验价值和应用前景。
为实现上述目的，本发明所采取的技术方案为：一种金属材料表面原位溶出改性方法，包括如下步骤：
(1)将基底金属与改性金属粉末混合，得到原料粉末；
(2)将步骤(1)得到的原料粉末通过非平衡条件下的制备手段制备得到金属材料；
(3)对步骤(2)制备得到的金属材料进行热处理，使之达到平衡状态，掺杂相即溶出到金属材料表面，得到改性后的金属材料。
本发明的设计原理如下：原位溶出是一种新兴的材料改性方法。它是指在一定非平衡条件下将掺杂粒子与基底混合制备成金属材料，随后改变条件使金属材料达到稳定状态，利用掺杂金属的性能差异使其从体相溶出到达表面、形成纳米岛状钉扎结构。这种溶出的纳米粒子与基底结合紧密、相互作用强，改性形成的结构稳定性高。同时，岛状纳米颗粒可以增加基底表面的粗糙度，增大比表面积，从而增加金属材料催化活性位点，提高金属材料催化性能。
优选地，所述步骤(1)中，基底金属为Mn、Fe、Co、Ni、Cu、Zn中的至少一种。
优选地，所述步骤(1)中，改性金属为Mo、Ru、Rh、Pd、Ag、Ir、Pt、Au中的至少一种。
优选地，所述步骤(1)中，改性金属在原料粉末中的质量百分比为0.1～15％。当含量小于0.1％，无法保证改性金属的表面溶出以确保改性的实现；当含量大于15％，容易引起表面颗粒的富集从而降低改性效果并提高成本。
优选地，所述步骤(2)中，非平衡条件下的制备手段为超音速火焰喷涂、爆炸喷涂、大气等离子喷涂、超音速等离子喷涂、(超)低压等离子喷涂、等离子喷涂-物理气相沉积、电子束沉积、冷喷涂、激光3D打印中的至少一种。
优选地，所述步骤(3)中，根据改性金属在基底中的扩散速度不同，热处理的温度为500-900℃，热处理的时长为1～24h。
优选地，所述步骤(1)中，混合的方式为机械混合或喷雾造粒。
优选地，所述步骤(3)中，热处理是在真空条件、保护气氛或还原气氛下的热处理。
同时，本发明还提供一种所述的改性方法制备得到的金属材料。本发明的原位溶出改性金属材料用途广泛，可应用于氢氧析出性能改性、氧还原性能改性、氢氧化性能改性、有机化合物催化裂解改性等多个方面金属催化剂催化性能的提高，且具有独特的结构稳定性，商业化价值显著。
优选地，掺杂金属以纳米结构钉扎在基底金属的表面。这种溶出的纳米粒子与基底结合紧密、相互作用强，改性形成的结构稳定性高。同时，岛状纳米颗粒可以增加基底表面的粗糙度，增大比表面积，从而增加金属材料催化活性位点，提高金属材料催化性能。
相对于现有技术，本发明的有益效果为：
(1)本发明的改性方法操作简单，仅需要掺入少量改性金属混合后作为原料进行制备，后续辅以热处理即可得到改性后的金属催化剂。
(2)本发明的改性方法适用范围广泛，超音速火焰喷涂、爆炸喷涂、大气等离子喷涂、超音速等离子喷涂、(超)低压等离子喷涂、等离子喷涂-物理气相沉积、电子束沉积、冷喷涂、激光3D打印等制备技术均可适用，应用价值高。
(3)本发明的原位溶出改性金属材料用途广泛，可应用于氢氧析出性能改性、氧还原性能改性、氢氧化性能改性、有机化合物催化裂解改性等多个方面金属催化剂催化性能的提高，且具有独特的结构稳定性，商业化价值显著。
附图说明
图1为本发明实施例1中所得未处理的涂层催化剂表面SEM图；
图2为本发明实施例1中所得热处理4h后的涂层催化剂表面SEM图；
图3为本发明实施例1中所得热处理8h后的涂层催化剂表面SEM图；
图4为本发明实施例1中所得未处理的涂层催化剂表面EDX结果图；
图5为本发明实施例1中所得热处理8h后的涂层催化剂表面EDX结果图；
图6为本发明实施例2中所得未处理的涂层催化剂表面SEM图；
图7为本发明实施例2中所得热处理4h后的涂层催化剂表面SEM图；
图8为本发明实施例2中所得热处理8h后的涂层催化剂表面SEM图；
图9为本发明实施例2中所得热处理8h后的涂层催化剂截面表层EDX结果图；
图10为本发明实施例2中所得热处理8h后的涂层催化剂截面体相EDX结果图。
具体实施方式
为更好的说明本发明的目的、技术方案和优点，下面将结合附图和具体实施例对本发明作进一步说明。
实施例1
本发明所述金属材料的一种实施例，本实施例所述金属材料通过以下方法制备所得：
称取287.5g金属Ni粉作为基底金属粉末，称取25g金属Ag粉作为改性金属粉末，改性金属粉末质量分数为8％。将称取的粉末移入V形混料机，在10r min -1的转速条件下混合24h，使之充分混合，作为原料粉末待用。将以上述原料粉末采用大气等离子喷涂设备(APS)制备涂层催化剂。将所制备的涂层催化剂在20ml min -1氢气的保护下升温至800℃并分别保温4h、8h，烧结程序结束后打开石英管取出样品，即得原位溶出改性金属材料。
对未经热处理的原始涂层催化剂、热处理4h后的涂层催化剂、热处理8h后的涂层催化剂的表面分别进行SEM测试，如附图1～3所示。从图1～3中可以看出，未处理的涂层催化剂表面有着较多的未溶粉末颗粒。在热处理4h后，表面的未溶颗粒明显减少，表面变得光滑且晶界开始浮现；同时，部分晶界处出现少量溶出的小颗粒。热处理8h后，未溶的不规则颗粒已经完全消失，同时大量的球状纳米Ag颗粒钉扎在Ni的晶界处。对未处理催化剂和热处理8h后催化剂的表面SEM所选区域分别进行EDX测试，如附图4、5所示，可以看出，热处理后表面Ag的含量明显增加，即图3中的溶出纳米颗粒为改性所用的Ag颗粒。上述结果说明，采用原位溶出改性方法可以得到具有原位溶出的纳米钉扎结构的改性催化剂。
实施例2
本发明所述金属材料的一种实施例，本实施例所述金属材料通过以下方法制备所得：
称取475g金属Ni粉作为基底金属粉末，称取25g金属Ag粉作为改性金属粉末，改性金属粉末质量分数为5％；将称取的粉末移入球磨罐中，以水作为分散剂，在400r min -1的转速条件下混合6h，使之充分混合，随后烘箱中烘干作为原料粉末待用；将以上述原料粉末采用冷喷涂设备(CS)制备涂层催化剂；将所制备的涂层催化剂封入石英管中，室温下抽至真空并回填300mbar的氩气；将封好的石英管在马弗炉中升温至800℃并分别保温4h、8h，烧结程序结束后打开石英管取出样品，即得原位溶出改性金属材料。
在制备过程中，对未经热处理的原始涂层催化剂、热处理4h后的涂层催化剂、热处理8h后的涂层催化剂的表面分别进行SEM测试，如附图6～8所示。从附图6～8可以看出，未处理的涂层催化剂表面有着较多的未溶粉末颗粒；在热处理4h后，表面的未溶颗粒明显减少，表面变得光滑且晶界开始浮现；同时，部分晶界处出现少量溶出的小颗粒。热处理8h后，未溶的不规则颗粒已经完全消失，同时大量的球状纳米Ag颗粒钉扎在Ni的晶界处。对热处理8h后涂层催化剂截面的表层和体相分别进行EDX测试(图9、10)，可以看出热处理后表层Ag的含量明显增加，即涂层体相中的Ag有向表面扩散的趋势。上述结果说明，采用原位溶出改性方法可以得到具有原位溶出的纳米钉扎结构的改性催化剂。
实施例3
本发明所述金属材料的一种实施例，本实施例所述金属材料通过以下方法制备所得：
称取499.5g金属Fe粉作为基底金属粉末，称取0.5g金属Au粉作为改性金属粉末，改性金属粉末质量分数为0.1％；将称取的粉末移入球磨罐中，以水作为分散剂，在400r min -1的转速条件下混合6h，使之充分混合，随后烘箱中烘干作为原料粉末待用；将以上述原料粉末采用大气等离子喷涂制备涂层催化剂； 将所制备的涂层催化剂封入石英管中，室温下抽至真空并回填300mbar的氩气；将封好的石英管在马弗炉中升温至500℃并分别保温8h、12h，烧结程序结束后打开石英管取出样品，即得原位溶出改性金属材料。
对制备得到的原位溶出改性金属材料的表面形态分析同实施例1和实施例2，于此不再赘述。
实施例4
本发明所述金属材料的一种实施例，本实施例所述金属材料通过以下方法制备所得：
称取425g金属Co粉作为基底金属粉末，称取75g金属Pt粉作为改性金属粉末，改性金属粉末质量分数为15％；将称取的粉末移入球磨罐中，以水作为分散剂，在400r min -1的转速条件下混合6h，使之充分混合，随后烘箱中烘干作为原料粉末待用；将以上述原料粉末采用电子束沉积制备涂层催化剂；将所制备的涂层催化剂封入石英管中，室温下抽至真空并回填300mbar的氩气；将封好的石英管在马弗炉中升温至900℃并分别保温4h、8h，烧结程序结束后打开石英管取出样品，即得原位溶出改性金属材料。
对制备得到的原位溶出改性金属材料的表面形态分析同实施例1和实施例2，于此不再赘述。
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。

Claims (10)

  1. 一种金属材料表面原位溶出改性方法，其特征在于，包括如下步骤：
    (1)将基底金属与改性金属粉末混合，得到原料粉末；
    (2)将步骤(1)得到的原料粉末通过非平衡条件下的制备手段制备得到金属材料；
    (3)对步骤(2)制备得到的金属材料进行热处理，使之达到平衡状态，掺杂相即溶出到金属材料表面，得到改性后的金属材料。
  2. 如权利要求1所述的金属材料表面原位溶出改性方法，其特征在于，所述步骤(1)中，基底金属为Mn、Fe、Co、Ni、Cu、Zn中的至少一种。
  3. 如权利要求1所述的金属材料表面原位溶出改性方法，其特征在于，所述步骤(1)中，改性金属为Mo、Ru、Rh、Pd、Ag、Ir、Pt、Au中的至少一种。
  4. 如权利要求1所述的金属材料表面原位溶出改性方法，其特征在于，所述步骤(1)中，改性金属在原料粉末中的质量百分比为0.1～15％。
  5. 如权利要求1所述的金属材料表面原位溶出改性方法，其特征在于，所述步骤(2)中，非平衡条件下的制备手段为超音速火焰喷涂、爆炸喷涂、大气等离子喷涂、超音速等离子喷涂、(超)低压等离子喷涂、等离子喷涂-物理气相沉积、电子束沉积、冷喷涂、激光3D打印中的至少一种。
  6. 如权利要求1所述的金属材料表面原位溶出改性方法，其特征在于，所述步骤(3)中，热处理的温度为500-900℃，热处理的时长为1～24h。
  7. 如权利要求1所述的金属材料表面原位溶出改性方法，其特征在于，所述步骤(1)中，混合的方式为机械混合或喷雾造粒。
  8. 如权利要求1所述的金属材料表面原位溶出改性方法，其特征在于，所述步骤(3)中，热处理是在真空条件、保护气氛或还原气氛下的热处理。
  9. 一种由权利要求1～8任一项所述的改性方法制备得到的金属材料。
  10. 如权利要求9所述的金属材料，其特征在于，掺杂金属以纳米结构钉 扎在基底金属的表面。
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