CN102925779B - Method for preparing cobalt-nickel-aluminum (Co-Ni-Al) alloy based on electroplating and thermal diffusion - Google Patents

Method for preparing cobalt-nickel-aluminum (Co-Ni-Al) alloy based on electroplating and thermal diffusion Download PDF

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CN102925779B
CN102925779B CN201210409311.4A CN201210409311A CN102925779B CN 102925779 B CN102925779 B CN 102925779B CN 201210409311 A CN201210409311 A CN 201210409311A CN 102925779 B CN102925779 B CN 102925779B
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alloy
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pure aluminum
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CN102925779A (en
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胡永俊
李昔强
郑辉庭
成晓玲
胡光辉
李风
何志泉
刘瑞强
陈铁文
庞建业
梁振标
甄余炳
林涌
黄晓争
徐志隆
钟彬强
何健楠
骆志捷
黄春檑
何远川
刘毅然
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Guangdong University of Technology
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Abstract

本发明公开了一种基于电镀热扩散制备Co-Ni-Al合金的方法,本发明以铝箔为基材进行复合电镀Co-Ni合金层,通过热处理扩散形成Co-Ni-Al磁控形状记忆合金;本发明提供的Co-Ni-Al合金制备方法工艺简单,性能稳定性好,较好地解决当前Co-Ni-Al磁控记忆合金尚存的驱动磁场大、磁致应变小等瓶颈技术,促进磁控记忆合金在大功率水下声纳、微位移器、震动和噪声控制、线性马达、微波器件、机器人等领域的实际应用。The invention discloses a method for preparing Co-Ni-Al alloy based on electroplating thermal diffusion. In the invention, aluminum foil is used as a base material for composite electroplating Co-Ni alloy layer, and Co-Ni-Al magnetic control shape memory alloy is formed by heat treatment and diffusion. The Co-Ni-Al alloy preparation method provided by the present invention has simple process and good performance stability, and can better solve the existing bottleneck technologies of the current Co-Ni-Al magnetron memory alloy such as large driving magnetic field and small magnetic strain, Promote the practical application of magnetic control memory alloys in high-power underwater sonar, micro-displacement, vibration and noise control, linear motors, microwave devices, robots and other fields.

Description

一种基于电镀热扩散制备Co-Ni-Al合金的方法A method for preparing Co-Ni-Al alloy based on electroplating thermal diffusion

技术领域 technical field

本发明涉及磁控形状记忆金属功能材料制备技术,具体涉及一种基于电镀热扩散制备Co-Ni-Al合金的方法。 The invention relates to the preparation technology of magnetically controlled shape memory metal functional materials, in particular to a method for preparing Co-Ni-Al alloys based on electroplating thermal diffusion.

背景技术 Background technique

磁性形状记忆合金,(Magnetic Shape Memory Alloy,MSMA)不但具有传统形状记忆合金受温度场控制的热弹性形状记忆效应,而且具有受磁场控制的磁性形状记忆效应。因此,合金兼有大恢复应变、大输出应力、高响应频率和可精确控制的综合特性,使其可能在大功率水下声纳、微位移器、震动和噪声控制、线性马达、微波器件、机器人等领域有重要应用,有望成为压电陶瓷和磁致伸缩材料之后的新一代驱动与传感材料。目前,已发现的磁性形状记忆合金主要包括:Ni系合金Ni-Mn-Ga,Ni-Al-Mn,Ni-Co-Al,Ni-Fe-Ga-Co等;Co系合金Co-Mn,Co-Ni,Co-Ni-Ga等;Fe系合金Fe-Pd,Fe-Mn-Si,Fe-Ni-Co-Ti,Fe-Pt,等.其中,Ni-Mn-Ga合金是最早发现的MSMA, 其研究较为成熟,已有应用于直线驱动器、直线电机等方面的报道,但合金性能的稳定性和重复性不够理想。 Magnetic shape memory alloy (Magnetic Shape Memory Alloy, MSMA) not only has the thermoelastic shape memory effect controlled by the temperature field of the traditional shape memory alloy, but also has the magnetic shape memory effect controlled by the magnetic field. Therefore, the alloy has the comprehensive characteristics of large recovery strain, large output stress, high response frequency and precise control, making it possible to be used in high-power underwater sonar, micro-displacement, vibration and noise control, linear motors, microwave devices, There are important applications in robotics and other fields, and it is expected to become a new generation of driving and sensing materials after piezoelectric ceramics and magnetostrictive materials. At present, the magnetic shape memory alloys that have been discovered mainly include: Ni-based alloys Ni-Mn-Ga, Ni-Al-Mn, Ni-Co-Al, Ni-Fe-Ga-Co, etc.; Co-based alloys Co-Mn, Co -Ni, Co-Ni-Ga, etc.; Fe-based alloys Fe-Pd, Fe-Mn-Si, Fe-Ni-Co-Ti, Fe-Pt, etc. Among them, Ni-Mn-Ga alloy is the earliest discovered MSMA , Its research is relatively mature, and there have been reports on linear drives, linear motors, etc., but the stability and repeatability of the alloy properties are not ideal.

    Co基铁磁形状记忆合金包括Co-Ni-Ga和Co-Ni-Al两类合金,具有磁晶各向异性能大和热加工性能优异等优点。Co-Ni-Al是唯一一种以共晶方式凝固的MSMA,且存在宽结晶范围的两相共存区,并在功能成分范围内展现出丰富的多相共存行为,制备方法相对简单,价格低廉,具有较大的应用前景。 Co-based ferromagnetic shape memory alloys include Co-Ni-Ga and Co-Ni-Al alloys, which have the advantages of large magnetocrystalline anisotropy and excellent thermal processing performance. Co-Ni-Al is the only MSMA that is solidified in a eutectic manner, and there is a two-phase coexistence region with a wide crystallization range, and exhibits rich multi-phase coexistence behavior within the range of functional components. The preparation method is relatively simple and the price is low. It is cheap and has great application prospects.

国内外研究学者采用常规凝固、深过冷凝固、定向凝固、快速凝固及粉末冶金的方法等制备条件下Co-Ni-Al合金,具有良好的应变诱发形状记忆效应,但仍未解决CoNiAl合金的驱动磁场大、磁致应变小的技术瓶颈。 Researchers at home and abroad have prepared Co-Ni-Al alloys under conventional solidification, deep supercooled solidification, directional solidification, rapid solidification, and powder metallurgy methods, which have good strain-induced shape memory effects, but have not yet solved the problem of CoNiAl alloys. The technical bottleneck of large driving magnetic field and small magnetic strain.

本发明利用在铝箔进行复合电镀Co-Ni合金,通过调整热处理工艺参数,最终制备出综合性能优良的Co-Ni-Al合金。 The invention utilizes the composite electroplating of Co-Ni alloy on the aluminum foil, and finally prepares the Co-Ni-Al alloy with excellent comprehensive performance by adjusting the heat treatment process parameters.

发明内容 Contents of the invention

本发明提供的一种基于电镀热扩散制备Co-Ni-Al合金的方法,有如下步骤: A method for preparing Co-Ni-Al alloy based on electroplating thermal diffusion provided by the present invention has the following steps:

1)在纯铝基材表面电镀Co-Ni合金镀层,上述Co-Ni合金镀层中镍的质量比为10~90%;   1) Co-Ni alloy coating is electroplated on the surface of pure aluminum substrate, and the mass ratio of nickel in the above Co-Ni alloy coating is 10-90%; 

2)将电镀后的Co-Ni/Al放入加热器中,在温度为250℃~600℃保温60~240小时,扩散形成均匀的Co-Ni-Al合金,随炉冷却至室温后取出。 2) Put the electroplated Co-Ni/Al into the heater, keep it at a temperature of 250°C-600°C for 60-240 hours, diffuse to form a uniform Co-Ni-Al alloy, and take it out after cooling to room temperature with the furnace.

上述步骤1)中纯铝基材厚度为0.01mm~0.3mm。 The thickness of the pure aluminum substrate in the above step 1) is 0.01mm-0.3mm.

上述步骤1)中电镀的工艺流程为:在室温下对纯铝基材表面用蒸馏水冲洗清洁除油,清洁除油后将其置于由体积比为20%的硝酸、体积比为1%的氢氟酸和余量去离子水组成的酸蚀液中,在室温下酸蚀时间为40小时;然后使用去离子水水洗;室温下,将试样放入由15 g/L硫酸镍和112 g/L柠檬酸钠混合组成的pH值为13的溶液中进行活化,之后置于电镀液中电镀;停止电镀试样洗涤吹干。 The electroplating process in the above step 1) is as follows: at room temperature, the surface of the pure aluminum substrate is cleaned and degreased with distilled water. In the acid etching solution composed of hydrofluoric acid and the remaining amount of deionized water, the etching time at room temperature is 40 hours; then use deionized water to wash; at room temperature, put the sample into a mixture of 15 g/L nickel sulfate and 112 g/L sodium citrate mixed in a solution with a pH value of 13 for activation, and then placed in the electroplating solution for electroplating; stop electroplating and wash and dry the samples.

上述电镀以纯铝为阳极,所述电镀液的配方是:硫酸镍100~250 g/L,氯化钠 10~20 g/L,硼酸20~40 g/L,硫酸钴10~120 g/L,糖精1g/L;电镀过程中恒电流,电流0.15A,镀液pH值为4.6。调整电镀液组成及电镀参数可在纯铝基材上获得不同成分的Co-Ni合金镀层。 The above-mentioned electroplating uses pure aluminum as the anode, and the formula of the electroplating solution is: nickel sulfate 100-250 g/L, sodium chloride 10-20 g/L, boric acid 20-40 g/L, cobalt sulfate 10-120 g/L , saccharin 1g/L; constant current during the electroplating process, the current is 0.15A, and the pH value of the plating solution is 4.6. Co-Ni alloy coatings with different compositions can be obtained on pure aluminum substrates by adjusting the composition of the electroplating solution and the electroplating parameters.

上述步骤2)中加热器为马弗炉或真空炉;马弗炉为避免镀层氧化,采取通入氮气、氩气或氢气保护性气体,或将Co-Ni/Al放入碳粉还原性物质中加热。 The heater in the above step 2) is a muffle furnace or a vacuum furnace; in order to avoid oxidation of the coating, the muffle furnace adopts nitrogen, argon or hydrogen protective gas, or puts Co-Ni/Al into carbon powder reducing substances medium heat.

上述步骤2)中保温时间根据纯铝基材和镀层厚度决定,加热至扩散得到成分均匀Co-Ni-Al合金。 The holding time in the above step 2) is determined according to the pure aluminum substrate and the thickness of the coating, and the Co-Ni-Al alloy with uniform composition is obtained by heating until diffusion.

本发明的有益效果: Beneficial effects of the present invention:

1.采用复合电镀的方法在铝基材上制备Co-Ni合金,控制热处理工艺、镀层的成分和基体的厚度等参数,制备出综合性能优良Co-Ni-Al合金。 1. The Co-Ni alloy is prepared on the aluminum substrate by the method of composite electroplating, and the parameters such as the heat treatment process, the composition of the coating and the thickness of the substrate are controlled to prepare a Co-Ni-Al alloy with excellent comprehensive properties.

2.制备Co-Ni-Al合金的设备成本和技术要求低,只需要简单的电源和加热器即可制备出Co-Ni-Al合金。 2. The equipment cost and technical requirements for preparing the Co-Ni-Al alloy are low, and the Co-Ni-Al alloy can be prepared only by a simple power supply and a heater.

3. 本发明制备方法工艺简单,性能稳定性好,较好地解决当前Co-Ni-Al磁控记忆合金尚存的驱动磁场大、磁致应变小等瓶颈技术难点。 3. The preparation method of the present invention has simple process and good performance stability, and can better solve the existing bottleneck technical difficulties of the current Co-Ni-Al magnetron memory alloy such as large driving magnetic field and small magnetic strain.

具体实施方式 Detailed ways

下面结合 具体实施例详述本发明。 The present invention is described in detail below in conjunction with specific embodiment.

实施例1 Example 1

1)在0.05mm厚度的纯铝基材表面,室温下对纯铝基材表面用蒸馏水冲洗清洁除油,清洁除油后将其置于由体积比为20%的硝酸、体积比为1%的氢氟酸和余量去离子水组成的酸蚀液中,在室温下酸蚀时间为40小时;然后使用去离子水水洗;室温下,将试样放入由15 g/L硫酸镍和112 g/L柠檬酸钠混合组成的pH值为13的溶液中进行活化,之后置于电镀液中电镀;停止电镀试样洗涤吹干。 1) On the surface of a pure aluminum substrate with a thickness of 0.05mm, wash and degrease the surface of the pure aluminum substrate with distilled water at room temperature. After cleaning and degreasing, place it in nitric acid with a volume ratio of 20% and a volume ratio of 1%. In the acid etching solution composed of hydrofluoric acid and the remaining amount of deionized water, the etching time at room temperature is 40 hours; then use deionized water to wash; at room temperature, put the sample into a mixture of 15 g/L nickel sulfate and 112 g/L sodium citrate mixture solution with a pH value of 13 was activated, and then placed in the electroplating solution for electroplating; the electroplating sample was stopped and washed and dried.

上述电镀液的组成配方是:硫酸镍250g/L,氯化钠10 g/L,硼酸40 g/L,硫酸钴55 g/L,糖精1g/L;电镀参数是:施镀过程中恒电流,电流0.15A,镀液pH值为4.6。停止电镀试样洗涤吹干,得到Co-54.2%Ni合金镀层,其中上述Co-Ni合金镀层中镍的质量比为54.2%;   The composition formula of above-mentioned electroplating solution is: nickel sulfate 250g/L, sodium chloride 10 g/L, boric acid 40 g/L, cobalt sulfate 55 g/L, saccharin 1g/L; , the current is 0.15A, and the pH value of the bath is 4.6. Stop electroplating sample washing and drying, obtain Co-54.2%Ni alloy coating, wherein the mass ratio of nickel in the above-mentioned Co-Ni alloy coating is 54.2%;

 2)将电镀后的Co-54.2%Ni /Al试样放入马弗炉,在温度为550℃、氩气气氛下保温60小时后得到成分为Co-45.0%Ni-17%Al合金。 2) Put the electroplated Co-54.2%Ni /Al sample into the muffle furnace, and keep it at a temperature of 550°C under an argon atmosphere for 60 hours to obtain a Co-45.0%Ni-17%Al alloy.

3)随炉冷却至室温后取出。 3) Take it out after cooling to room temperature with the furnace.

实施例2 Example 2

1)    在0.1mm厚度的纯铝基材表面,室温下对纯铝基材表面用蒸馏水冲洗清洁除油,清洁除油后将其置于由体积比为20%的硝酸、体积比为1%的氢氟酸和余量去离子水组成的酸蚀液中,在室温下酸蚀时间为40小时;然后使用去离子水水洗;室温下,将试样放入由15 g/L硫酸镍和112 g/L柠檬酸钠混合组成的pH值为13的溶液中进行活化,之后置于电镀液中电镀;停止电镀试样洗涤吹干。 1) On the surface of a pure aluminum substrate with a thickness of 0.1 mm, wash the surface of the pure aluminum substrate with distilled water to remove oil at room temperature, and place it in nitric acid with a volume ratio of 20% and a volume ratio of 1% after cleaning and degreasing In the acid etching solution composed of hydrofluoric acid and the remaining amount of deionized water, the etching time at room temperature is 40 hours; then use deionized water to wash; at room temperature, put the sample into a mixture of 15 g/L nickel sulfate and 112 g/L sodium citrate mixture solution with a pH value of 13 was activated, and then placed in the electroplating solution for electroplating; the electroplating sample was stopped and washed and dried.

上述电镀液的组成配方是:硫酸镍100g/L,氯化钠20 g/L,硼酸40 g/L,硫酸钴120 g/L,糖精1g/L;电镀参数是:施镀过程中恒电流,电流0.15A,镀液pH值为4.6。 停止电镀试样洗涤吹干,得到Co-9.9%Ni合金镀层,其中上述Co-Ni合金镀层中镍的质量比为9.9%;   The composition formula of above-mentioned electroplating solution is: nickel sulfate 100g/L, sodium chloride 20 g/L, boric acid 40 g/L, cobalt sulfate 120 g/L, saccharin 1g/L; Electroplating parameter is: constant current during plating process , the current is 0.15A, and the pH value of the bath is 4.6. Stop washing and drying the electroplating sample to obtain a Co-9.9%Ni alloy coating, wherein the mass ratio of nickel in the above-mentioned Co-Ni alloy coating is 9.9%;

2) 将电镀后的Co-9.9%Ni /Al试样放入真空热出炉中,在温度为300℃下保温200小时后得到成分为Co-6.0%Ni-40.0%Al合金。 2) Put the electroplated Co-9.9%Ni /Al sample into a vacuum hot furnace, and keep it at 300°C for 200 hours to obtain a Co-6.0%Ni-40.0%Al alloy.

3)随炉冷却至室温后取出。 3) Take it out after cooling to room temperature with the furnace.

实施例3 Example 3

1)              在0.2mm厚度的纯铝基材表面,室温下对纯铝基材表面用蒸馏水冲洗清洁除油,清洁除油后将其置于由体积比为20%的硝酸、体积比为1%的氢氟酸和余量去离子水组成的酸蚀液中,在室温下酸蚀时间为40小时;然后使用去离子水水洗;室温下,将试样放入由15 g/L硫酸镍和112 g/L柠檬酸钠混合组成的pH值为13的溶液中进行活化,之后置于电镀液中电镀;停止电镀试样洗涤吹干。 1) On the surface of a pure aluminum substrate with a thickness of 0.2mm, wash and degrease the surface of the pure aluminum substrate with distilled water at room temperature. After cleaning and degreasing, place it in nitric acid with a volume ratio of 20% and a volume ratio of 1%. In the acid etching solution composed of hydrofluoric acid and the remaining amount of deionized water, the etching time at room temperature is 40 hours; then use deionized water to wash; at room temperature, put the sample into a mixture of 15 g/L nickel sulfate and 112 g/L sodium citrate mixture solution with a pH value of 13 was activated, and then placed in the electroplating solution for electroplating; the electroplating sample was stopped and washed and dried.

上述电镀液的组成配方是:硫酸镍175g/L,氯化钠20 g/L,硼酸20 g/L,硫酸钴10 g/L,糖精1g/L;电镀参数是:施镀过程中恒电流,电流0.15A,镀液pH值为4.6。 停止电镀试样洗涤吹干,得到Co-41.5%Ni合金镀层,其中上述Co-Ni合金镀层中镍的质量比为41.5%;   The composition formula of above-mentioned electroplating solution is: nickel sulfate 175g/L, sodium chloride 20 g/L, boric acid 20 g/L, cobalt sulfate 10 g/L, saccharin 1g/L; , the current is 0.15A, and the pH value of the bath is 4.6. Stop washing and drying the electroplating sample to obtain a Co-41.5%Ni alloy coating, wherein the mass ratio of nickel in the above-mentioned Co-Ni alloy coating is 41.5%;

2)将电镀后的Co-41.5%Ni /Al试样放入马弗炉中,在温度为400℃、氮气气氛保温180小时后得到成分为Co-35.0%Ni-14.5%Al合金。 2) Put the electroplated Co-41.5%Ni /Al sample into a muffle furnace, and keep it at a temperature of 400°C in a nitrogen atmosphere for 180 hours to obtain a Co-35.0%Ni-14.5%Al alloy.

3)随炉冷却至室温后取出。 3) Take it out after cooling to room temperature with the furnace.

实施例4 Example 4

1)    在0.15mm厚度的纯铝基材表面,室温下对纯铝基材表面用蒸馏水冲洗清洁除油,清洁除油后将其置于由体积比为20%的硝酸、体积比为1%的氢氟酸和余量去离子水组成的酸蚀液中,在室温下酸蚀时间为40小时;然后使用去离子水水洗;室温下,将试样放入由15 g/L硫酸镍和112 g/L柠檬酸钠混合组成的pH值为13的溶液中进行活化,之后置于电镀液中电镀;停止电镀试样洗涤吹干。  1) On the surface of a pure aluminum substrate with a thickness of 0.15mm, wash and degrease the surface of the pure aluminum substrate with distilled water at room temperature. After cleaning and degreasing, place it in nitric acid with a volume ratio of 20% and a volume ratio of 1%. In the acid etching solution composed of hydrofluoric acid and the remaining amount of deionized water, the etching time at room temperature is 40 hours; then use deionized water to wash; at room temperature, put the sample into a mixture of 15 g/L nickel sulfate and 112 g/L sodium citrate mixture solution with a pH value of 13 was activated, and then placed in the electroplating solution for electroplating; the electroplating sample was stopped and washed and dried. the

上述电镀液的组成配方是:硫酸镍250g/L,氯化钠20 g/L,硼酸30 g/L,硫酸钴10 g/L,糖精1g/L;电镀参数是:施镀过程中恒电流,电流0.15A,镀液pH值为4.6。停止电镀试样洗涤吹干,得到Co-88.3%Ni合金镀层,其中上述Co-Ni合金镀层中镍的质量比为88.3%;   The composition formula of above-mentioned electroplating solution is: nickel sulfate 250g/L, sodium chloride 20 g/L, boric acid 30 g/L, cobalt sulfate 10 g/L, saccharin 1g/L; , the current is 0.15A, and the pH value of the bath is 4.6. Stop electroplating sample washing and drying, obtain Co-88.3%Ni alloy coating, wherein the mass ratio of nickel in the above-mentioned Co-Ni alloy coating is 88.3%;

2)将电镀后的Co-88.3%Ni /Al试样放入马弗炉中,在温度为600℃、碳粉包覆下保温80小时后得到成分为Co-80%Ni-9.4%Al合金。 2) Put the electroplated Co-88.3%Ni /Al sample into a muffle furnace, and keep it at 600°C for 80 hours under carbon powder coating to obtain a Co-80%Ni-9.4%Al alloy .

3)随炉冷却至室温后取出。 3) Take it out after cooling to room temperature with the furnace.

实施例5 Example 5

1)    在0.3mm厚度的纯铝基材表面,室温下对纯铝基材表面用蒸馏水冲洗清洁除油,清洁除油后将其置于由体积比为20%的硝酸、体积比为1%的氢氟酸和余量去离子水组成的酸蚀液中,在室温下酸蚀时间为40小时;然后使用去离子水水洗;室温下,将试样放入由15 g/L硫酸镍和112 g/L柠檬酸钠混合组成的pH值为13的溶液中进行活化,之后置于电镀液中电镀;停止电镀试样洗涤吹干。 1) On the surface of a pure aluminum substrate with a thickness of 0.3mm, wash and degrease the surface of the pure aluminum substrate with distilled water at room temperature. After cleaning and degreasing, place it in nitric acid with a volume ratio of 20% and a volume ratio of 1%. In the acid etching solution composed of hydrofluoric acid and the remaining amount of deionized water, the etching time at room temperature is 40 hours; then use deionized water to wash; at room temperature, put the sample into a mixture of 15 g/L nickel sulfate and 112 g/L sodium citrate mixture solution with a pH value of 13 was activated, and then placed in the electroplating solution for electroplating; the electroplating sample was stopped and washed and dried.

上述电镀液的组成配方是:硫酸镍220g/L,氯化钠15 g/L,硼酸40 g/L,硫酸钴50 g/L,糖精1g/L;电镀参数是:施镀过程中恒电流,电流0.15A,镀液pH值为4.6。停止电镀试样洗涤吹干,得到Co-49.9%Ni合金镀层,其中上述Co-Ni合金镀层中镍的质量比为49.9%;   The composition formula of above-mentioned electroplating solution is: nickel sulfate 220g/L, sodium chloride 15 g/L, boric acid 40 g/L, cobalt sulfate 50 g/L, saccharin 1g/L; , the current is 0.15A, and the pH value of the bath is 4.6. Stop electroplating sample washing and drying, obtain Co-49.9%Ni alloy coating, wherein the mass ratio of nickel in the above-mentioned Co-Ni alloy coating is 49.9%;

2)将电镀后的Co-49.9%Ni /Al试样放入马弗炉中,在温度为450℃、在真空热出炉内保温240小时后得到成分为Co-14.9%Ni-70.2%Al合金。 2) Put the electroplated Co-49.9%Ni /Al sample into a muffle furnace, and keep it in a vacuum heat furnace for 240 hours at a temperature of 450°C to obtain a Co-14.9%Ni-70.2%Al alloy .

3)随炉冷却至室温后取出。 3) Take it out after cooling to room temperature with the furnace.

Claims (4)

1.一种基于电镀热扩散制备Co-Ni-Al合金的方法,其特征在于该方法有如下步骤: 1. A method for preparing Co-Ni-Al alloy based on electroplating thermal diffusion, is characterized in that the method has the following steps: 1)在纯铝基材表面电镀Co-Ni合金镀层,上述Co-Ni合金镀层中镍的质量比为10~90%;  上述电镀的工艺流程为:在室温下对纯铝基材表面用蒸馏水冲洗清洁除油,清洁除油后将其置于由体积比为20%的硝酸、体积比为1%的氢氟酸和余量去离子水组成的酸蚀液中,在室温下酸蚀时间为40小时;然后使用去离子水水洗;室温下,将试样放入由15 g/L硫酸镍和112 g/L柠檬酸钠混合组成的pH值为13的溶液中进行活化,之后置于电镀液中电镀;停止电镀试样洗涤吹干;上述电镀以纯铝为阳极;所述电镀液的配方是:硫酸镍100~250 g/L,氯化钠 10~20 g/L,硼酸20~40 g/L,硫酸钴10~120 g/L,糖精1g/L;电镀过程中恒电流,电流0.15A,镀液pH值为4.6; 1) Co-Ni alloy coating is electroplated on the surface of pure aluminum substrate, the mass ratio of nickel in the above Co-Ni alloy coating is 10-90%; the above electroplating process is: use distilled water on the surface of pure aluminum substrate at room temperature After cleaning and degreasing, place it in an acid etching solution consisting of 20% nitric acid by volume, 1% hydrofluoric acid by volume and the rest of deionized water. Etch time at room temperature for 40 hours; then wash with deionized water; at room temperature, put the sample into a solution with a pH value of 13 consisting of 15 g/L nickel sulfate and 112 g/L sodium citrate for activation, and then place it in Electroplating in the electroplating solution; stop washing and drying the electroplating sample; the above-mentioned electroplating uses pure aluminum as the anode; the formula of the electroplating solution is: nickel sulfate 100-250 g/L, sodium chloride 10-20 g/L, boric acid 20-20 g/L 40 g/L, cobalt sulfate 10-120 g/L, saccharin 1g/L; constant current during the electroplating process, the current is 0.15A, and the pH value of the plating solution is 4.6; 2)将电镀后的Co-Ni/Al放入加热器中,在温度为250℃~600℃保温60~240小时,扩散形成均匀的Co-Ni-Al合金,随炉冷却至室温后取出。 2) Put the electroplated Co-Ni/Al into the heater, keep it at a temperature of 250°C-600°C for 60-240 hours, diffuse to form a uniform Co-Ni-Al alloy, and take it out after cooling to room temperature with the furnace. 2.根据权利要求1所述的方法,其特征在于:上述步骤1)中纯铝基材厚度为0.01mm~0.3mm。 2. The method according to claim 1, characterized in that: the thickness of the pure aluminum substrate in the above step 1) is 0.01mm-0.3mm. 3.根据权利要求1所述的方法,其特征在于:上述步骤2)中加热器为马弗炉或真空炉;马弗炉为避免镀层氧化,采取通入氮气、氩气或氢气保护性气体,或将Co-Ni/Al放入碳粉还原性物质中加热。 3. The method according to claim 1, characterized in that: the heater in the above step 2) is a muffle furnace or a vacuum furnace; in order to avoid oxidation of the coating, the muffle furnace adopts nitrogen, argon or hydrogen protective gas , or put Co-Ni/Al into the carbon powder reducing substance and heat it. 4.根据权利要求1所述的方法,其特征在于:上述步骤2)中保温时间根据纯铝基材和镀层厚度决定,加热至扩散得到成分均匀Co-Ni-Al合金。 4. The method according to claim 1, characterized in that: the holding time in the above step 2) is determined according to the pure aluminum substrate and the thickness of the coating, and the Co-Ni-Al alloy with uniform composition is obtained by heating until diffusion.
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