熔盐电镀铝镍合金和铝锰合金
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摘要
铝合金具有优异的耐腐蚀性、强度、加工性等,而且合金元素的加入能有效抑制铝的结晶生长。熔盐电镀过程热应力小,对基体材料几乎无损伤且结合力好,可以再进行焊接等加工；镀层的厚度也可以根据需要进行控制,对基体材料没有什么限制,可广泛应用于钢铁、铜、镍,板材、棒材等各种材料各种形状的表面,具有广阔的应用前景。
本文研究了低温氯化物熔盐体系中,在不锈钢板上电镀Al-Ni合金的电镀工艺,讨论了工艺参数对电镀Al-Ni合金的沉积速率、镀层组成、电流效率等的影响。利用电子扫描显微镜(SEM)、X射线热场能谱仪(EDS)、X射线荧光光谱仪(XRF)和多晶X射线衍射仪(XRD)对制得的合金镀层的表面形貌及微观成分结构进行了表征及分析。采用电化学阳极极化曲线和HV-1000型显微维氏硬度计对Al-Ni合金和Al-Mn合金镀层的耐蚀性和硬度等性能进行了检测。研究了Al-Ni合金在不锈钢钢电极上的沉积机理。
实验结果表明,NiCl2在熔盐体系中的添加量对合金镀层的性能有明显作用,NiCl2的加入可使晶粒更加细致紧密,从而改善镀层形貌,利于Al、Ni合金相的形成,可大大提高耐蚀性和硬度,当镀层中Ni含量达6.19%时,硬度可高达7200Mpa。对循环伏安曲线分析可知Al-Ni合金在钢电极上是分三步沉积的。当镀层中Mn含量在32.21%左右时Al-Mn合金镀层有最佳耐蚀性及硬度值。Al-Mn合金镀层的耐蚀性要比Al-Ni合金镀层好,但Al-Ni合金的硬度值较大,几乎是Al-Mn合金的2倍。
Aluminum alloy has great corrosion resistance, strength and processing, etc., other elements are adding to inhibit effectively the crystal growth of aluminum. The plating process has small thermal stress, well binding force, and almost no damage to the substrate material. Coating thickness can be controlled as need, the plating has no restrictions to the base material, can be widely used on the surface of various of materials and shapes such as steel, copper, nickel, plates, rods, etc., has broad application prospects.
The technology of electroplating aluminum-nickel alloy layers from low temperature chloride molten salts was studied in this paper. The process parameters' effects on the deposit-ion rate, the coating composition and the current efficiency of Al-Ni alloy coating were discussed. The surface morphology and microcosmic phase composition were characterized and analyzed by scanning electron microscopy (SEM), X-ray thermal field energy dispersive spectrometer (EDS), X-ray fluorescence spectrometer (XRF) and polycrystalline X-ray diff-raction (XRD). The properties such as corrosion resistance and hardness of the Al-Ni alloy and Al-Mn alloy were detected using electrochemical anodic polarization curve and HV-1000 type Vickers hardness tester. The parper also studied the mechanism of deposition process of the Al-Ni alloy on steel electrode.
The experiment results have show that the addition of NiCl2 in the molten salt has a direct impact on the performance of the alloy coatings. It can perfect the coating morphology, help the formation of Al, Ni alloy phase, greatly improve the corrosion resistance and hardness, and the maximum hardness value can reach 7200Mpa when the Ni content in the coating was 6.19%. The cyclic voltammetry curves show that the Al-Ni alloy coating on steel electrode was deposited in three stages. The Al-Mn alloy coating had the best corrosion resistance and hardness when the Mn content was about 32.21%. Al-Mn alloy coating have the better corrosion resistance than Al-Ni alloy coating, but the hardness of Al-Ni alloy coating is large, almost is two times higher than the Al-Mn alloy coating.
本文研究了低温氯化物熔盐体系中,在不锈钢板上电镀Al-Ni合金的电镀工艺,讨论了工艺参数对电镀Al-Ni合金的沉积速率、镀层组成、电流效率等的影响。利用电子扫描显微镜(SEM)、X射线热场能谱仪(EDS)、X射线荧光光谱仪(XRF)和多晶X射线衍射仪(XRD)对制得的合金镀层的表面形貌及微观成分结构进行了表征及分析。采用电化学阳极极化曲线和HV-1000型显微维氏硬度计对Al-Ni合金和Al-Mn合金镀层的耐蚀性和硬度等性能进行了检测。研究了Al-Ni合金在不锈钢钢电极上的沉积机理。
实验结果表明,NiCl2在熔盐体系中的添加量对合金镀层的性能有明显作用,NiCl2的加入可使晶粒更加细致紧密,从而改善镀层形貌,利于Al、Ni合金相的形成,可大大提高耐蚀性和硬度,当镀层中Ni含量达6.19%时,硬度可高达7200Mpa。对循环伏安曲线分析可知Al-Ni合金在钢电极上是分三步沉积的。当镀层中Mn含量在32.21%左右时Al-Mn合金镀层有最佳耐蚀性及硬度值。Al-Mn合金镀层的耐蚀性要比Al-Ni合金镀层好,但Al-Ni合金的硬度值较大,几乎是Al-Mn合金的2倍。
Aluminum alloy has great corrosion resistance, strength and processing, etc., other elements are adding to inhibit effectively the crystal growth of aluminum. The plating process has small thermal stress, well binding force, and almost no damage to the substrate material. Coating thickness can be controlled as need, the plating has no restrictions to the base material, can be widely used on the surface of various of materials and shapes such as steel, copper, nickel, plates, rods, etc., has broad application prospects.
The technology of electroplating aluminum-nickel alloy layers from low temperature chloride molten salts was studied in this paper. The process parameters' effects on the deposit-ion rate, the coating composition and the current efficiency of Al-Ni alloy coating were discussed. The surface morphology and microcosmic phase composition were characterized and analyzed by scanning electron microscopy (SEM), X-ray thermal field energy dispersive spectrometer (EDS), X-ray fluorescence spectrometer (XRF) and polycrystalline X-ray diff-raction (XRD). The properties such as corrosion resistance and hardness of the Al-Ni alloy and Al-Mn alloy were detected using electrochemical anodic polarization curve and HV-1000 type Vickers hardness tester. The parper also studied the mechanism of deposition process of the Al-Ni alloy on steel electrode.
The experiment results have show that the addition of NiCl2 in the molten salt has a direct impact on the performance of the alloy coatings. It can perfect the coating morphology, help the formation of Al, Ni alloy phase, greatly improve the corrosion resistance and hardness, and the maximum hardness value can reach 7200Mpa when the Ni content in the coating was 6.19%. The cyclic voltammetry curves show that the Al-Ni alloy coating on steel electrode was deposited in three stages. The Al-Mn alloy coating had the best corrosion resistance and hardness when the Mn content was about 32.21%. Al-Mn alloy coating have the better corrosion resistance than Al-Ni alloy coating, but the hardness of Al-Ni alloy coating is large, almost is two times higher than the Al-Mn alloy coating.
引文
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[4]Mamantov G, Mamatov C B. Advances in molten salt chemistry[C]. Amsterdam; Elsevier press, 1993,112-115.
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[6]Haeng S C, Mok J H, Seok C S, et al. Hot corrosion behavior of Ni-base alloys in a molten salt under an oxidizing atmosphere[J]. Journal of Alloys and Compounds,2009,15(5):263-269.
[7]屠振密,安茂忠,张景双等.电镀合金的应用及前景展望[A].天津市电镀工程学会第九届学术年会论文集[C].2002,13-19.
[8]Dvais G L. Eletrodeposition of tungsten in oxide molten salt[J]. Metallurgy Letter,1956,53(3): 3-17.
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[11]冯秋元，丁志敏.熔融盐电镀铝的研究进展[J].电镀与环保2003,23(5)：1-4.
[12]孙淑萍.熔盐电镀Al-Mn合金-电镀参数对合金镀层组成和结构的影响[J].轻合金加工技术,1999,20(4)：395-397.
[13]Muhammad R A, Atshushi N, Tooru T. Electrodeposition of Al-Ni intermetallic compounds from aluminum chloride-N-(n-butyl) pyridinium chloride roomtemperature molten salt[J]. Journal of Electroanalytical Chemistry,2005,513(5):111-118.
[14]过家驹,魏振强,郭乃名.Al-Ti合金粉的含Ti量及其结构[J].腐蚀科学与防护技术2000,12(2)：98-100.
[15]Inman D and White S H. The production of refratory metal by the electrolysis of molten salts; design factory and limitations[J]. Applied Electrochemistry,2008,24(8):375-390.
[16]颜永得，张密林,KCl-LiCl-MgCl2熔盐体系中共沉积制备Mg-Li合金及理论分析[J].无机化学学报2008,6(24),902-906.
[17]Jafarian M, Maleki A, Danaee I, et al. Electrodeposition of Al, Mn, and Al-Mn Alloy on aluminum electrodes from molten salt(AlCl3-NaCl-KCl)[J]. Journal of Applied Electrochem-istry,2009,39(4):1297-1303.
[18]Mikito U, Hideki H, Toshiaki O. Electrodeposition of Al-Pt alloys using contant potential eletrolysis in AlCl3-NaCl-KCl molten salt containing PtCl2[J]. Surface and Coating Technology, 2011,239(3):202-208.
[19]路伟龙，孙淑萍.钢板熔盐电镀Al-Co合金的研究[D].河北：燕山大学,2007,1-3.
[20]Takahisa I, Toshiyuki N, Yasuhiko I. Electrochemical formation of Yb-Ni alloy films by Li codeposition method in a molten LiCl-KCl-YbCl3 system[J]. Electrochimica Acta 2003,48(3): 1531-1536.
[21]Yukihiro K, Nobukazu F, Masato Y, et al. Long-term corrosion resistance of Al-Ni-plated mate rial and Al-plated material in molten carbonate environment[J]. Journal of Power Sources,2000, 86 (12):324-328.
[22]Capuano G. A. and Ducasse R. Electrodeposition of aluminum-copper alloys from alkyl benzene electrolytes[J]. Journal of Applied electrochemistry,1999,7(9):7-13.
[23]N Godshall. Molten salts metalliding of nickel alloys[J] Journal of Electrochemical Society, 2006,123 (4):137-147.
[24]杜道斌.熔盐电镀铝过程及性能研究[J].金属热处理,1993,56(10)：16-21.
[25]牛洪军,孙国恩,宋国泰.AlCl3-NaCl熔盐电解渗铝及其耐蚀性[J].腐蚀与防护,1994,66(2)：61-63.
[26]Nayak B, Misra M M. The Electrode position of Aluminiumon Brass from a Molten Aluminium Chloride-Sodium Chloride Bath[J]. Journal of Applied Electrochemistry,1997,4 (7): 45-50.
[27]Nayak B, Misra M M. The Electrode position of Aluminiumon Mild Steel from a Molten Aluminium Chloride- Sodium Chloride Bath[J]. Journal of Applied Electrochemistry,1999,8 (9):699-706.
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