低温快速少渣磷化液研究及应用
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摘要
金属表面磷化处理是在酸性磷酸盐溶液中进行化学处理，在其表面生成一层难溶的磷酸盐膜层，它能大大提高涂层的耐蚀性和附着力，在汽车涂装表面处理工艺中得到了广泛应用。全球大部分汽车前处理生产线多采用中温磷化(40℃～50℃)工艺，该工艺主要缺点是能耗大、成本高、效率低、污染重。为此，国内外一直在研究低温磷化，到目前为止，仅有日本部分汽车制造厂采用，在欧洲、美洲的汽车制造厂基本上都采用中温磷化工艺。低温、少渣、快速磷化技术的研究和应用是21世纪汽车涂装前处理发展的趋势。
本文在分析国内外有关低温磷化技术状况的基础上，通过实验优化分析，研究出一种新型低温、少渣、快速磷化液，并通过一系列工艺实验验证了该种磷化液在汽车涂装前处理中使用的可行性。其主要工作和结论如下：
1．通过实验优选，确立了新型低温、少渣、快速磷化液(DKL2000)的主要成分配方。
2．在磷化液配方确定的基础上进行了工艺验证实验，主要验证了磷化膜外观、膜重、晶向结构、耐盐水性、耐碱性、与电泳配套性、成渣量，以及与前后工序的适应性等。通过以上实验表明：1)DKL2000磷化液，工作温度低，节约大量能源；2)DKL2000磷化液，工作时产生的沉渣少，显著减少沉渣量，有利于提高产品质量，节约原辅材料，减少环境污染；3)DKL2000磷化液成膜速度快，磷化时间在120s～180s之间，能满足生产线提速的需要；4)DKL2000磷化液，形成的磷化膜结晶形状好、耐盐水性能好，且其它各项性能均达到了工艺技术要求。因此，认为采用DKL2000磷化液，技术上是可行的、是合理的。
3．对低温、少渣、快速磷化中的组分进行分析及机理讨论认为：通过提高促进剂的氧化性，提高总酸，降低游离酸浓度，改变金属离子浓度增加其活性，控制PO_4~(3-)／NO_3~-的浓度比，添加酒石酸、柠檬酸、F~-等添加剂可以达到低温少渣快速的磷化要求。
Surface's phosphate treatment of metal is a chemical treatment in acid phosphate Solution. It will produce an undissolved phosphate film on the surface of metal. This film can improve the rust proofing and adhering of the coating. It uses general in the auto's surface treatment process before coating. Most of this process in the world use middle temperature phosphate solution(40 ~50 ). The main disadvantages of middle temperature process are: energy-waste, high cost, low efficiency and heavy pollution. So there are many people study the low temperature phosphate treatment. Until today only a little Japanese auto factories use low temperature phosphate Solution. Most of the auto factories in Europe and America use middle temperature process. The study and appliance of the low temperature, less dregs and quick phosphate solution is the main trend of the pre-treatment for the auto coating in 21 century.
This article is based on: at first analysing the present situation of the low temperature phosphate solution in the world, then according to a series experiments analyse the result of those experiments and get a new formulation of the low temperature, less dregs and quick phosphate solution. The appliance possibility of this phosphate solution that is used in pre-treatment of auto coating industry is proved through a series experiments. The main conclusions of the article are:
1.According to the experiments, make sured the formulation of the new low temperature, less dregs and quick phosphate solution (DKL2000). 2.Based on the new formulation, the appearance of the phosphate film, weight of the film, film structure, anti-salt, anti-alkalinity, adaptability with electrophoretic coating, dregs producing and the adaptation with whole process were proved through a series experiments. Below are main advantages, which are proved through all the experiments:1) Working temperature is low. It can spare a lot of energy.2) It can produce less dregs than the other process. It is good for the product quality. It can spare raw material and reduce the environmental pollution. 3) Less time to produce the film, phosphate time is between 120s~180s. It can improve the speed of the produce line.4) The shape of the phosphate film is good, anti-salt is good too. It can mix with the present phosphate solution. All the other characters are satisfied with the auto process.
So, DKL2000 is reasonable and feasible.
3. Based on the formulation analyse of the new low temperature, less dregs and quick phosphate Solution, and according to the theory analyse of the phosphating, we get the results: Increasing the oxygenation of the catalyse, improving the total acidity, reducing the concentration of free acid, changing the concentration of metal ion, improving their activity, controlling the concentration proportion of P043-/NO3-, adding dihydroxybutanedioic acid, adding citric acid and F" can reach the process requirement of the low temperature,less dregs and quick phosphating.
本文在分析国内外有关低温磷化技术状况的基础上，通过实验优化分析，研究出一种新型低温、少渣、快速磷化液，并通过一系列工艺实验验证了该种磷化液在汽车涂装前处理中使用的可行性。其主要工作和结论如下：
1．通过实验优选，确立了新型低温、少渣、快速磷化液(DKL2000)的主要成分配方。
2．在磷化液配方确定的基础上进行了工艺验证实验，主要验证了磷化膜外观、膜重、晶向结构、耐盐水性、耐碱性、与电泳配套性、成渣量，以及与前后工序的适应性等。通过以上实验表明：1)DKL2000磷化液，工作温度低，节约大量能源；2)DKL2000磷化液，工作时产生的沉渣少，显著减少沉渣量，有利于提高产品质量，节约原辅材料，减少环境污染；3)DKL2000磷化液成膜速度快，磷化时间在120s～180s之间，能满足生产线提速的需要；4)DKL2000磷化液，形成的磷化膜结晶形状好、耐盐水性能好，且其它各项性能均达到了工艺技术要求。因此，认为采用DKL2000磷化液，技术上是可行的、是合理的。
3．对低温、少渣、快速磷化中的组分进行分析及机理讨论认为：通过提高促进剂的氧化性，提高总酸，降低游离酸浓度，改变金属离子浓度增加其活性，控制PO_4~(3-)／NO_3~-的浓度比，添加酒石酸、柠檬酸、F~-等添加剂可以达到低温少渣快速的磷化要求。
Surface's phosphate treatment of metal is a chemical treatment in acid phosphate Solution. It will produce an undissolved phosphate film on the surface of metal. This film can improve the rust proofing and adhering of the coating. It uses general in the auto's surface treatment process before coating. Most of this process in the world use middle temperature phosphate solution(40 ~50 ). The main disadvantages of middle temperature process are: energy-waste, high cost, low efficiency and heavy pollution. So there are many people study the low temperature phosphate treatment. Until today only a little Japanese auto factories use low temperature phosphate Solution. Most of the auto factories in Europe and America use middle temperature process. The study and appliance of the low temperature, less dregs and quick phosphate solution is the main trend of the pre-treatment for the auto coating in 21 century.
This article is based on: at first analysing the present situation of the low temperature phosphate solution in the world, then according to a series experiments analyse the result of those experiments and get a new formulation of the low temperature, less dregs and quick phosphate solution. The appliance possibility of this phosphate solution that is used in pre-treatment of auto coating industry is proved through a series experiments. The main conclusions of the article are:
1.According to the experiments, make sured the formulation of the new low temperature, less dregs and quick phosphate solution (DKL2000). 2.Based on the new formulation, the appearance of the phosphate film, weight of the film, film structure, anti-salt, anti-alkalinity, adaptability with electrophoretic coating, dregs producing and the adaptation with whole process were proved through a series experiments. Below are main advantages, which are proved through all the experiments:1) Working temperature is low. It can spare a lot of energy.2) It can produce less dregs than the other process. It is good for the product quality. It can spare raw material and reduce the environmental pollution. 3) Less time to produce the film, phosphate time is between 120s~180s. It can improve the speed of the produce line.4) The shape of the phosphate film is good, anti-salt is good too. It can mix with the present phosphate solution. All the other characters are satisfied with the auto process.
So, DKL2000 is reasonable and feasible.
3. Based on the formulation analyse of the new low temperature, less dregs and quick phosphate Solution, and according to the theory analyse of the phosphating, we get the results: Increasing the oxygenation of the catalyse, improving the total acidity, reducing the concentration of free acid, changing the concentration of metal ion, improving their activity, controlling the concentration proportion of P043-/NO3-, adding dihydroxybutanedioic acid, adding citric acid and F" can reach the process requirement of the low temperature,less dregs and quick phosphating.
引文
[1] 张安富．磷化工艺剖析与低温化．材料保护，1991，24(2)：18
[2] 周谟银．利用电流和电压和变化研究磷化膜的生产过程．腐蚀科学与防护技术，1995，7(4)：341-345
[3] Ang K F et al. Development of Phosphate Coatings on Mild SteeI. TIMF. 1991,69(2):58- -65
[4] 张景双等．含有稀土复合促进剂简单低温磷化工艺．电镀与环保．1995，15(2)：26—28
[5] 李方杰，汽车车身的低温磷化工艺，电镀与精饰，1996，18(3)：39-40
[6] 张红，新型室温少渣磷化液的应用，材料保护，1995，28(4)：36
[7] 陈云同，古绪鹏，低温快速磷化添加剂的合成与应用，材料保护，1995，28(4)：8—10
[8] 曾德芳，刘志明，单海华，环保单组分低温磷化液的研制及应用，电镀与精饰，2001，23 ：8—10
[9] 张在富，XZ高耐蚀低温磷化工艺，材料保护，1998，31(8)：33-34
[10] 郭良生，SL-6A型常温锌系磷化液研究，材料保护，1996，29(12)：10-11
[11] 陈慕祖，陈卫华，涂装前处理材料的最新成果，现代涂料与涂装，1999，1：15—21
[12] 王锡春，汽车涂装前磷化处理技术及其发展趋势，汽车车身涂装技术，中国汽车工程学会制造技术分会汽车涂装专委会山版社，162-170
[13] 夏正斌，涂伟萍，杨卓如，陈焕钦，常温磷化技术，材料保护，1999，32(8)：16—19
[14] 周谟银，几种磷化膜的抗碱性能，材料保护，1994，27(8)：18—21
[15] 唐晖，李红，张惠荣，二乙撑三胺五甲撑基膦酸在低温磷化中的应用，材料保护，1999， 32 (11)：27
[16] 陈刚，低温快速(锌、钙)磷化工艺，表面技术，1998，27(5)：41-42
[17] 罗霞，高保娇，宋军，表面技术，2001，30(1)：38—40
[18] M. Gebbardt, Uber Phasenbestand, Textur, Epitaxibezichungen und Haftverband von Phosphatiering as chichtan auf Eisenplechen Dissertation, Bonn, 1962
[19] W. Machu. chem. favrik, 1940, 13, 451
[20] G Dale cheever. J , Paint Tech. 1967, 30. (504): 1-13
[21] W. Machu, Die Phosphatiering Varlag chemie, 1950, Weinheim, Bergstrsse Seite, 165
[22] W. Jaenicke, B .Lorenz, werkstoffs u Korrosion 1959, 10, 681-761
[23] I.I .Kbain .J .Appl, Chem, Ussr , 32, 1959,2531,2542,2662
[24] 王锡春，杨必暖，林鸣玉，最新汽车涂装技术，机械工业出版社，1998，70
[25] 王锡春，磷化膜与阴极电泳的配套性研究，汽车车身涂装技术，2000，53—56
[26] 王锡春，杨必暖，林鸣玉，最新汽车涂装技术，机械工业出版社，1998，73—74
[27] U.S.P 4153479, May 8,1979
[28] U.S.P 405440, November 8,1977
[29] U.S.P 4052232, October 4,1977
[30] 等特公昭 53-44408
[31] 特公昭 55-5589
[32] W. Machu, chem. Fabrik 1940, 15, 451,
[33] 王锡春，杨必暖，林鸣玉，最新汽车涂装技术，机械工业出版社，1998，70—71
[34] B. sathyanandham and K. Balakrish man, Metal Finishing, August 1967,65, NO.8.
[35] Roesner. G .Schuster L. Krause R, Korrosior U .Metallsch, 1941, 17, 174-178
[36] 陈慕祖，陈卫华，涂装前处理材料的最新成果，现代涂料与涂装，1999，1，15—21
[37] U.S.P, 2, 293, 716
[38] Folders, A. Korrosion. U. Metallsch, 1951, 19, 281
[39] Lapatukhim, W.S. Zh, Prikl. Khim 1957, 24,375-382
[40] 王锡春，杨必暖，林鸣玉，最新汽车涂装技术，机械工业出版社，1998，78—79
[41] G.W. Jernsteat .Trans .Electrochem. Soc ,1943,83,361
[42] U.S.P. 4152.176. May. 1. 1979
[43] Guy .Lorin, phosphating of , Metals
[44] W. J. Van. Surface and Coatings Technoloy, 1989:39-40
[45] Zantout, B. and Gabe, D.R.,Trans. Inst. Met. Fin. 1983, 61:88.
[46] Miyawaski, T., Okita, H., Umehara, S. and Okabe, M.,Proc. Interfinish Kyoto, 1980,80.
[47] Richardson, M. O. W., Freeman, D. B., Brown, K. and Djaroud, N., Trans. Inst. Met. Fin. 611983,61:183
[48] Kojima, R., Nomura,. K. and Ujihara, Y., J. Jap. Soc. Col. Mat. 1982,52:365
[49] Cooke, B. A., Ⅸth Proc. Int. Conf. Org. Cost. Sci.&Tech.,Athens, July 1983,29:82
[50] Ghali, E.L. and Potvin, J.R.,Cvorrosion Science, 1972, 12:583.
[2] 周谟银．利用电流和电压和变化研究磷化膜的生产过程．腐蚀科学与防护技术，1995，7(4)：341-345
[3] Ang K F et al. Development of Phosphate Coatings on Mild SteeI. TIMF. 1991,69(2):58- -65
[4] 张景双等．含有稀土复合促进剂简单低温磷化工艺．电镀与环保．1995，15(2)：26—28
[5] 李方杰，汽车车身的低温磷化工艺，电镀与精饰，1996，18(3)：39-40
[6] 张红，新型室温少渣磷化液的应用，材料保护，1995，28(4)：36
[7] 陈云同，古绪鹏，低温快速磷化添加剂的合成与应用，材料保护，1995，28(4)：8—10
[8] 曾德芳，刘志明，单海华，环保单组分低温磷化液的研制及应用，电镀与精饰，2001，23 ：8—10
[9] 张在富，XZ高耐蚀低温磷化工艺，材料保护，1998，31(8)：33-34
[10] 郭良生，SL-6A型常温锌系磷化液研究，材料保护，1996，29(12)：10-11
[11] 陈慕祖，陈卫华，涂装前处理材料的最新成果，现代涂料与涂装，1999，1：15—21
[12] 王锡春，汽车涂装前磷化处理技术及其发展趋势，汽车车身涂装技术，中国汽车工程学会制造技术分会汽车涂装专委会山版社，162-170
[13] 夏正斌，涂伟萍，杨卓如，陈焕钦，常温磷化技术，材料保护，1999，32(8)：16—19
[14] 周谟银，几种磷化膜的抗碱性能，材料保护，1994，27(8)：18—21
[15] 唐晖，李红，张惠荣，二乙撑三胺五甲撑基膦酸在低温磷化中的应用，材料保护，1999， 32 (11)：27
[16] 陈刚，低温快速(锌、钙)磷化工艺，表面技术，1998，27(5)：41-42
[17] 罗霞，高保娇，宋军，表面技术，2001，30(1)：38—40
[18] M. Gebbardt, Uber Phasenbestand, Textur, Epitaxibezichungen und Haftverband von Phosphatiering as chichtan auf Eisenplechen Dissertation, Bonn, 1962
[19] W. Machu. chem. favrik, 1940, 13, 451
[20] G Dale cheever. J , Paint Tech. 1967, 30. (504): 1-13
[21] W. Machu, Die Phosphatiering Varlag chemie, 1950, Weinheim, Bergstrsse Seite, 165
[22] W. Jaenicke, B .Lorenz, werkstoffs u Korrosion 1959, 10, 681-761
[23] I.I .Kbain .J .Appl, Chem, Ussr , 32, 1959,2531,2542,2662
[24] 王锡春，杨必暖，林鸣玉，最新汽车涂装技术，机械工业出版社，1998，70
[25] 王锡春，磷化膜与阴极电泳的配套性研究，汽车车身涂装技术，2000，53—56
[26] 王锡春，杨必暖，林鸣玉，最新汽车涂装技术，机械工业出版社，1998，73—74
[27] U.S.P 4153479, May 8,1979
[28] U.S.P 405440, November 8,1977
[29] U.S.P 4052232, October 4,1977
[30] 等特公昭 53-44408
[31] 特公昭 55-5589
[32] W. Machu, chem. Fabrik 1940, 15, 451,
[33] 王锡春，杨必暖，林鸣玉，最新汽车涂装技术，机械工业出版社，1998，70—71
[34] B. sathyanandham and K. Balakrish man, Metal Finishing, August 1967,65, NO.8.
[35] Roesner. G .Schuster L. Krause R, Korrosior U .Metallsch, 1941, 17, 174-178
[36] 陈慕祖，陈卫华，涂装前处理材料的最新成果，现代涂料与涂装，1999，1，15—21
[37] U.S.P, 2, 293, 716
[38] Folders, A. Korrosion. U. Metallsch, 1951, 19, 281
[39] Lapatukhim, W.S. Zh, Prikl. Khim 1957, 24,375-382
[40] 王锡春，杨必暖，林鸣玉，最新汽车涂装技术，机械工业出版社，1998，78—79
[41] G.W. Jernsteat .Trans .Electrochem. Soc ,1943,83,361
[42] U.S.P. 4152.176. May. 1. 1979
[43] Guy .Lorin, phosphating of , Metals
[44] W. J. Van. Surface and Coatings Technoloy, 1989:39-40
[45] Zantout, B. and Gabe, D.R.,Trans. Inst. Met. Fin. 1983, 61:88.
[46] Miyawaski, T., Okita, H., Umehara, S. and Okabe, M.,Proc. Interfinish Kyoto, 1980,80.
[47] Richardson, M. O. W., Freeman, D. B., Brown, K. and Djaroud, N., Trans. Inst. Met. Fin. 611983,61:183
[48] Kojima, R., Nomura,. K. and Ujihara, Y., J. Jap. Soc. Col. Mat. 1982,52:365
[49] Cooke, B. A., Ⅸth Proc. Int. Conf. Org. Cost. Sci.&Tech.,Athens, July 1983,29:82
[50] Ghali, E.L. and Potvin, J.R.,Cvorrosion Science, 1972, 12:583.