水性无铬锌铝涂层的制备与性能研究
摘要
防腐涂层是避免金属制品腐蚀的有效手段。水性无铬锌铝涂层具有施工简单、成本低廉、防腐效果好等特点,从而得到了广泛关注和大力推广。随着科技的不断进步,金属防护工业受到了出于环保节能等方面的日益严峻的压力,涂料工业向环保型发展已成定局。以铬酸盐作为粘结剂的达克罗涂层技术越来越受到限制,无铬化成为了该涂层的发展趋势。
首先,本文从涂层的粘结剂开始研究,选择并确定了粘结剂的基本组分,并最终制得了稳定的无机基液。无铬化是本实验的重点,也是难点。本文研究了反应温度、搅拌方式和试剂的滴加速度等对混合型硅溶胶溶液制备的影响。结果表明：反应温度为50℃左右,采用磁力搅拌方式,控制滴加速度有利于制备透明度和稳定性较高的硅溶胶溶液。
其次,本文从理论上研究了铝粉的改性方法；分析了在片状铝粉粒子表面包覆惰性的硅三维网状低聚物膜,使铝粉颜料粒子适用于水性涂料的过程；讨论了包覆改性的条件,反应温度为45℃,反应时间为9h。经包膜的片状铝粉颜料粒子通过扫描电镜(SEM)、能谱(EDS)、激光粒度测试仪和X射线衍射分析(XRD)等检测手段进行了分析和表征。结果表明：片状铝粉颜料粒子表面包覆了惰性膜层后,铝粉颜料表面由疏水性变成了亲水性。
最后,本文对涂层的制备工艺和影响因素进行了研究。采用SEM、EDS及XRD检测手段对涂层腐蚀前后的微观形貌和成份进行了分析。结果表明：锌、铝粉用量比为3:1,粘结剂用量比例为20%时为制备无铬锌铝涂层的最佳工艺条件。同时对涂层的耐腐蚀性能、结合力强度及外观等进行了综合评价。
水性无铬锌铝涂层作为新型的环境友好型涂层,有很广阔的市场前景。由于本试验是自行研制,时间及条件较为紧迫,在分析及性能检测等方面还有待深入研究。因此,该技术产业化还有许多工作需进一步讨论及完善。
Anti-corrosion coating of metal produce is effective means for corrosion. The anti-corrosion coating relied on constructing simply the low-cost, well anti-corrosion and so on, has attracted widely attention. With the development of technology, industry metallic anti-corrosion is confronted with the pressure from both environment protection and energy-conservation. Dacromet coating will be forbidden in further, so, it is necessary to find a substitute for chromate.
Firstly, the basic components have been selected, after lots of experiment. We get the watering bonding. The selection of substitute for chromate was the key and the most difficult work in the experiment. Impact of reaction temperature, type of agitation, speed of adding solution and so on has been studied. Results show that reaction temperature around 50℃, produced with magnetic agitation, control the adding speed is proper to prepare the products of the stability and transparence.
Secondly, the silica encapsulation of aluminum flakes provided aluminum pigments used in the water-based coating by thesis. The effect of the relate factors of the process is studied, the reaction temperature is 45℃, the reaction time is 9 hours. Encapsulated aluminum flakes were characterized by scanning electron microscopy (SEM), energy spectrum instrument (EDS), laser particle size and XRD measurer.The results showed that aluminum flakes turned to being water-inert and hydrophilic after being coated by layer of silica.
Finally, the processing parameters of preparation for non-chrome coating have been studied. We used SEM EDS and XRD to observe and analyze the element of the coating. Produced the water-based coating with different proportion of zinc and aluminum powder, then, researched by contrasting the performance of these coatings. After the researched on the components and preparation process, the non-chrome zinc-aluminum coating with the best performances was prepared. The proportion of zinc and aluminum powder is 3:1, and the binder is 20%. The anti-corrosion performance cohesion as well as appearance were tested.
Watering non-chrome Zinc-Aluminum coating, as a new type of environmental-friendly protection coating must have broad market prospects. But there are many things to be done before putting this process into industrial use, because the experiment needs much further research and amelioration.
首先,本文从涂层的粘结剂开始研究,选择并确定了粘结剂的基本组分,并最终制得了稳定的无机基液。无铬化是本实验的重点,也是难点。本文研究了反应温度、搅拌方式和试剂的滴加速度等对混合型硅溶胶溶液制备的影响。结果表明：反应温度为50℃左右,采用磁力搅拌方式,控制滴加速度有利于制备透明度和稳定性较高的硅溶胶溶液。
其次,本文从理论上研究了铝粉的改性方法；分析了在片状铝粉粒子表面包覆惰性的硅三维网状低聚物膜,使铝粉颜料粒子适用于水性涂料的过程；讨论了包覆改性的条件,反应温度为45℃,反应时间为9h。经包膜的片状铝粉颜料粒子通过扫描电镜(SEM)、能谱(EDS)、激光粒度测试仪和X射线衍射分析(XRD)等检测手段进行了分析和表征。结果表明：片状铝粉颜料粒子表面包覆了惰性膜层后,铝粉颜料表面由疏水性变成了亲水性。
最后,本文对涂层的制备工艺和影响因素进行了研究。采用SEM、EDS及XRD检测手段对涂层腐蚀前后的微观形貌和成份进行了分析。结果表明：锌、铝粉用量比为3:1,粘结剂用量比例为20%时为制备无铬锌铝涂层的最佳工艺条件。同时对涂层的耐腐蚀性能、结合力强度及外观等进行了综合评价。
水性无铬锌铝涂层作为新型的环境友好型涂层,有很广阔的市场前景。由于本试验是自行研制,时间及条件较为紧迫,在分析及性能检测等方面还有待深入研究。因此,该技术产业化还有许多工作需进一步讨论及完善。
Anti-corrosion coating of metal produce is effective means for corrosion. The anti-corrosion coating relied on constructing simply the low-cost, well anti-corrosion and so on, has attracted widely attention. With the development of technology, industry metallic anti-corrosion is confronted with the pressure from both environment protection and energy-conservation. Dacromet coating will be forbidden in further, so, it is necessary to find a substitute for chromate.
Firstly, the basic components have been selected, after lots of experiment. We get the watering bonding. The selection of substitute for chromate was the key and the most difficult work in the experiment. Impact of reaction temperature, type of agitation, speed of adding solution and so on has been studied. Results show that reaction temperature around 50℃, produced with magnetic agitation, control the adding speed is proper to prepare the products of the stability and transparence.
Secondly, the silica encapsulation of aluminum flakes provided aluminum pigments used in the water-based coating by thesis. The effect of the relate factors of the process is studied, the reaction temperature is 45℃, the reaction time is 9 hours. Encapsulated aluminum flakes were characterized by scanning electron microscopy (SEM), energy spectrum instrument (EDS), laser particle size and XRD measurer.The results showed that aluminum flakes turned to being water-inert and hydrophilic after being coated by layer of silica.
Finally, the processing parameters of preparation for non-chrome coating have been studied. We used SEM EDS and XRD to observe and analyze the element of the coating. Produced the water-based coating with different proportion of zinc and aluminum powder, then, researched by contrasting the performance of these coatings. After the researched on the components and preparation process, the non-chrome zinc-aluminum coating with the best performances was prepared. The proportion of zinc and aluminum powder is 3:1, and the binder is 20%. The anti-corrosion performance cohesion as well as appearance were tested.
Watering non-chrome Zinc-Aluminum coating, as a new type of environmental-friendly protection coating must have broad market prospects. But there are many things to be done before putting this process into industrial use, because the experiment needs much further research and amelioration.
引文
[1]候保荣.腐蚀研究与防护技术[M].北京：海洋出版社,1998.1
[2]徐滨士.发展再制造工程,构建循环经济,建设节约型社会[A].2005中国机械工程学会年会重点报告[C].重庆：中国机械工程学会,2005:1-20
[3]刘光复.绿色制造科技发展[A].2005中国机械工程学会年会论文集[C].重庆：中国机械工程学会,2005:16-27
[4]王杏卿.热力设备的腐蚀与防护.北京：水利电力出版社,1988:1
[5]曹楚南.腐蚀电化学.北京：化学工业出版社,1994:1
[6]刘永辉,张佩芬.金属腐蚀学原理[M].北京：航空工业出版社,1993.249-253
[7]徐峰.无机涂料与涂装技术.第二化学工业出版社,2002
[8]虞兆年.防腐蚀涂料与涂装.第二版化学工业出版社,2001
[9]周海晖,许岩.我国防腐蚀涂料的现状及其发展,表面技术,2002,31(1):5-8
[10]叶康民.金属腐蚀与防护概论[M].北京：高等教育出版社,1993.180-197
[11]高谨,张震宇.水性丙烯酸富锌涂料的研究,山西防腐蚀工程,2000,16(1)18-20
[12]李劲,张淑贤,海峰.水性无机富锌涂料,上海涂料2002,17(5):73-75
[13]刘红伟.水性防腐涂料,中国涂料,2001,(1):27-28
[14]徐峰.无机涂料与涂装技术.第二版化学工业出版社,2002
[15]希时俊.富锌底漆评估,中国涂料,2000.11(2):23-38
[16]郭晓军,何渔游.水性硅酸镒富锌涂料的研制及应用[J].涂料工业,2002,32(4)：37
[17]李光玉,陈建设.锌铝涂层的研究开发与应用[J],金属热处理,2003 28:8-12
[18]胡会利,李宁,韩家军,程瑞宁.达克罗的研究现状[J].电镀与涂饰,2005,24：31-33
[19]Ikegami; Makoto; Homi; Makoto. Zinc powder diapersible in water and zinc powder containing water base paint [P]; United States Patent:6,770,124,2004
[20]Endo, Yasuhike,Tomio, Shimada, Saburo. Surface coated aluminum fine powder and aqueous chromium-free corrosion inhibiting coating composition including the same [p]. United States Patent:6,740,424,2004
[21]T.Prosck and D.Thierry. Mobility and Mode of Inhibition of Chromate at Defected Area of Organic Coatings Under Atmospheric Conditions[J];CORROSION Vol.60,NO.12
[22]魏计文.金属防腐新工艺—达克罗,武钢技术[J].2002:40:58-60
[23]张伟明.达克罗—当今世界表面处理的高新技术[J].材料保护,1995,28,(8)：19-20
[24]Krause Heringer H. Dacromet-a new corrosion protection for fansteners [J]. Product Finishing,1997,5:29-32
[25]危恒毅,岳庆磊等.水性防腐涂料体系.精细石油化工进展.2002,3(4):44-46
[26]陶俑忠,陈 ,顾国芳.室温固化水性环氧树脂涂料.涂料工业.2001,(1):36-38
[27]屠德容,李健,刘红伟等.关于水性无机锌铝涂料的若干问题.涂料技术与文摘2003,(1)：13-16
[28]张伟明.交美特—取代达克罗的表面处理新技术[J].材料保护,2003,36(4)：15-16
[29]孙贺民.锌铬膜—一种特殊的表面处理新技术[J].材料保护,1994,27(8):21-23
[30]马颐军,李家柱.镀锌层大气腐蚀试验研究,材料保护,1998,31(9):4-6
[31]QB/T3823—1999轻工产品金属镀层的孔隙率测试方法
[32]U.R.Evans著,华保定译.金属的腐蚀与氧化,机械工艺出版社,北京,1976,688-772
[33]杨文治,黄魁元,王涛等.缓蚀剂[M].北京：化学工业出版社,1989:119-120
[34]韩克平,叶向荣,方景礼.镀锌层表面硅酸盐防腐膜的研究[J].腐蚀科学与防腐技术,1997,9(2)：167-169
[35]周金宝.镀锌层无铬钝化的新进展[J].电镀与环保,1991,11(5):7-9
[36]D·J·古德,T·E·多赛特,D·A·奥伯林恩,W·H·古恩,V·V·吉曼诺.可提供防腐保护的水可稀释性涂料组合物[P]CN 1172135A,1998
[37]Eido,Yasunhiko,SaKai,Tomio,Takase Kengo. Chromium-free water reducible rust inhibitive paint for metals[P],United States Patent:6,960,247,2005
[38]Ralph K.Iler, Wilmington. Process for preparing sols of colloidal particles of reached amorphous silica and products hereof. [P] US 2786042,1957
[39]Roger A.Assink,Bruce D.Kay.J.Non-Cryst.Solids,1998,(99):935-371
[40]Wheeler I.Metallic Pigments in Polymer. Rapra Technology Limited,1999
[41]Chmipion Y, Bigot J,Synthesis and structral analysis of aluminum nanocrystalline powder Nanostructured Materials,1998,10(7):1097-1110
[42]Lessard R B, Berglund K A, Nocera D. Highly Emissive Lanthanide Compounds in Sol-gel Derived Materials [J].Mater Res Soc Sym Proc,1989,(115):119
[43]Y.Aton,H.Suznki,Y,Kimyra.Novel method for the preparation of silicon oxide layer on TiO2 particle and dynamic behavior of silicon oxide layer on TiO2 particle.physical E,2003(16):179-189
[44]Zhu Yingchun,Ding Chuanxian,Yukimura. K,et al.Deposition and Charaterization of Nanostructured WC-Co Coating[J].Cermics International, 2001,27(6):669-674
[45]姜炜,吴垠,李风生等.铝粉颜料的改性研究[J].纳米科技,2007,7(3):62-65
[46]杨宗志.效应颜料工艺学.北京：化工工业出版社,2002
[47]Russell L. Ferguson. American Pain & Coating Journal,1996,81(11):15-16
[48]徐溢,唐首渊,陈立军.反射吸收红外光谱法研究铝粉表面预处理中的应用[J].腐蚀科学与防护技术,2001,13(2):96-100
[49]王喜贵,赵慧,张强等.硅烷水解过程的研究进展.内蒙古石油化工,2001,(27)：17-19
[50]W. K. Asbeck, M. Van Loo. Critical pigment volume relationships. Ind. Chem. 1949, (41):1470
[2]徐滨士.发展再制造工程,构建循环经济,建设节约型社会[A].2005中国机械工程学会年会重点报告[C].重庆：中国机械工程学会,2005:1-20
[3]刘光复.绿色制造科技发展[A].2005中国机械工程学会年会论文集[C].重庆：中国机械工程学会,2005:16-27
[4]王杏卿.热力设备的腐蚀与防护.北京：水利电力出版社,1988:1
[5]曹楚南.腐蚀电化学.北京：化学工业出版社,1994:1
[6]刘永辉,张佩芬.金属腐蚀学原理[M].北京：航空工业出版社,1993.249-253
[7]徐峰.无机涂料与涂装技术.第二化学工业出版社,2002
[8]虞兆年.防腐蚀涂料与涂装.第二版化学工业出版社,2001
[9]周海晖,许岩.我国防腐蚀涂料的现状及其发展,表面技术,2002,31(1):5-8
[10]叶康民.金属腐蚀与防护概论[M].北京：高等教育出版社,1993.180-197
[11]高谨,张震宇.水性丙烯酸富锌涂料的研究,山西防腐蚀工程,2000,16(1)18-20
[12]李劲,张淑贤,海峰.水性无机富锌涂料,上海涂料2002,17(5):73-75
[13]刘红伟.水性防腐涂料,中国涂料,2001,(1):27-28
[14]徐峰.无机涂料与涂装技术.第二版化学工业出版社,2002
[15]希时俊.富锌底漆评估,中国涂料,2000.11(2):23-38
[16]郭晓军,何渔游.水性硅酸镒富锌涂料的研制及应用[J].涂料工业,2002,32(4)：37
[17]李光玉,陈建设.锌铝涂层的研究开发与应用[J],金属热处理,2003 28:8-12
[18]胡会利,李宁,韩家军,程瑞宁.达克罗的研究现状[J].电镀与涂饰,2005,24：31-33
[19]Ikegami; Makoto; Homi; Makoto. Zinc powder diapersible in water and zinc powder containing water base paint [P]; United States Patent:6,770,124,2004
[20]Endo, Yasuhike,Tomio, Shimada, Saburo. Surface coated aluminum fine powder and aqueous chromium-free corrosion inhibiting coating composition including the same [p]. United States Patent:6,740,424,2004
[21]T.Prosck and D.Thierry. Mobility and Mode of Inhibition of Chromate at Defected Area of Organic Coatings Under Atmospheric Conditions[J];CORROSION Vol.60,NO.12
[22]魏计文.金属防腐新工艺—达克罗,武钢技术[J].2002:40:58-60
[23]张伟明.达克罗—当今世界表面处理的高新技术[J].材料保护,1995,28,(8)：19-20
[24]Krause Heringer H. Dacromet-a new corrosion protection for fansteners [J]. Product Finishing,1997,5:29-32
[25]危恒毅,岳庆磊等.水性防腐涂料体系.精细石油化工进展.2002,3(4):44-46
[26]陶俑忠,陈 ,顾国芳.室温固化水性环氧树脂涂料.涂料工业.2001,(1):36-38
[27]屠德容,李健,刘红伟等.关于水性无机锌铝涂料的若干问题.涂料技术与文摘2003,(1)：13-16
[28]张伟明.交美特—取代达克罗的表面处理新技术[J].材料保护,2003,36(4)：15-16
[29]孙贺民.锌铬膜—一种特殊的表面处理新技术[J].材料保护,1994,27(8):21-23
[30]马颐军,李家柱.镀锌层大气腐蚀试验研究,材料保护,1998,31(9):4-6
[31]QB/T3823—1999轻工产品金属镀层的孔隙率测试方法
[32]U.R.Evans著,华保定译.金属的腐蚀与氧化,机械工艺出版社,北京,1976,688-772
[33]杨文治,黄魁元,王涛等.缓蚀剂[M].北京：化学工业出版社,1989:119-120
[34]韩克平,叶向荣,方景礼.镀锌层表面硅酸盐防腐膜的研究[J].腐蚀科学与防腐技术,1997,9(2)：167-169
[35]周金宝.镀锌层无铬钝化的新进展[J].电镀与环保,1991,11(5):7-9
[36]D·J·古德,T·E·多赛特,D·A·奥伯林恩,W·H·古恩,V·V·吉曼诺.可提供防腐保护的水可稀释性涂料组合物[P]CN 1172135A,1998
[37]Eido,Yasunhiko,SaKai,Tomio,Takase Kengo. Chromium-free water reducible rust inhibitive paint for metals[P],United States Patent:6,960,247,2005
[38]Ralph K.Iler, Wilmington. Process for preparing sols of colloidal particles of reached amorphous silica and products hereof. [P] US 2786042,1957
[39]Roger A.Assink,Bruce D.Kay.J.Non-Cryst.Solids,1998,(99):935-371
[40]Wheeler I.Metallic Pigments in Polymer. Rapra Technology Limited,1999
[41]Chmipion Y, Bigot J,Synthesis and structral analysis of aluminum nanocrystalline powder Nanostructured Materials,1998,10(7):1097-1110
[42]Lessard R B, Berglund K A, Nocera D. Highly Emissive Lanthanide Compounds in Sol-gel Derived Materials [J].Mater Res Soc Sym Proc,1989,(115):119
[43]Y.Aton,H.Suznki,Y,Kimyra.Novel method for the preparation of silicon oxide layer on TiO2 particle and dynamic behavior of silicon oxide layer on TiO2 particle.physical E,2003(16):179-189
[44]Zhu Yingchun,Ding Chuanxian,Yukimura. K,et al.Deposition and Charaterization of Nanostructured WC-Co Coating[J].Cermics International, 2001,27(6):669-674
[45]姜炜,吴垠,李风生等.铝粉颜料的改性研究[J].纳米科技,2007,7(3):62-65
[46]杨宗志.效应颜料工艺学.北京：化工工业出版社,2002
[47]Russell L. Ferguson. American Pain & Coating Journal,1996,81(11):15-16
[48]徐溢,唐首渊,陈立军.反射吸收红外光谱法研究铝粉表面预处理中的应用[J].腐蚀科学与防护技术,2001,13(2):96-100
[49]王喜贵,赵慧,张强等.硅烷水解过程的研究进展.内蒙古石油化工,2001,(27)：17-19
[50]W. K. Asbeck, M. Van Loo. Critical pigment volume relationships. Ind. Chem. 1949, (41):1470
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |