以聚合物乳液为成膜物的特性涂料的制备及其应用研究
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摘要
涂料是指涂覆于物体的表面,形成具有装饰、保护作用或赋予物体某种特殊功能的材料。以聚合物乳液为成膜物的水性涂料作为水性涂料的一个重要分支,其应用研究越来越受到涂料科研技术人员的重视,以聚合物乳液为成膜物的水性涂料的应用领域也愈加广泛。
本论文研究了以聚合物乳液为成膜物的三种涂料的制备及其应用性能,提出了一种用Photoshop软件进行涂层附着力分级和生锈面积检测的方法。论文主要包括以下几方面的工作：
1.以双组分环氧乳液涂料为底漆,含氟丙烯酸乳液涂料、硅丙乳液涂料、苯丙乳液涂料为面漆制备了水性裂纹漆。该水性涂料与传统的溶剂型裂纹漆相比具有环保无毒的优点,可应用于墙面、玻璃、家具或艺术品之类的表面的装饰性涂装。论文对裂纹图案产生的机理进行了分析,对裂纹间距和裂纹形状的影响因素进行了研究。试验中通过改变膜厚、面漆类型、颜料含量、涂层表面空气流通速度等因素制备了不同裂纹间距和裂纹形状的裂纹图案。含氟涂料、苯丙涂料和硅丙涂料的面漆可分别制备主要为Y-型交叉、T-型交叉和混合型交叉的裂纹图案。面漆越厚,裂纹间距越大；颜填料的含量越高,即颜基比越大,面漆越不容易开裂。在面漆干燥成膜的过程中,涂膜表面的空气流通速率的增加可使面漆产生裂纹图案的裂纹间距变小。而且,对裂纹漆的实际应用的性质,如附着力、耐水性和耐洗刷性进行了检测,检测结果表明涂料有良好的实际应用性能。
2.利用含氟乳液制备了水性耐候外墙涂料,对涂料的配方进行了设计,对涂料综合性能特别是耐候性进行了表征。耐候性主要通过涂料样板的颜色变化、光泽变化、亲疏水性变化的比较来确定。颜色变化、光泽变化、亲疏水性的变化分别用白度仪,光泽度仪和接触角测定仪进行了表征。通过人工氙灯照射老化试验研究了不同钛白粉和不同乳液制备的涂料的耐候性、耐沾污、耐水性的差异,在1000h的人工老化试验中,使用耐候的杜邦R706金红石形钛白粉配制的含氟涂料无脱落、无起泡,变色轻微。在户外暴晒、雨淋、昼夜变化等自然条件下老化1年,含氟涂料样板的涂膜无脱落、无起泡,无变色。涂料样品在北京国家化学建筑材料测试中心按照《GB/T9755-2001合成树脂乳液外墙涂料》进行了人工氙灯老化试验、耐沾污、耐水性、耐洗刷等综合性能检测,涂料性能达到或超过合成树脂乳液外墙涂料优等品标准。
3.针对目前硅钢涂料含铬的环保问题,采用纯丙乳液,金属多齿螯合剂等制备了无铬环保的硅钢薄层涂料。采用金属多齿螯合剂作为防锈组分,替代传统的有毒的含铬组分,成膜过程中在硅钢表面络合形成多个螯合环,形成坚固致密的单分子保护膜,能有效地防止O2、水等进入硅钢的表面,抑制硅钢的氧化腐蚀。硅钢片涂层样板在广州国家日用电器质量监督检验中心进行了耐热性和耐制冷剂性能检验,检测结果完全达到了硅钢涂层的要求。
4.将图像处理软件引入到涂层性能的检测中,提出了利用Photoshop软件和扫描仪进行涂膜附着力分级和生锈面积测量的方法。基于Photoshop软件的灵活的选择图像的功能和对图像像素的统计功能,采用像素代替相对面积的方法,提出了利用Photoshop软件和扫描仪进行涂膜附着力分级的方法,该方法比目前常用的图像对比的方法更为准确；Photoshop测量的剥落区域的像素占划格区域的像素百分率和ASTM标准中给出的剥离率有良好的相关性,其相关系数为0.997。同样基于Photoshop软件的灵活的选择图像的功能和对图像像素的统计功能,结合Photoshop软件“信息”面板对图像的高与宽的测量功能,通过公式对生锈面积进行计算。对规则的生锈区域,将Photoshop软件测量得到的面积和用游标卡尺测量的计算得到的面积进行了对比,相对误差在3.0%以下,证明了Photoshop软件测量结果的准确性。
Coatings are a kind of materials coated on the surface of an object, which can provide the object decorative, protective or particular functions. Waterborne coatings that use polymer emulsion as film-forming component are being paid attention to by more and more scientific and technical personnel and the application field of waterboene coatings has become more widely.
The preparation and application performance of three waterborne coatings which use different polymer emulsions as film-forming component have been investigated in this paper, and a classification method of coating adhesion and measuring method of rust area of coatings based on the Photoshop software have also been proposed. The main work of this paper is as follows:
1. The waterborne crack decorative coatings were prepared by two-component epoxy basecoat and topcoat made from one of the fluorine-containing acrylic emulsion, silicone-acrylic emulsion and styrene-acrylic emulsion. Compared with the traditional solvent-based paint, the waterborne coatings are environmental friendly and non-toxic. Crack decorative coatings can be applied to the surface of wall, glass, furniture or works of art and so on. The mechanism of crack patterns generation was analyzed. The factors that influence the crack spacing and crack shape of crack patterns were investigated. Different crack spacing and crack shape of the crack pattern were prepared by changing the film thickness, topcoat type, pigment content, the air flow rate of coating surface and other factors. Three junction types of crack patterns were prepared by the three top coatings, which were T-junction, Y-junction and mixed junction. T-junction type was made from styrene-acrylic emulsion. Y-junction type was made from fluorine-containing acrylic emulsion and mixed junctions type was made from silicone-acrylic emulsion. The crack spacing increased with the increase of the thickness of topcoat. The higher content of pigments and fillers, namely the greater the pigment to binder ratio, the more difficult of topcoat cracking. In the process of film drying, the increase of air flow speed on coating surface can result in smaller crack spacing of crack patterns. The properties of coating film including adhesion, water resistance, scrub resistance and so on were tested. The results showed that the crackle coatings possessed satisfactory properties for practical application.
2. The waterborne fluorine-containing exterior coatings were prepared using fluorine-containing polymer emulsion, whose preparation and application performance, especially the coatings' weathering durability was investigated. The coatings' weathering durability mainly determined by the changes of color, gloss and hydrophobicity. Color change, gloss change and change in hydrophobicity were measured by whiteness meter, gloss meter, and contact angle measuring instrument. Artificial aging test of coatings was carried out for 1000h in Xeon Lamp Aging Test Chamber. The fluorine-containing coatings made from weather-resistant rutile TiO2, DuPont R706, were without peeling, no blistering, and color changed slightly. After the outdoor aging under natural conditions for one year, during which the coatings undergoing sunlight, rain, diurnal variation, the fluorine-containing coating film were without peeling, no blistering and no color change. The fluorine-containing coatings were tested by National Test Center of Polymer and Chemical Building Materials in Beijing, the test results met or exceeded national standard for synthetic latex wall paint of GB/T 9755-2001 synthetic resin emulsion coatings for exterior wall.
3. To solve the environmental problem of Cr in silicon steel sheet coatings, silicon steel sheet coatings without Cr were prepared by using acrylate polymer emulsion and a multi-tooth metal chelating agent. The multi-tooth metal chelating agent was used as anti-rust component, instead of the traditional components of toxic Cr. The chelating agent formed many chelate rings on the surface of silicon steel during film forming, which forming compact single-molecule protective film. This film can effectively prevent the O2 and the water getting into the silicon steel surface, and sequentially inhibit the oxidation corrosion of silicon steel. The templets of chrome free silicon steel sheet coatings were tested by the Guangzhou National Quality Supervision and Inspection Center for Household Electrical Appliances for the hot-resistance and refrigerant-resistance performance. The test results showed that the coatings fully met the requirements of coating for silicon steel sheet.
4. A method of paint adhesion classification and coatings rust area measurement was proposed, in which the Photoshop processing software and a scanner were introduced. Based on the flexible select image methods and the statistical function to the image pixel of Photoshop software, the classing method of film adhesion by using Photoshop software and scanner was proposed. The pixel was the relative area in this method. This method was more accurate than the commonly used method of image comparison. The percent area removed given by ASTM standard and the percent pixels removed measured by Photoshop was correlated, with the correlation coefficient being 0.997. Likewise, based on the flexible select image methods and the statistical function for the image pixel, combined with the height and width measurement function in "Info" panel for the image, the rusty areas can be quantitatively determined by using A'=X'/X×A. For regular rust area, the area calculated by Photoshop software and that measured by a vernier caliper and were compared. The determining error of rusty areas was under 3.0%. This proved the veracity of the result measured by Photoshop software.
本论文研究了以聚合物乳液为成膜物的三种涂料的制备及其应用性能,提出了一种用Photoshop软件进行涂层附着力分级和生锈面积检测的方法。论文主要包括以下几方面的工作：
1.以双组分环氧乳液涂料为底漆,含氟丙烯酸乳液涂料、硅丙乳液涂料、苯丙乳液涂料为面漆制备了水性裂纹漆。该水性涂料与传统的溶剂型裂纹漆相比具有环保无毒的优点,可应用于墙面、玻璃、家具或艺术品之类的表面的装饰性涂装。论文对裂纹图案产生的机理进行了分析,对裂纹间距和裂纹形状的影响因素进行了研究。试验中通过改变膜厚、面漆类型、颜料含量、涂层表面空气流通速度等因素制备了不同裂纹间距和裂纹形状的裂纹图案。含氟涂料、苯丙涂料和硅丙涂料的面漆可分别制备主要为Y-型交叉、T-型交叉和混合型交叉的裂纹图案。面漆越厚,裂纹间距越大；颜填料的含量越高,即颜基比越大,面漆越不容易开裂。在面漆干燥成膜的过程中,涂膜表面的空气流通速率的增加可使面漆产生裂纹图案的裂纹间距变小。而且,对裂纹漆的实际应用的性质,如附着力、耐水性和耐洗刷性进行了检测,检测结果表明涂料有良好的实际应用性能。
2.利用含氟乳液制备了水性耐候外墙涂料,对涂料的配方进行了设计,对涂料综合性能特别是耐候性进行了表征。耐候性主要通过涂料样板的颜色变化、光泽变化、亲疏水性变化的比较来确定。颜色变化、光泽变化、亲疏水性的变化分别用白度仪,光泽度仪和接触角测定仪进行了表征。通过人工氙灯照射老化试验研究了不同钛白粉和不同乳液制备的涂料的耐候性、耐沾污、耐水性的差异,在1000h的人工老化试验中,使用耐候的杜邦R706金红石形钛白粉配制的含氟涂料无脱落、无起泡,变色轻微。在户外暴晒、雨淋、昼夜变化等自然条件下老化1年,含氟涂料样板的涂膜无脱落、无起泡,无变色。涂料样品在北京国家化学建筑材料测试中心按照《GB/T9755-2001合成树脂乳液外墙涂料》进行了人工氙灯老化试验、耐沾污、耐水性、耐洗刷等综合性能检测,涂料性能达到或超过合成树脂乳液外墙涂料优等品标准。
3.针对目前硅钢涂料含铬的环保问题,采用纯丙乳液,金属多齿螯合剂等制备了无铬环保的硅钢薄层涂料。采用金属多齿螯合剂作为防锈组分,替代传统的有毒的含铬组分,成膜过程中在硅钢表面络合形成多个螯合环,形成坚固致密的单分子保护膜,能有效地防止O2、水等进入硅钢的表面,抑制硅钢的氧化腐蚀。硅钢片涂层样板在广州国家日用电器质量监督检验中心进行了耐热性和耐制冷剂性能检验,检测结果完全达到了硅钢涂层的要求。
4.将图像处理软件引入到涂层性能的检测中,提出了利用Photoshop软件和扫描仪进行涂膜附着力分级和生锈面积测量的方法。基于Photoshop软件的灵活的选择图像的功能和对图像像素的统计功能,采用像素代替相对面积的方法,提出了利用Photoshop软件和扫描仪进行涂膜附着力分级的方法,该方法比目前常用的图像对比的方法更为准确；Photoshop测量的剥落区域的像素占划格区域的像素百分率和ASTM标准中给出的剥离率有良好的相关性,其相关系数为0.997。同样基于Photoshop软件的灵活的选择图像的功能和对图像像素的统计功能,结合Photoshop软件“信息”面板对图像的高与宽的测量功能,通过公式对生锈面积进行计算。对规则的生锈区域,将Photoshop软件测量得到的面积和用游标卡尺测量的计算得到的面积进行了对比,相对误差在3.0%以下,证明了Photoshop软件测量结果的准确性。
Coatings are a kind of materials coated on the surface of an object, which can provide the object decorative, protective or particular functions. Waterborne coatings that use polymer emulsion as film-forming component are being paid attention to by more and more scientific and technical personnel and the application field of waterboene coatings has become more widely.
The preparation and application performance of three waterborne coatings which use different polymer emulsions as film-forming component have been investigated in this paper, and a classification method of coating adhesion and measuring method of rust area of coatings based on the Photoshop software have also been proposed. The main work of this paper is as follows:
1. The waterborne crack decorative coatings were prepared by two-component epoxy basecoat and topcoat made from one of the fluorine-containing acrylic emulsion, silicone-acrylic emulsion and styrene-acrylic emulsion. Compared with the traditional solvent-based paint, the waterborne coatings are environmental friendly and non-toxic. Crack decorative coatings can be applied to the surface of wall, glass, furniture or works of art and so on. The mechanism of crack patterns generation was analyzed. The factors that influence the crack spacing and crack shape of crack patterns were investigated. Different crack spacing and crack shape of the crack pattern were prepared by changing the film thickness, topcoat type, pigment content, the air flow rate of coating surface and other factors. Three junction types of crack patterns were prepared by the three top coatings, which were T-junction, Y-junction and mixed junction. T-junction type was made from styrene-acrylic emulsion. Y-junction type was made from fluorine-containing acrylic emulsion and mixed junctions type was made from silicone-acrylic emulsion. The crack spacing increased with the increase of the thickness of topcoat. The higher content of pigments and fillers, namely the greater the pigment to binder ratio, the more difficult of topcoat cracking. In the process of film drying, the increase of air flow speed on coating surface can result in smaller crack spacing of crack patterns. The properties of coating film including adhesion, water resistance, scrub resistance and so on were tested. The results showed that the crackle coatings possessed satisfactory properties for practical application.
2. The waterborne fluorine-containing exterior coatings were prepared using fluorine-containing polymer emulsion, whose preparation and application performance, especially the coatings' weathering durability was investigated. The coatings' weathering durability mainly determined by the changes of color, gloss and hydrophobicity. Color change, gloss change and change in hydrophobicity were measured by whiteness meter, gloss meter, and contact angle measuring instrument. Artificial aging test of coatings was carried out for 1000h in Xeon Lamp Aging Test Chamber. The fluorine-containing coatings made from weather-resistant rutile TiO2, DuPont R706, were without peeling, no blistering, and color changed slightly. After the outdoor aging under natural conditions for one year, during which the coatings undergoing sunlight, rain, diurnal variation, the fluorine-containing coating film were without peeling, no blistering and no color change. The fluorine-containing coatings were tested by National Test Center of Polymer and Chemical Building Materials in Beijing, the test results met or exceeded national standard for synthetic latex wall paint of GB/T 9755-2001 synthetic resin emulsion coatings for exterior wall.
3. To solve the environmental problem of Cr in silicon steel sheet coatings, silicon steel sheet coatings without Cr were prepared by using acrylate polymer emulsion and a multi-tooth metal chelating agent. The multi-tooth metal chelating agent was used as anti-rust component, instead of the traditional components of toxic Cr. The chelating agent formed many chelate rings on the surface of silicon steel during film forming, which forming compact single-molecule protective film. This film can effectively prevent the O2 and the water getting into the silicon steel surface, and sequentially inhibit the oxidation corrosion of silicon steel. The templets of chrome free silicon steel sheet coatings were tested by the Guangzhou National Quality Supervision and Inspection Center for Household Electrical Appliances for the hot-resistance and refrigerant-resistance performance. The test results showed that the coatings fully met the requirements of coating for silicon steel sheet.
4. A method of paint adhesion classification and coatings rust area measurement was proposed, in which the Photoshop processing software and a scanner were introduced. Based on the flexible select image methods and the statistical function to the image pixel of Photoshop software, the classing method of film adhesion by using Photoshop software and scanner was proposed. The pixel was the relative area in this method. This method was more accurate than the commonly used method of image comparison. The percent area removed given by ASTM standard and the percent pixels removed measured by Photoshop was correlated, with the correlation coefficient being 0.997. Likewise, based on the flexible select image methods and the statistical function for the image pixel, combined with the height and width measurement function in "Info" panel for the image, the rusty areas can be quantitatively determined by using A'=X'/X×A. For regular rust area, the area calculated by Photoshop software and that measured by a vernier caliper and were compared. The determining error of rusty areas was under 3.0%. This proved the veracity of the result measured by Photoshop software.
引文
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