CN106282999B - 一种金属表面水性聚合物涂层制备方法及改性金属材料 - Google Patents
一种金属表面水性聚合物涂层制备方法及改性金属材料 Download PDFInfo
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Abstract
本发明涉及一种金属表面水性聚合物涂层制备方法及改性金属材料，提供了一种金属表面环保水性聚合物的涂装方法，包括如下步骤：(1)将金属基底洗涤后，浸泡于有机磷化液，取出干燥后金属基底的表面制得环保磷化膜；(2)将步骤(1)处理后的金属基底洗涤后放置于水性环保聚合物溶液浸泡，取出干燥后制得环保水性聚合物涂层。本发明以化学链接为主要结合方式的涂装方法可实现环保水性聚合物快速稳固的涂覆，从而完成环保水性聚合物的制备。
Description
技术领域
本发明涉及金属表面涂层的制备，特别是涉及一种金属表面水性聚合物涂层及制备方法。
背景技术
目前，水性油漆就是以水做为稀释剂、不含有机溶剂的涂料，不含苯、甲苯、二甲苯、甲醛、游离TDI有毒重金属，无毒无刺激气味，对人体无害，不污染环境等特点。可使用在：木器、金属、塑料、玻璃、建筑表面等多中材质上。但水性油漆与基底特别是金属基底的结合较差，从而成为技术瓶颈。聚乙烯醇，无毒，对人体皮肤无刺激性，是一种低成本的水性聚合物。尤其是医药级聚乙烯醇，是一种极安全的高分子有机物，对人体无毒，无副作用，具有良好的生物相容性，尤其在医疗中的如其水性凝胶在眼科、伤口敷料和人工关节方面的有广泛应用，同时在聚乙烯醇薄膜在药用膜，人工肾膜等方面也有使用。其安全性可以从用于伤口皮肤修复，和眼部滴眼液产品可见一斑。其中一些型号也常被用在化妆品中的面膜、洁面膏、化妆水及乳液中，是一种常用的安全性成膜剂。羟基乙叉二膦酸，不易水解，也不受体内酶作用。低毒并易排出体外，是一种环保的有机膦酸。
发明内容
本发明的目的是解决现有金属基底表面成膜技术中存在的部分问题，提供一种金属表面度生物兼容性的水性聚合物涂层及制备方法。
本发明的目的是通过以下技术方案实现的：
一种金属表面水性聚合物涂层的制备方法，包括如下步骤：
((1)将金属基底洗涤后，浸泡于有机磷化液，取出干燥后金属基底的金属表面制得化学反应层和磷化膜；
(2)将步骤(1)处理后的金属基底洗涤后放置于水性聚合物溶液浸泡，取出干燥后磷化膜表面制得环保聚合物涂层。
优选地，所述步骤(1)中有机磷化液的组成及体积含量如下：浓度为0.6-5mol/l的羟基乙叉二膦酸溶液1份，浓度为0.05-0.1mol/l的磷酸溶液1份或浓度为0.02-0.5mol/l的焦磷酸溶液1份。
优选地，所述有机磷化液还包括1份浓度为0.5-1g/l的磷酸二氢锌溶液或1份浓度为0.1-0.2g/l的氧化锌溶液。
优选地，所述步骤(1)中的二膦酸磷化膜的厚度为10-1000纳米。
优选地，所述步骤(1)中的洗涤为去离子水超声洗涤；浸泡温度为20-30℃，时间为1-5分钟。
优选地，所述步骤(2)中的水性聚合物溶液的浓度为0.1-10％；水性聚合物为水溶性聚乙烯醇，平均摩尔质量为30000-70000。
优选地，所述步骤(2)中的浸泡温度为20-30℃，时间为1-2分钟。
优选地，所述步骤(1)和步骤(2)中的干燥均为放置于燥箱中50-70℃干燥1-5分钟或20-30℃空气中干燥0.5-1小时。
优选地，所述步骤(2)中的聚乙烯醇涂层的厚度为10-1000微米。
本发明的另一方面为一种金属表面环保水性聚合物涂层，依次包括金属基底、化学反应层、磷化膜和水性聚合物涂层，所述磷化膜的厚度为10-1000纳米，水性聚合物涂层的厚度为10-1000微米。
本发明的有益效果：本发明提供的一种高效、简易的聚乙烯醇涂层在金属表面成膜方法，实现其与金属基底的化学链接，提高金属表面的生物兼容性能。本发明适用于各种尺寸、各类金属基底，如不锈钢，碳钢，螺纹钢，冷轧钢，热轧钢，锰钢，铝，铝合金，钛，钛合金，钴合金，镁铝合金等的一种。多数的金属表面不易与水性聚合物进行有效化学结合，本发明可有效改进此问题，当二膦酸磷化膜为主的磷化膜形成转换化学层后，在金属的表面可以吸附水溶性聚乙烯醇成膜。这种以化学链接为主要结合方式的涂装方法可实现水溶性聚乙烯醇快速稳固的涂覆，从而完成水性聚合物涂层的制备，不同于利用有机溶剂的非环保涂层方法。
附图说明
图1是本发明产品的层结构示意图；
图2是实施例1产品的光电子能谱全谱；
图3是实施例1产品的光电子能谱碳元素的高分辨图谱；
图4是实施例2产品的光电子能谱全谱；
图5是实施例2产品的光电子能谱碳元素的高分辨图谱；
图6是实施例3产品的光电子能谱全谱；
图7是实施例3产品的光电子能谱碳元素的高分辨图谱；
图8是实施例4产品的光电子能谱全谱；
图9是实施例4产品的光电子能谱碳元素的高分辨图谱。
具体实施方式
为了更好地说明本发明，下面结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述。
一种金属表面高度生物兼容性涂层，包括金属基底12、金属表面13、化学反应层14、磷化膜18和水性聚合物涂层16，磷化膜18厚度可控制在10-1000纳米，水性聚合物涂层16的厚度为10-1000微米。
制备方法如下：金属基底12与表面氧化物(如铁锈)等杂物或污染物，其中间分界为金属表面13；将金属基底12用去离子水超声洗涤后，放入常温0.6mol/l羟基乙叉二膦酸与0.05mol/l焦磷酸溶液所配置的有机磷化液中，浸泡2分钟，除去表面氧化物(铁锈)等杂物，并在金属表面13上形成一层以二膦酸盐为主的化学反应层14。这层盐的形成可参考引用文献，必要时可采用除氧装置。
将处理过的金属基底12取出在空气中干燥，化学反应层14上会形成一层二膦酸为主的磷化膜18，厚度为500纳米，多余的磷化膜必要时可通过水流冲洗掉。
磷化膜18形成后，将上述处理过的金属基底12在20℃下1％聚乙烯醇溶液中放置1分钟，水溶性聚乙烯醇将在二膦酸为主的磷化膜18的表面形成水性聚合物涂层16，厚度为500微米。
实施例1：
(1)将SPCC冷轧钢金属基底用去离子水超声洗涤后，20℃浸泡于0.6mol/l羟基乙叉二膦酸溶液1l与0.05mol/l焦磷酸溶液1l所配置的有机磷化液中2分钟后取出放置于70℃干燥箱中干燥5分钟；
(2)将(1)步骤所得冷轧钢金属基底用去离子水洗涤后，放置于1％的水溶性聚乙烯醇中，20℃浸泡2分钟；
(3)将(2)步骤所得冷轧钢金属基底放置于干燥箱中60℃温度干燥1分钟；
(4)将(3)步骤所得产品取后用去离子水洗涤1分钟；
(5)将(4)步骤所得产品放置于干燥箱中55℃温度干燥5分钟；
(6)将(5)步骤所得产品取后放入光电子能谱仪(XPS)进行检测。
实施例2：
(1)将1％的水溶性聚乙烯醇干燥制样；
(2)将(1)步骤所得样品放入光电子能谱仪(XPS)进行检测。
实施例3：
(1)将SPCC冷轧钢金属基底用去离子水超声洗涤后，放置于70℃干燥箱中干燥2分钟；
(2)将(1)步骤所得冷轧钢金属基底用去离子水洗涤后，放置于1％的水溶性聚乙烯醇中，20℃浸泡2分钟；
(3)将(2)步骤所得冷轧钢金属基底放置于干燥箱中60℃温度干燥1分钟；
(4)将(3)步骤所得样品取后用去离子水洗涤1分钟；
(5)将(4)步骤所得样品放置于干燥箱中60℃温度干燥3分钟；
(6)将(5)步骤所得样品取后放入光电子能谱仪(XPS)进行检测。
实施例4：
(1)将SPCC冷轧钢金属基底用去离子水超声洗涤后，20℃浸泡于0.6mol/l羟基乙叉二膦酸与0.05mol/l焦磷酸溶液所配置的有机磷化液中2分钟后取出放置于60℃干燥箱中干燥3分钟；
(2)将(1)步骤所得冷轧钢金属基底用去离子水洗涤后，放置于0.1％的水溶性聚乙烯醇中，20℃浸泡2分钟；
(3)将(2)步骤所得冷轧钢金属基底放置于干燥箱中60℃温度干燥1分钟；
(4)将(3)步骤所得样品取后用去离子水洗涤5分钟，并在去离子水中浸泡24小时；
(5)将(4)步骤所得样品放置于25℃空气中干燥30分钟；
(6)将(5)步骤所得样品取后放入光电子能谱仪(XPS)进行检测。
图2与图4，图3与图5基本相同，显示实施例1产品的表面与实施例2元素成分与比例相同，表明实施例1应用磷化膜后金属表面生成的聚乙烯醇膜和实施例2中的聚乙烯醇膜成分相同。同时，图6与图4，图7与图5存在根本的不同，显示显示实施例3产品的表面与实施例2元素成分与比例不同，即不使用磷化膜后金属表面无法形成聚乙烯醇膜。即磷化膜的形成是聚乙烯醇成膜的关键步骤。
图8显示实施例4产品在低浓度，长时间水溶环境下的聚乙烯醇成膜情况。结果表明通过减少表面聚乙烯醇膜厚度的办法，可以探测到化学反应层的存在。图9显示实施例4产品出现了与图3、图5与图7均不相同的碳元素的化合价态，即实施例4的产品中出现了新的元素化合价态，从而证实了二膦酸为主形成磷化膜和化学反应层的存在。实施例1存在聚乙烯醇膜，且较厚，XPS的有效探测深度只有10纳米，是看不到化学反应层和膦化膜层的，只能看到聚乙烯醇膜，所以与实例2是相同的。实施例4虽然也存在聚乙烯醇膜，但浓度低，清洗时间长，所以聚乙烯醇膜较薄，不足10纳米，XPS的有效探测深度为10纳米，因此实施例4可以看到化学反应层和磷化膜。
测试结果说明，本发明实施例1在使用了二膦酸为主形成的磷化膜和化学反应层，可以有效吸附水溶性聚乙烯醇形成水性聚合物涂层；而不使用本发明的实施例3则无法进行涂覆。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明披露的技术范围内，可轻易想到的变化或替换，都应该涵盖在本发明的保护范围之内。因此，本发明的保护范围应该以权利要求书的保护范围为准。
Claims (8)
1.一种金属表面水性聚合物涂层的制备方法，其特征在于，包括如下步骤：
(1)将金属基底洗涤后，浸泡于有机磷化液，取出干燥后在金属基底的金属表面制得化学反应层和磷化膜；
(2)将步骤(1)处理后的金属基底洗涤后放置于水性聚合物溶液浸泡，取出干燥后在磷化膜表面制得水性聚合物涂层；
所述步骤(1)中有机磷化液的组成及体积含量如下：浓度为0.6-5mol/L的羟基乙叉二膦酸溶液1份，浓度为0.05-0.1mol/L的磷酸溶液1份或浓度为0.02-0.5mol/L的焦磷酸溶液1份；所述有机磷化液还包括1份浓度为0.5-1g/L的磷酸二氢锌溶液或1份浓度为0.1-0.2g/L的氧化锌溶液。
2.根据权利要求1所述的制备方法，其特征在于，所述步骤(1)中的磷化膜的厚度为10-1000纳米。
3.根据权利要求1所述的制备方法，其特征在于，所述步骤(1)中的洗涤为去离子水超声洗涤；浸泡温度为20-30℃，时间为1-5分钟。
4.根据权利要求1所述的制备方法，其特征在于，所述步骤(2)中的水性聚合物溶液的浓度为0.1-10％；水性聚合物为水溶性聚乙烯醇，平均摩尔质量为30000-70000。
5.根据权利要求1所述的制备方法，其特征在于，所述步骤(2)中的浸泡温度为20-30℃，时间为1-2分钟。
6.根据权利要求1所述的制备方法，其特征在于，所述步骤(1)和步骤(2)中的干燥均为放置于干燥箱中50-70℃干燥1-5分钟或20-30℃空气中干燥0.5-1小时。
7.根据权利要求1所述的制备方法，其特征在于，所述步骤(2)中的水性聚合物涂层的厚度为10-1000微米。
8.一种带有根据权利要求1-7任一所述方法制备的金属表面水性聚合物涂层的改性金属材料，依次包括金属基底、化学反应层、磷化膜和水性聚合物涂层，所述磷化膜的厚度为10-1000纳米，水性聚合物涂层的厚度为10-1000微米。
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