CN107151780B - 一种聚合物表面的处理方法 - Google Patents
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Abstract
本发明涉及一种聚合物的表面处理方法。该方法采用电弧离子镀在聚合物基体表面沉积铬膜层，得到的铬膜层呈银白色外观，与利用电镀工艺制得的六价铬膜层的外观类似，同时结合离子束轰击聚合物表面以及利用磁控溅射沉积氮化物硬质膜层技术，大大提高了膜基结合力与膜层的耐磨防腐性能，在聚合物表面获得具有强膜基结合力，且耐磨、耐刮擦性、耐蚀性等性能均优异的仿电镀铬膜层，从而实现对聚合物基材的装饰与防护功能，并且是一种无废水排放的全干式绿色表面处理方法。
Description
技术领域
本发明涉及材料表面处理技术，尤其涉及一种聚合物表面的仿电镀铬镀层绿色制备方法。
背景技术
聚合物材料具有成本较低、轻量质等特点，被广泛应用于光学、汽车、包装、微电子、医疗等领域。但是，聚合物材料相对较软，为提高其耐候、抗划痕、耐腐蚀等性能以及兼顾美观效果，往往对其表面进行处理，制备金属或陶瓷膜等。
聚合物材料的表面处理技术中，电镀铬膜是常用的一种方法，尤其被广泛应用于汽车、卫浴等领域。
目前，在塑料等聚合物材料表面电镀铬膜时，通常首先电镀铜、镍，然后电镀铬膜，即电镀铬膜包含铜-镍-铬三层，其厚度约为30μm，表面硬度约为600Hv，该镀膜层不仅能够覆盖塑料表面缺陷，同时还能够赋予塑料金属光泽以及外观。然而，电镀工艺是致癌物六价铬的主要形成因素。2007年欧盟发布了“有害物质限制”的RoHS指令，明确要求在欧洲电子设备及汽车行业中禁止使用六价铬工艺，六价铬同时也被美国环保署EPA严格控制，这极大的限制了我国电镀铬产品的出口。
另外，传统湿法电镀工艺还存在的不足有：耗水耗能大；向环境排放大量含重金属离子、氰化物、酸碱和有机污染物的废水废液，以及含各类酸雾和粉尘的有毒废气；容易引发火灾，造成重大损失，而且由于现场有大量化学物质，火势难以控制且极易发生爆炸，危害极大。
因此，在健康、能源和环境问题的双重压力下，利用湿法电镀技术在聚合物材料表面电镀铬膜严重受阻，迫切需要一种干式、绿色、无毒的新型仿电镀铬或替代电镀铬的表面处理技术。
发明内容
本发明的技术目的是提供一种聚合物表面的处理方法，该方法无废液排放，是一种绿色无污染新方法，利用该方法能够得到聚合物表面膜层，其具有与电镀铬膜类似的外观效果与耐磨性能。
为了实现上述技术目的，经过大量实验探索，本发明人发现采用电弧离子镀在聚合物基体表面沉积铬膜时，其外观接近利用电镀工艺制得的六价铬膜的银白色外观颜色。但是，由于聚合物基材硬度极低，需要铬膜具有良好的耐磨性，而真空镀膜涂层的厚度一般较低，小于电镀膜厚度的十分之一，因此利用电弧离子镀得到的极薄的铬膜无法达到与电镀厚铬膜相近的耐磨性。为此，本发明人提出首先利用磁控溅射沉积氮化物硬质膜，以提高整体膜层的耐磨性。另外，为了提高聚合物基体与膜层间的结合力，本发明人还提出在制备膜层之前，首先用离子束轰击聚合物基体表面。
即，本发明所采用的技术方案为：一种聚合物表面的处理方法，其特征是：对聚合物表面依次进行如下处理步骤：
(1)采用离子束进行轰击；
(2)采用磁控溅射沉积氮化物硬质膜；
(3)采用电弧离子镀沉积铬膜。
所述聚合物不限，包括ABS、PC、PMMA、PP、PET等。
所述步骤(1)中，离子束不限，可以是氩离子束，氧离子束以及氮离子束等中的一种或者几种。
所述步骤(2)中，磁控溅射技术不限，包括直流磁控溅射、中频磁控溅射、高功率脉冲磁控溅射等，优选为高功率脉冲磁控溅射。
所述步骤(2)中，氮化物硬质膜包括氮化铬、氮化钛、铝钛氮、铝铬氮、铝钛硅氮等中的一种或者几种的混合膜层。
所述步骤(2)中，作为优选，氮化物硬质膜层厚度为1μm～3μm。
由于氮化物硬质膜层材料与聚合物基材热膨胀系数不匹配，如沉积过程中温度过高，会导致涂层表面出现龟裂纹，因此在所述步骤(2)的氮化物硬质膜层的沉积过程中，优选将温度控制在70℃以内以避免出现该现象，例如在氮化物硬质膜层沉积过程不加热，如因离子轰击导致真空腔体内温度超过70℃时，应间歇冷却后再继续镀膜。
为了进一步提高氮化物硬质膜层的致密度、硬度以及与基体的结合力，在所述步骤(2)的氮化物硬质膜的沉积过程中，作为优选，采用Ar离子束辅助沉积。
所述步骤(3)中，由于电弧离子镀沉积过程中会导致快速温升，因此电弧离子镀沉积铬膜层的时间优选为1～2min。
作为优选，在所述步骤(3)之后进行步骤(4)：采用等离子体增强化学气相沉积在铬膜层上沉积氧化硅膜层，以进一步对铬膜层形成表面保护，提高膜层表面的耐刮擦性以及耐蚀性。所述的步骤(4)中，优化的气体比例以及氧化硅膜层厚度能够保证氧化硅膜层优异的性能，并且外观透明，不改变铬涂层颜色。作为优选，所述的氧化硅膜层厚度为3μm～10μm。
所述步骤(4)中，作为一种优选的实现方式，采用等离子体增强化学气相沉积制备氧化硅透明膜层的方法是：将沉积氮化物硬质膜层以及铬膜层的基体放入真空室内，抽气到5×10-3Pa以下；将加热蒸发后的六甲基二硅氧烷及氧气混合气体通入腔体，采用流量计控制两种气体流量，使混合气体中氧气比例大于30％；开启射频电源，功率为50～300W，使气体离化后在基材表面成膜。
作为优选，在所述步骤(1)之前，即在离子束轰击之前，对基材进行喷底漆处理。
综上所述，本发明采用电弧离子镀在聚合物基体表面沉积铬膜层，得到的铬膜层呈银白色外观，与利用电镀工艺制得的六价铬膜层的外观类似，同时结合离子束轰击聚合物表面，以及利用磁控溅射沉积氮化物硬质膜层技术，大大提高了膜层的耐磨防腐性能，具有如下有益效果：
(1)采用离子束对聚合物表面进行轰击，能够对聚合物表面进行清洁和活化，轰击后将在聚合物表面形成碳空键、碳氧双键或者其他活化基团(例如氨或亚氨等极性基团)，将与膜层之间形成化学键力或偶极力等，这些作用力的大小是物理吸附作用的数倍，因此有效提高了膜层与聚合物之间的表面结合力；
(2)氮化物硬质膜层的硬度比纯金属铬膜层的硬度高2～4倍，采用离子束对聚合物表面进行轰击之后利用磁控溅射沉积氮化物硬质膜层一方面能够有效提高整个涂层的耐磨防腐性能，达到甚至超过电镀厚铬涂层的耐磨性；另一方面，由于纯金属铬不具有偶极性，无法与聚合物表面的活化基团形成偶极力，而氮化物硬质膜层能够与极性基团之间形成化学键力或偶极力等，从而有效能够提高膜层与聚合物基体的结合力。
(3)作为优选，采用电弧离子镀沉积铬膜层之后再采用等离子体增强化学气相沉积在铬膜层上沉积透明的氧化硅膜层，能够进一步对铬膜层形成表面保护，提高膜层表面的耐刮擦性以及耐蚀性；
因此，该制备方法通过氮化物硬质膜层的支撑以及优化的氧化硅透明保护膜层协同作用，达到了取代透明面漆的效果，既起到了增加膜层性能，又不改变铬膜层颜色的目的，同时与喷涂面漆相比更加绿色环保，膜层工艺、性能更加稳定，并且大大降低了成本，能够在聚合物表面获得具有强膜基结合力的，且外观以及耐磨、耐刮擦性、耐蚀性等性能均优异的仿电镀铬膜层，能够达到汽车、卫浴领域对于聚合物件镀铬表面处理的装饰以及防护功能要求，并且是一种无废水排放的全干式绿色表面处理方法。
具体实施方式
下面结合实施例对本发明作进一步详细描述，需要指出的是，以下所述实施例旨在便于对本发明的理解，而对其不起任何限定作用。
实施例1：
本实施例中，对PC基片表面依次进行如下处理：
(1)首先，采用氧离子束对该PC基片表面进行轰击，在表面形成碳氧双键极性基团。轰击工艺参数为：氧气流量50sccm，线性离子束电流0.2A，基体偏压-100V，轰击时间8min。
(2)采用中频磁控溅射沉积氮化铬膜层，其厚度为3μm，沉积过程中保持温度低于70℃。沉积工艺参数为：氩气流量50sccm，氮气流量20sccm，铬靶溅射电流3A，沉积时间180min，沉积过程中冷却六次，每次冷却时间10min。
(3)采用电弧离子镀沉积铬膜层，沉积时间为1min。沉积工艺参数为：氩气流量100sccm，铬靶弧流50A，基体偏压-40V。
(4)将经过(1)(2)(3)处理的PC基片放入真空室内，抽气到5×10-3Pa以下；将加热蒸发后的六甲基二硅氧烷及氧气混合气体通入腔体，采用流量计控制两种气体流量，六甲基二硅氧烷流量为50sccm，氧气流量为25sccm，开启射频电源，功率为100W，使气体离化后在PC基片表面成膜，沉积氧化硅膜层3μm。
经过上述处理后在PC基片表面得到膜层，其外观呈银白色，与电镀铬膜外观相似。经检测，该膜层的显微硬度达到1200HV；经48小时CSAA盐雾实验后该膜层无变化；在100克载荷下2000次纸带摩擦后未见基底。
实施例2：
本实施例中，对PMMA基片表面依次进行如下处理：
(1)首先，采用氮离子束对该PMMA基片表面进行轰击，在表面形成氨基团。轰击工艺参数为：氮气流量50sccm，线性离子束电流0.2A，基体偏压-100V，轰击时间8min。
(2)采用高功率脉冲磁控溅射沉积氮化钛膜层，其厚度为2μm，沉积过程中保持温度低于70℃。沉积工艺参数为：氩气流量50sccm，氮气流量20sccm，钛靶脉冲电压1000V，脉冲频率200Hz，脉宽200μs，沉积时间120min，沉积过程中冷却四次，每次冷却时间10min。
(3)采用电弧离子镀沉积铬膜层，沉积时间为1min。沉积工艺参数为：氩气流量100sccm，铬靶弧流50A，基体偏压-40V。
(4)将经过(1)(2)(3)处理的PMMA基片放入真空室内，抽气到5×10-3Pa以下；将加热蒸发后的六甲基二硅氧烷及氧气混合气体通入腔体，采用流量计控制两种气体流量，六甲基二硅氧烷流量为50sccm，氧气流量为50sccm,开启射频电源，功率为200W，使气体离化后在基片表面成膜，沉积氧化硅膜层7μm。
经过上述处理后在PMMA基片表面得到膜层，其外观呈银白色，与电镀铬膜外观相似。经检测，该膜层的显微硬度达到1500HV；经48小时CSAA盐雾实验后该膜层无变化；100克载荷下2000次纸带摩擦后未见基底。
实施例3：
本实施例中，对ABS基片表面依次进行如下处理：
(1)首先，采用氧离子束对该ABS基片表面进行轰击，在表面形成碳氧双键极性基团。轰击工艺参数为：氧气流量50sccm，线性离子束电流0.2A，基体偏压-100V，轰击时间8min。
(2)采用直流磁控溅射沉积铝钛氮膜层，采用Ar离子束辅助沉积，使膜层厚度为2μm，沉积过程中保持温度低于70℃。沉积工艺参数为：氩气流量50sccm，氮气流量20sccm，铝钛靶原子比为67:33，靶溅射电流3A，沉积时间120min，沉积过程中冷却四次，每次冷却时间10min。
(3)采用电弧离子镀沉积铬膜层，沉积时间为1.5min。沉积工艺参数为：氩气流量100sccm，铬靶弧流50A，基体偏压-40V。
(4)将经过(1)(2)(3)处理的ABS基片放入真空室内，抽气到5×10-3Pa以下；将加热蒸发后的六甲基二硅氧烷及氧气混合气体通入腔体，采用流量计控制两种气体流量，六甲基二硅氧烷流量为100sccm，氧气流量为70sccm,开启射频电源，功率为300W，使气体离化后在基片表面成膜，沉积氧化硅膜层8μm。
经过上述处理后在ABS基片表面得到膜层，其外观呈银白色，与电镀铬膜外观相似。经检测，该膜层的显微硬度达到1700HV；经48小时CSAA盐雾实验后表面膜层无变化；在100克载荷下2000次纸带摩擦后未见基底。
实施例4：
本实施例中，对ABS基片表面依次进行如下处理：
(1)首先，在ABS基片表面喷膜UV底漆，然后采用氩离子束对该ABS基片表面进行轰击，在表面形成碳空键。轰击工艺参数为：氩气流量50sccm，线性离子束电流0.2A，基体偏压-100V，轰击时间8min。
(2)采用高功率脉冲磁控溅射沉积铝铬氮膜层，采用Ar离子束辅助沉积，使膜层厚度为1μm，沉积过程中保持温度低于70℃。沉积工艺参数为：氩气流量100sccm，氮气流量20sccm，铝铬靶脉冲电压800V，脉冲频率150Hz，脉宽200μs，线性离子束电流0.1A，沉积时间60min，沉积过程中冷却一次，冷却时间10min。
(3)采用电弧离子镀沉积铬膜层，沉积时间为1min。沉积工艺参数为：氩气流量100sccm，铬靶弧流50A，基体偏压-40V。
(4)将经过(1)(2)(3)处理的ABS基片放入真空室内，抽气到5×10-3Pa以下；将加热蒸发后的六甲基二硅氧烷及氧气混合气体通入腔体，采用流量计控制两种气体流量，六甲基二硅氧烷流量为80sccm，氧气流量为50sccm，开启射频电源，功率为200W，使气体离化后在基片表面成膜，沉积氧化硅膜层5μm。
经过上述处理后在ABS基片表面得到膜层，其外观呈银白色，与电镀铬膜外观相似。经检测，该膜层的显微硬度达到1300HV；48小时CSAA盐雾实验后表面膜层无变化；100克载荷下2000次纸带摩擦后未见基底。
以上所述的实施例对本发明的技术方案进行了详细说明，应理解的是以上所述仅为本发明的具体实施例，并不用于限制本发明，凡在本发明的原则范围内所做的任何修改、补充或类似方式替代等，均应包含在本发明的保护范围之内。
Claims (12)
1.一种聚合物表面耐磨防腐的银白色膜层的制备方法，其特征是：对聚合物表面依次进行如下处理步骤：
(1)采用离子束进行轰击；
(2)采用磁控溅射沉积氮化物硬质膜，所述氮化物硬质膜包括氮化铬、铝钛氮、铝铬氮、铝钛硅氮中的一种或者几种的混合膜层；
(3)采用电弧离子镀沉积铬膜。
2.根据权利要求1所述的聚合物表面耐磨防腐的银白色膜层的制备方法，其特征是：所述聚合物包括ABS、PC、PMMA、PP、PET中的一种或者两种以上的混合。
3.根据权利要求1所述的聚合物表面耐磨防腐的银白色膜层的制备方法，其特征是：所述步骤(1)中，离子束是氩离子束、氧离子束或者氮离子束。
4.根据权利要求1所述的聚合物表面耐磨防腐的银白色膜层的制备方法，其特征是：所述步骤(2)中，磁控溅射技术包括直流磁控溅射、中频磁控溅射，或者高功率脉冲磁控溅射。
5.根据权利要求1所述的聚合物表面耐磨防腐的银白色膜层的制备方法，其特征是：所述步骤(2)中，氮化物硬质膜层厚度为1～3μm。
6.根据权利要求1所述的聚合物表面耐磨防腐的银白色膜层的制备方法，其特征是：所述步骤(2)的氮化物硬质膜层的沉积过程中，将温度控制在70℃以内。
7.根据权利要求1所述的聚合物表面耐磨防腐的银白色膜层的制备方法，其特征是：所述步骤(2)的氮化物硬质膜的沉积过程中，采用Ar离子束辅助沉积。
8.根据权利要求1所述的聚合物表面耐磨防腐的银白色膜层的制备方法，其特征是：所述步骤(3)中，电弧离子镀沉积铬膜层的时间为1～2min。
9.根据权利要求1至8中任一权利要求所述的聚合物表面耐磨防腐的银白色膜层的制备方法，其特征是：所述步骤(3)之后进行步骤(4)：采用等离子体增强化学气相沉积在铬膜层上沉积氧化硅膜层。
10.根据权利要求9所述的聚合物表面耐磨防腐的银白色膜层的制备方法，其特征是：所述步骤(4)中，氧化硅透明膜层的厚度为3μm～10μm。
11.根据权利要求9所述的聚合物表面耐磨防腐的银白色膜层的制备方法，其特征是：所述的步骤(4)中，采用等离子体增强化学气相沉积制备氧化硅透明膜层的方法是：将沉积氮化物硬质膜层以及铬膜层的基体放入真空室内，抽气到5×10-3Pa 以下；将加热蒸发后的六甲基二硅氧烷及氧气混合气体通入腔体，采用流量计控制两种气体流量，使混合气体中氧气比例大于30％；开启射频电源，功率为50～300W，使气体离化后在基材表面成膜。
12.根据权利要求1至8中任一权利要求所述的聚合物表面耐磨防腐的银白色膜层的制备方法，其特征是：在所述步骤(1)之前，即在离子束轰击之前，对基材进行喷底漆处理。
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