CN105949836A - 一种栅控等离子体引发气相聚合表面涂层的装置及方法 - Google Patents
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Abstract
一种栅控等离子体引发气相聚合表面涂层的装置及方法，属于等离子体技术领域，用于在基材表面制备聚合物涂层。其特征是，用金属栅网将真空室分隔为放电腔和处理室两部分；金属栅网与真空室绝缘；载体气体和单体蒸汽经不同管路分别送入放电腔和处理室内；待处理的基材放在处理室内；在放电腔内产生连续放电的等离子体，在金属栅网上施加脉冲正偏压释放等离子体进入处理室以引发单体聚合。该方法具有电源结构简单、价格低、调试容易，等离子体稳定，等离子体作用时间可以缩短到微秒级等优点。
Description
技术领域
本发明属于等离子体技术领域，涉及到一种用于在基材表面制备聚合物涂层的栅控等离子体引发聚合表面涂层的装置及方法。
背景技术
等离子体聚合是利用放电把有机类气态单体等离子体化,使其产生各类活性种,由这些活性种之间或活性种与单体之间进行加成反应形成聚合物的方法。等离子体聚合可分为等离子体态聚合和等离子体引发聚合两种形式，它们的区别是：等离子体态聚合整个反应过程中单体完全暴露于等离子体环境，而等离子体引发聚合中气体只在短时间内通过辉光放电形成的等离子体,使单体蒸气发生气相反应生成活性中心，引发单体蒸气在长时间无等离子体的后续过程中进行聚合反应。与等离子体态聚合产物存在结构复杂，反应重现性差，处理效果随时间衰减的问题相比，等离子体引发聚合方式可以较少破坏单体的结构，保留单体优良性能，使聚合产物结构较为单一，易于形成线性大分子产物；另一方面，通过与材料表面发生接枝反应，能够增强表面的附着力，使涂层效果不随时间衰减。
现有的等离子体引发聚合技术是通过脉冲调制高频辉光放电实现的。例如文献《表面涂层》(CN 1190545C)公开了一种疏水和/或疏油基材，其中包括利用脉冲调制高频辉光放电制备聚合物涂层的方法；文献《通过低压等离子体工艺施加保形纳米涂层的方法》(CN201180015332.1)也涉及利用脉冲调制高频辉光放电制备聚合物涂层的方法。这些现有技术均采用脉冲调制高频辉光放电， 是因为采用高频放电能够避免由于电极被聚合产物绝缘所造成的放电终止(高频放电即使电极被聚合产物绝缘情况下也可以维持)，而采用脉冲调制使高频放电周期性开启/关断是为了满足等离子体引发聚合所需要的短时间放电和长时间无放电聚合，其中为了尽可能减少脉冲放电开启阶段等离子体作用于单体而产生的单体碎片，应尽可能缩短脉冲放电开启阶段时间(现有技术已将等离子体作用时间缩短到几十微秒)。然而，现有技术所采用的脉冲调制高频辉光放电的方法需要使用具有脉冲调制功能的高频电源，其缺点是：脉冲调制高频电源结构复杂、价格高、不易调试；等离子体不稳定；由于等离子体起辉到维持至少需要几十微秒的时间，等离子体作用时间不能进一步缩短。
发明内容
本发明要解决的技术问题是提供一种栅控等离子体引发气相聚合表面涂层的装置及方法，以解决现有技术电源结构复杂、价格高、不易调试；等离子体不稳定；等离子体作用时间不能短于几十微秒的问题。
本发明为实现上述目的所采用的技术方案是：一种栅控等离子体引发气相聚合表面涂层的装置，其特征在于：金属栅网将真空室分隔为放电腔和处理室两部分；金属栅网连接脉冲偏压电源，金属栅网与真空室绝缘；放电腔分别连接载体气体管道与灯丝电极，灯丝电极连接电源；可放置待处理基材的处理室的远离放电腔的一侧连接排气管的一端，排气管的另一端与真空泵相连，处理室的靠近放电腔的一侧连接单体蒸汽管道，处理室与真空排气孔连通。
所述金属栅网由普通钢丝，不锈钢丝，镍丝，铜丝中的一种编织制成或由普通钢薄片，不锈钢薄片，镍薄片，铜薄片的一种打孔制成，金属栅网的网丝直径为0.02-0.5mm，网孔尺寸为0.1-1mm。
一种利用所述的栅控等离子体引发气相聚合表面涂层的装置引发气相聚合 表面涂层的方法，其特征在于：包括以下步骤：
1)将待处理基材放在处理室内；
2)载体气体和单体蒸气分别经载体气体管道、单体蒸汽管道被送入放电腔和处理室内，同时电源加热灯丝电极并提供高电压，在放电腔内产生连续辉光放电，脉冲偏压电源产生的脉冲正偏压施加在金属栅网上；
3)在放电腔内产生连续放电的稳定等离子体，在金属栅网上施加的脉冲正偏压控制和释放等离子体进入处理室以引发单体蒸汽发生聚合并沉积在基材表面形成聚合物涂层；
所述的单体的结构单元至少含有一个不饱和碳碳键，且其中一个不饱和碳原子不含取代基团；
所述形成的聚合涂层的性能与单体结构中的特征官能团性质保持一致。
所述单体包括乙烯基硅烷，乙烯基烷烃，丙烯酸酯类烷烃，甲基丙烯酸酯类烷烃中的一种或多种。
所述单体的结构中可以含有卤素官能团或其他官能团，所述卤素官能团为F,Cl,Br,I中一种或多种，其他官能团为羟基，羧基，环氧基团，硅氧基团中一种或多种。
所述等离子体由交流电压、射频感应耦合、微波、灯丝、热阴极方法中一种或组合产生。
所述脉冲正偏压幅度为10-150V，宽度为10-100μs。
所述载体气体可以是氢气、氮气、氦气、氩气中的一种或多种的混合物，优选氦气。
所述待处理基材是塑料，橡胶，环氧玻纤板，聚合物涂层，金属，纸材，木材，玻璃，织物中的一种或多种组合，且待处理基材的表面可以有化学涂层， 所述化学涂层为丙烯酸树脂涂层，醇酸树脂涂层，聚氨酯涂层中的一种。
所述特征官能团性质包括亲水，疏油，耐酸碱，生物相容，也可以作为连续阻隔覆膜延缓腐蚀。
本发明用金属栅网将真空室分隔为放电腔和处理室两部分，金属栅网与真空室绝缘，载体气体和单体蒸汽经不同管路分别送入放电腔和处理室内，待处理的基材放在处理室内，在放电腔内产生连续放电的等离子体，通过在金属栅网上施加脉冲正偏压释放等离子体进入处理室以引发处理室内的单体蒸汽发生聚合并沉积在基材表面形成聚合物涂层。本发明电源结构简单、价格低、调试容易；等离子体稳定；等离子体作用时间可以缩短到微秒级。
附图说明
图1是一种栅控等离子体引发气相聚合表面涂层的装置的结构示意图。
图中：1、金属栅网，2、放电腔，3、处理室，4、载体气体管道，5、单体蒸汽管道，6、排气管，7、真空泵，8、电源，9、灯丝电极，10、脉冲偏压电源。
具体实施方式
下面结合技术方案和附图详细叙述本发明的具体实施例。
实施例1
如图1所示的一种栅控等离子体引发气相聚合表面涂层的装置，金属栅网1将真空室分隔为放电腔2和处理室3两部分，金属栅网1由普通钢丝编织制成，金属栅网的网丝直径为0.5mm，网孔尺寸为1mm；金属栅网1连接脉冲偏压电源10，金属栅网1与真空室绝缘；放电腔2分别连接载体气体管道4与灯丝电极9，灯丝电极9连接电源8；可放置待处理基材的处理室3的远离放电腔2的一侧连接排气管6的一端，排气管6的另一端与真空泵7相连，处理室3的靠 近放电腔2的一侧连接单体蒸汽管道5，处理室3与真空排气孔连通。
实施例2
一种利用实施例1中所述的栅控等离子体引发气相聚合表面涂层的装置引发气相聚合表面涂层的方法，包括以下步骤：
1)将待处理基材放在处理室3内；
2)载体气体和单体蒸气分别经载体气体管道4、单体蒸汽管道5被送入放电腔2和处理室3内，同时电源8加热灯丝电极9并提供高电压，在放电腔2内产生连续辉光放电，脉冲偏压电源10产生的脉冲正偏压施加在金属栅网上；
3)在放电腔2内产生连续放电的稳定等离子体，脉冲正偏压关断的期间，金属栅网1自动处于等离子体的悬浮电势，阻挡等离子体穿过金属栅网1进入处理室3；脉冲正偏压开启后，金属栅网1的电势相对于放电腔内等离子体处于高电势，金属栅网1上的聚合物涂层等效于一个电容。由于电容两端电势不能突变，金属栅网1上的聚合物涂层表面瞬间也处于高电势，使等离子体穿过金属栅网1扩散进入处理室3引发单体聚合。随着等离子体中的电子对金属栅网1上的聚合物涂层充电，该聚合物表面电势下降，直到低于等离子体空间电势，等离子体被阻挡进入处理室3。
所述的单体的结构单元含有一个不饱和碳碳键，且其中一个不饱和碳碳原子不含取代基团；
所述形成的聚合涂层的性能与单体结构中的特征官能团性质保持一致。
所述单体为二甲基乙烯基乙氧基硅烷(VDMES)。
为了达到适合应用要求的化学性能，所述单体的结构中含有卤素官能团，所述卤素官能团为F。
所述等离子体由交流电压产生。
所述脉冲正偏压幅度为10V，宽度为10μs。
所述载体气体是氦气。
所述待处理基材是塑料，且待处理基材的表面有化学涂层，所述化学涂层为丙烯酸树脂涂层。
所述特征官能团性质包括亲水，疏油，耐酸碱，生物相容等，也可以作为连续阻隔覆膜延缓腐蚀。
实施例3
本实施例中所述的一种栅控等离子体引发气相聚合表面涂层的装置各部分结构与连接关系均与实施例1中相同，不同的技术参数为：
1)金属栅网1由镍丝编织制成；
2)金属栅网的网丝直径为0.02mm，网孔尺寸为0.1mm。
实施例4
本实施例中所述为一种利用实施例3中所述的栅控等离子体引发气相聚合表面涂层的装置引发气相聚合表面涂层的方法，各步骤内容与实施例2中相同，不同的技术参数为：
1)所述的单体的结构单元含有2个不饱和碳碳键；
2)所述单体为丙烯酸(AA)与甲基丙烯酸(MAA)；
3)所述单体的结构中含有羧基；
4)所述等离子体由射频感应耦合产生；
5)所述载体气体是氢气与氮气的混合物；
6)所述脉冲正偏压幅度为80V，宽度为55μs；
7)所述待处理基材是环氧玻纤板与纸材；
8)所述待处理基材的表面的化学涂层为醇酸树脂涂层。
实施例5
本实施例中所述的一种栅控等离子体引发气相聚合表面涂层的装置各部分结构与连接关系均与实施例1、实施例3中均相同，不同的技术参数为：
1)金属栅网1由铜薄片打孔制成；
2)金属栅网的网孔尺寸为0.5mm。
实施例6
本实施例中所述为一种利用实施例5中所述的栅控等离子体引发气相聚合表面涂层的装置引发气相聚合表面涂层的方法，各步骤内容与实施例2、实施例4中均相同，不同的技术参数为：
1)所述的单体的结构单元含有3个不饱和碳碳键；
2)所述单体为甲基丙烯酸甲酯(MMA),甲基丙烯酸-2-羟乙酯(HEMA)，甲基丙烯酸正辛酯(PAMOE)；
3)所述单体的结构中含有Cl,Br,I，羟基，羧基；
4)所述等离子体由微波、灯丝、热阴极方法组合产生；
5)所述载体气体是氦气与氩气的混合物；
6)所述脉冲正偏压幅度为150V，宽度为100μs；
7)所述待处理基材是金属，玻璃，织物；
8)所述待处理基材的表面的化学涂层为聚氨酯涂层。
Claims (10)
1.一种栅控等离子体引发气相聚合表面涂层的装置，其特征在于：金属栅网(1)将真空室分隔为放电腔(2)和处理室(3)两部分；金属栅网(1)连接脉冲偏压电源(10)，金属栅网(1)与真空室绝缘；放电腔(2)分别连接载体气体管道(4)与灯丝电极(9)，灯丝电极(9)连接电源(8)；可放置待处理基材的处理室(3)的远离放电腔(2)的一侧连接排气管(6)的一端，排气管(6)的另一端与真空泵(7)相连，处理室(3)的靠近放电腔(2)的一侧连接单体蒸汽管道(5)，处理室(3)与真空排气孔连通。
2.根据权利要求1所述的一种栅控等离子体引发气相聚合表面涂层的装置，其特征在于：所述金属栅网(1)由普通钢丝，不锈钢丝，镍丝，铜丝中的一种编织制成或由普通钢薄片，不锈钢薄片，镍薄片，铜薄片的一种打孔制成，金属栅网(1)的网丝直径为0.02-0.5mm，网孔尺寸为0.1-1mm。
3.一种利用如权利要求1所述的栅控等离子体引发气相聚合表面涂层的装置引发气相聚合表面涂层的方法，其特征在于：包括以下步骤：
1)将待处理基材放在处理室(3)内；
2)载体气体和单体蒸气分别经载体气体管道(4)、单体蒸汽管道(5)被送入放电腔(2)和处理室(3)内，同时电源(8)加热灯丝电极(9)并提供高电压，在放电腔(2)内产生连续辉光放电，脉冲偏压电源(10)产生的脉冲正偏压施加在金属栅网(1)上；
3)在放电腔(2)内产生连续放电的稳定等离子体，在金属栅网(1)上施加的脉冲正偏压控制和释放等离子体进入处理室(3)以引发单体蒸汽发生聚合并沉积在待处理基材表面形成聚合物涂层；
所述的单体的结构单元至少含有一个不饱和碳碳键，且其中一个不饱和碳原子不含取代基团；
所述形成的聚合涂层的性能与单体结构中的特征官能团性质保持一致。
4.根据权利要求3所述的一种栅控等离子体引发气相聚合表面涂层的方法，其特征在于：所述单体包括乙烯基硅烷，乙烯基烷烃，丙烯酸酯类烷烃，甲基丙烯酸酯类烷烃中的一种或多种。
5.根据权利要求3或4所述的一种栅控等离子体引发气相聚合表面涂层的方法，其特征在于：所述单体的结构中可以含有卤素官能团或其他官能团，所述卤素官能团为F,Cl,Br,I中一种或多种，其他官能团为羟基，羧基，环氧基团，硅氧基团中一种或多种。
6.根据权利要求3或4所述的一种栅控等离子体引发气相聚合表面涂层的方法，其特征在于：所述等离子体由交流电压、射频感应耦合、微波、灯丝热阴极方法中一种或组合产生。
7.根据权利要求3或4所述的一种栅控等离子体引发气相聚合表面涂层的方法，其特征在于：所述脉冲正偏压幅度为10-150V，宽度为10-100μs。
8.根据权利要求3或4所述的一种栅控等离子体引发气相聚合表面涂层的方法，其特征在于：所述载体气体可以是氢气、氮气、氦气、氩气中的一种或多种的混合物。
9.根据权利要求3或4所述的一种栅控等离子体引发气相聚合表面涂层的方法，其特征在于：所述待处理基材是塑料，橡胶，环氧玻纤板，聚合物涂层，金属，纸材，木材，玻璃，织物中的一种或多种组合，且待处理基材的表面可以有化学涂层，所述化学涂层为丙烯酸树脂涂层，醇酸树脂涂层，聚氨酯涂层中的一种。
10.根据权利要求3或4所述的一种栅控等离子体引发气相聚合表面涂层的方法，其特征在于：所述特征官能团性质包括亲水，疏油，耐酸碱，生物相容， 也可以作为连续阻隔覆膜延缓腐蚀。
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| CN106622824B (zh) * | 2016-11-30 | 2018-10-12 | 江苏菲沃泰纳米科技有限公司 | 一种等离子体聚合涂层装置 |
| CN107058979A (zh) * | 2017-01-23 | 2017-08-18 | 无锡荣坚五金工具有限公司 | 一种防水耐电击穿涂层的制备方法 |
| CN107058979B (zh) * | 2017-01-23 | 2018-05-11 | 江苏菲沃泰纳米科技有限公司 | 一种防水耐电击穿涂层的制备方法 |
| WO2020082680A1 (zh) * | 2018-10-24 | 2020-04-30 | 江苏菲沃泰纳米科技有限公司 | 一种聚氨酯纳米涂层及其制备方法 |
| CN114836735A (zh) * | 2021-02-01 | 2022-08-02 | 江苏菲沃泰纳米科技股份有限公司 | 基于icp的等离子体镀膜装置及其方法 |
| CN114836735B (zh) * | 2021-02-01 | 2024-01-19 | 江苏菲沃泰纳米科技股份有限公司 | 基于icp的等离子体镀膜装置及其方法 |
| CN113275217A (zh) * | 2021-05-18 | 2021-08-20 | 佛山市思博睿科技有限公司 | 等离子体接枝共聚膜层的制备方法 |
| CN113275217B (zh) * | 2021-05-18 | 2022-06-24 | 佛山市思博睿科技有限公司 | 等离子体接枝共聚膜层的制备方法 |
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| Publication number | Publication date |
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| US20180330922A1 (en) | 2018-11-15 |
| WO2017193561A1 (zh) | 2017-11-16 |
| CN105949836B (zh) | 2017-06-16 |
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