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中国 发明授权 有效

一种聚合物表面的处理方法 【EN】A kind of processing method of polymer surfaces

申请(专利)号:CN201610124028.5国省代码:浙江 33
申请(专利权)人:【中文】中国科学院宁波材料技术与工程研究所【EN】Ningbo Institute of Material Technology and Engineering Chinese Academy of Scien
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摘要:
【中文】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。 【EN】Paragraph:The present invention relates to a kind of surface treatment methods of polymer.This method is plated in polymeric body surface deposition chromium film layer using arc ions, obtained chromium film layer is silvery white in color appearance, it is similar with using the appearance of Cr VI film layer made from electroplating technology, in combination with ion beam bombardment polymer surfaces and utilize magnetron sputtering cvd nitride object hard film layer technology, substantially increase the wear-and corrosion-resistant performance of film-substrate cohesion and film layer, obtaining in polymer surfaces has strong film-substrate cohesion, and it is wear-resisting, scratch resistance, the excellent imitative electrodeposited chromium film layer of the performances such as corrosion resistance, to realize decoration and safeguard function to polymeric substrate, it and is a kind of dry type green surface treatment method of non-wastewater discharge.

主权项:
【中文】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。 【EN】1. a kind of preparation method of the silvery white film layer of polymer surfaces wear-and corrosion-resistant, it is characterized in that: successively to polymer surfaces Step is handled as follows: (1) it is bombarded using ion beam; (2) use magnetron sputtering cvd nitride object hard films, the nitride hard film include chromium nitride, aluminium titanium nitrogen, aluminium chromium nitrogen, One of aluminium titanium-silicon-nitrogen or several mixed membranous layers; (3) electric arc ion-plating deposition chromium film is used.


说明书

【中文】

一种聚合物表面的处理方法

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。

【EN】

A kind of processing method of polymer surfaces

Technical field

The present invention relates to the imitative plating chrome plating green systems of surface treatment technology of material more particularly to a kind of polymer surfaces

Preparation Method.

Background technique

Polymer material has the characteristics that cost is relatively low, light weight matter, is widely used in optics, automobile, packaging, micro- electricity

The fields such as son, medical treatment.But polymer material is relatively soft, to improve its performance such as weather-proof, anti-scratch, corrosion-resistant and simultaneous

Aesthetic effect is cared for, often its surface is handled, prepares metal or ceramic membrane etc..

In the process for treating surface of polymer material, electrodeposited chromium film is a kind of common method, is especially widely used in

The fields such as automobile, bathroom.

Currently, in the surface of polymer material electrodeposited chromium film such as plastics, usually electro-coppering, nickel first, then electrodeposited chromium film,

I.e. electrodeposited chromium film includes three layers of copper-nickel-chrome, and thickness is about 30 μm, and surface hardness is about 600Hv, which can not only

Plastic covering surface defect, while plastic-metal gloss and appearance can also be assigned.However, electroplating technology is carcinogenic substance sexavalence

Chromium primarily forms factor.European Union in 2007 has issued the RoHS instruction of " harmful substance limitation ", is distinctly claimed in European electronics

Sexavalence chromium process is forbidden to use in equipment and automobile industry, Cr VI is simultaneously also by Environmental Protection Agency's EPA strict control, this is greatly

Limit the outlet of China's electrodeposited chromium product.

In addition, conventional wet electroplating technology there is also deficiency have: water consumption energy consumption is big;Largely contain heavy metal to environmental emission

The waste water and waste liquid of ion, cyanide, soda acid and organic pollutant, and the poisonous fume containing all kinds of acid mists and dust;It is easy to draw

Ignition calamity causes heavy losses, and since there are a large amount of chemical substances at scene, the intensity of a fire is difficult to control and easily explodes, and endangers

Evil is very big.

Therefore, under health, the dual-pressure of energy and environmental problem, using wet process electroplating technology in polymer material table

Face electrodeposited chromium film is seriously obstructed, there is an urgent need to a kind of dry type, green, nontoxic Novel imitation electrodeposited chromium or replacing electroplating chromium surface

Processing technique.

Summary of the invention

Technical purpose of the invention is to provide a kind of processing method of polymer surfaces, and this method is one without discharging of waste liquid

Kind green non-pollution new method, can obtain polymer surfaces film layer using this method, outside similar with electrodeposited chromium film

See effect and wear-resisting property.

In order to achieve the above technical purposes, it is explored by many experiments, the inventors discovered that being plated in using arc ions poly-

When closing object matrix surface deposition chromium film, the close silvery-white appearance color using hexavalent chromium films made from electroplating technology of appearance.

But since polymeric substrate hardness is extremely low, need chromium film that there is good wearability, and the thickness of vacuum coating coating is general

It is lower, it is unable to reach and electricity less than 1/10th of plating film thickness, therefore using the very thin chromium film that arc ion plating obtains

Plate wearability similar in hard chromium film.For this purpose, the present inventor proposes first with magnetron sputtering cvd nitride object hard films, to improve

The wearability of whole film layer.In addition, in order to improve the binding force between polymeric matrix and film layer, the present inventor also proposes preparing

Before film layer, ion beam bombardment polymeric body surface is used first.

That is, the technical scheme adopted by the invention is as follows: a kind of processing method of polymer surfaces, it is characterized in that: to polymerization

Step is successively handled as follows in object surface:

(1) it is bombarded using ion beam;

(2) magnetron sputtering cvd nitride object hard films are used;

(3) electric arc ion-plating deposition chromium film is used.

The polymer is unlimited, including ABS, PC, PMMA, PP, PET etc..

In the step (1), ion beam is unlimited, can be ar-ion beam, and one in oxygen ion beam and nitrogen ion beam etc.

Kind is several.

In the step (2), magnetron sputtering technique is unlimited, including magnetically controlled DC sputtering, medium frequency magnetron sputtering, high power arteries and veins

Rush magnetron sputtering etc., preferably high-power impulse magnetron sputtering.

In the step (2), nitride hard film includes chromium nitride, titanium nitride, aluminium titanium nitrogen, aluminium chromium nitrogen, aluminium titanium-silicon-nitrogen etc.

One of or several mixed membranous layers.

In the step (2), preferably, nitride hard thicknesses of layers is 1 μm~3 μm.

Since nitride hard film material and polymeric substrate thermal expansion coefficient mismatch, as deposition process medium temperature is spent

Height will lead to coating surface and segmentation crack occurs, therefore in the deposition process of the nitride hard film layer in the step (2), excellent

Is there is the phenomenon within 70 DEG C by choosing in temperature control, such as is not heated in nitride hard film deposition process, such as

When causing vacuum chamber body temperature to be more than 70 DEG C because of ion bombardment, plated film is further continued for after answering intermittent cooling.

In order to further increase the consistency of nitride hard film layer, hardness and with the binding force of matrix, in the step

Suddenly in the deposition process of the nitride hard film of (2), preferably, using Ar ion beam assisted depositing.

In the step (3), due to will lead to rapid warm raising during electric arc ion-plating deposition, arc ion plating is heavy

The time of product chromium film layer is preferably 1~2min.

Preferably, carrying out step (4) after the step (3): using plasma enhancing chemical vapor deposition exists

Deposit silicon oxide in chromium film layer, with further to chromium film layer formed surface protection, improve the scratch resistance of film surface with

And corrosion resistance.In the step (4), the gas ratio and membranous layer of silicon oxide thickness of optimization can guarantee that membranous layer of silicon oxide is excellent

Different performance, and appearance transparent do not change chrome coating color.Preferably, the membranous layer of silicon oxide is with a thickness of 3 μm~10

μm。

In the step (4), implementation as one preferred, using plasma enhances chemical vapor deposition preparation

The method of silica transparent film layer is: the matrix of cvd nitride object hard film layer and chromium film layer being put into vacuum chamber, is evacuated

To 5 × 10-3PaBelow;By after heating evaporation hexamethyldisiloxane and oxygen mixed gas be passed through cavity, using flowmeter

Two kinds of gas flows are controlled, oxygen proportion in mixed gas is made to be greater than 30%;Radio-frequency power supply is opened, power is 50~300W, is made

It forms a film after gas ionization in substrate surface.

Preferably, that is, before ion beam bombardment, carrying out primer spray processing to substrate before the step (1).

In conclusion the present invention is plated in polymeric body surface deposition chromium film layer, obtained chromium film layer using arc ions

Be silvery white in color appearance, similar with using the appearance of Cr VI film layer made from electroplating technology, polymerize in combination with ion beam bombardment

Object surface, and magnetron sputtering cvd nitride object hard film layer technology is utilized, the wear-and corrosion-resistant performance of film layer is substantially increased, is had

It has the advantages that:

(1) polymer surfaces are bombarded using ion beam, polymer surfaces can be cleaned and be activated, bombarded

After will form carbon dead key, C=O bond or other activated groups (such as ammonia or imido isopolarity group) in polymer surfaces,

Chemical bond force or dipolar forces etc. will be formed between film layer, the size of these active forces is the several times of physisorption, therefore

Effectively increase the surface binding force between film layer and polymer;

(2) hardness of nitride hard film layer is 2~4 times higher than the hardness of pure metal chromium film layer, using ion beam to polymerization

On the one hand object surface using magnetron sputtering cvd nitride object hard film layer can effectively improve entire coating after being bombarded

Wear-and corrosion-resistant performance meets or exceeds the wearability of plating thick chrome coating;On the other hand, since pure metal chromium does not have dipole

Property, can not with the activated group of polymer surfaces formed dipolar forces, and nitride hard film layer can between polar group shape

At chemical bond force or dipolar forces etc., to effectively can be improved the binding force of film layer and polymeric matrix.

(3) preferably, using using plasma enhances chemical vapor deposition again after electric arc ion-plating deposition chromium film layer

Product deposits transparent membranous layer of silicon oxide in chromium film layer, further can form surface protection to chromium film layer, improve film surface

Scratch resistance and corrosion resistance;

Therefore, the silica clear protective film layer association which passes through support and the optimization of nitride hard film layer

Same-action has achieved the effect that replace clear finish, had not only played increase film performance, but also do not change the mesh of chromium Film color

, while it is more environmentally protective compared with spray paint, film layer technique, performance are more stable, and greatly reduce cost, energy

Enough obtain in polymer surfaces has strong film-substrate cohesion, and the performances such as appearance and wear-resisting, scratch resistance, corrosion resistance are excellent

Different imitative electrodeposited chromium film layer can reach decoration and protection that automobile, bathroom field handle polymer member chrome-plated surface

Functional requirement, and be a kind of dry type green surface treatment method of non-wastewater discharge.

Specific embodiment

Below with reference to embodiment, present invention is further described in detail, it should be pointed out that embodiment described below purport

It is being convenient for the understanding of the present invention, and is not playing any restriction effect to it.

Embodiment 1:

In the present embodiment, PC substrate surface is successively handled as follows:

(1) firstly, bombarding using oxygen ion beam the PC substrate surface, C=O bond polar group is formed on surface

Group.Bombard technological parameter are as follows: oxygen flow 50sccm, linear ion beam current 0.2A, substrate bias -100V, bombardment time

8min。

(2) medium frequency magnetron sputtering sedimenting chromium chloride film layer is used, with a thickness of 3 μm, keeps temperature to be lower than in deposition process

70℃.Deposition process parameters are as follows: argon flow 50sccm, nitrogen flow 20sccm, chromium target sputtering current 3A, sedimentation time

180min, six times cooling in deposition process, each 10min cooling time.

(3) electric arc ion-plating deposition chromium film layer, sedimentation time 1min are used.Deposition process parameters are as follows: argon flow

100sccm, chromium target arc stream 50A, substrate bias -40V.

(4) it will be put into vacuum chamber by the PC substrate of (1) (2) (3) processing, be evacuated to 5 × 10-3PaBelow;It will heating

Hexamethyldisiloxane and oxygen mixed gas after evaporation are passed through cavity, control two kinds of gas flows, pregnancy using flowmeter

Base disiloxane flow is 50sccm, oxygen flow 25sccm, opens radio-frequency power supply, power 100W, after making gas ionization

It forms a film in PC substrate surface, 3 μm of deposit silicon oxide.

Film layer is obtained in PC substrate surface after above-mentioned processing, appearance is silvery white in color, similar to electrodeposited chromium film outward appearance.

Through detecting, the microhardness of the film layer reaches 1200HV;The film layer is unchanged after 48 hours CSAA salt mist experiments;At 100 grams

Substrate is had no after the lower 2000 paper tapes friction of load.

Embodiment 2:

In the present embodiment, PMMA substrate surface is successively handled as follows:

(1) firstly, bombarding using nitrogen ion beam the PMMA substrate surface, amine groups are formed on surface.Bombard work

Skill parameter are as follows: nitrogen flow 50sccm, linear ion beam current 0.2A, substrate bias -100V, bombardment time 8min.

(2) high-power impulse magnetron sputtering depositing titanium nitride film layer is used, with a thickness of 2 μm, temperature is kept in deposition process

Degree is lower than 70 DEG C.Deposition process parameters are as follows: argon flow 50sccm, nitrogen flow 20sccm, titanium target pulse voltage 1000V, arteries and veins

Rush frequency 200Hz, pulsewidth 200 μ s, sedimentation time 120min, four times cooling, each 10min cooling time in deposition process.

(3) electric arc ion-plating deposition chromium film layer, sedimentation time 1min are used.Deposition process parameters are as follows: argon flow

100sccm, chromium target arc stream 50A, substrate bias -40V.

(4) it will be put into vacuum chamber by the PMMA substrate of (1) (2) (3) processing, be evacuated to 5 × 10-3PaBelow;It will add

Hexamethyldisiloxane and oxygen mixed gas after thermal evaporation are passed through cavity, using flowmeter control two kinds of gas flows, six

Tetramethyldisiloxane flow is 50sccm, oxygen flow 50sccm, opens radio-frequency power supply, and power 200W makes gas ionization

It forms a film afterwards in substrate surface, 7 μm of deposit silicon oxide.

Film layer is obtained in PMMA substrate surface after above-mentioned processing, appearance is silvery white in color, with electrodeposited chromium film outward appearance phase

Seemingly.Through detecting, the microhardness of the film layer reaches 1500HV;The film layer is unchanged after 48 hours CSAA salt mist experiments;100 grams

Substrate is had no after the lower 2000 paper tapes friction of load.

Embodiment 3:

In the present embodiment, ABS substrate surface is successively handled as follows:

(1) firstly, bombarding using oxygen ion beam the ABS substrate surface, C=O bond polar group is formed on surface

Group.Bombard technological parameter are as follows: oxygen flow 50sccm, linear ion beam current 0.2A, substrate bias -100V, bombardment time

8min。

(2) 2 μ of thicknesses of layers is made using Ar ion beam assisted depositing using Deposited By Dc Magnetron Sputtering aluminium titanium nitrogen film layer

M keeps temperature to be lower than 70 DEG C in deposition process.Deposition process parameters are as follows: argon flow 50sccm, nitrogen flow 20sccm, aluminium

Titanium target atomic ratio is 67:33, target sputtering current 3A, sedimentation time 120min, four times cooling, each cooling time in deposition process

10min。

(3) electric arc ion-plating deposition chromium film layer, sedimentation time 1.5min are used.Deposition process parameters are as follows: argon flow

100sccm, chromium target arc stream 50A, substrate bias -40V.

(4) it will be put into vacuum chamber by the ABS substrate of (1) (2) (3) processing, be evacuated to 5 × 10-3PaBelow;It will heating

Hexamethyldisiloxane and oxygen mixed gas after evaporation are passed through cavity, control two kinds of gas flows, pregnancy using flowmeter

Base disiloxane flow is 100sccm, oxygen flow 70sccm, opens radio-frequency power supply, power 300W, after making gas ionization

It forms a film in substrate surface, 8 μm of deposit silicon oxide.

Film layer is obtained in ABS substrate surface after above-mentioned processing, appearance is silvery white in color, with electrodeposited chromium film outward appearance phase

Seemingly.Through detecting, the microhardness of the film layer reaches 1700HV;It is unchanged through 48 hours CSAA salt mist experiment rear surface film layers;?

Substrate is had no after the lower 2000 paper tapes friction of 100 grams of load.

Embodiment 4:

In the present embodiment, ABS substrate surface is successively handled as follows:

(1) firstly, spraying film UV priming paint in ABS substrate surface, then the ABS substrate surface is banged using ar-ion beam

It hits, forms carbon dead key on surface.Bombard technological parameter are as follows: argon flow 50sccm, linear ion beam current 0.2A, matrix are inclined

Pressure -100V, bombardment time 8min.

(2) high-power impulse magnetron sputtering deposition of aluminum chromium nitrogen film layer is used, using Ar ion beam assisted depositing, keeps film layer thick

Degree is 1 μm, keeps temperature to be lower than 70 DEG C in deposition process.Deposition process parameters are as follows: argon flow 100sccm, nitrogen flow

20sccm, aluminium chromium target pulse voltage 800V, pulse frequency 150Hz, pulsewidth 200 μ s, linear ion beam current 0.1A, sedimentation time

60min, it is cooling primary in deposition process, cooling time 10min.

(3) electric arc ion-plating deposition chromium film layer, sedimentation time 1min are used.Deposition process parameters are as follows: argon flow

100sccm, chromium target arc stream 50A, substrate bias -40V.

(4) it will be put into vacuum chamber by the ABS substrate of (1) (2) (3) processing, be evacuated to 5 × 10-3PaBelow;It will heating

Hexamethyldisiloxane and oxygen mixed gas after evaporation are passed through cavity, control two kinds of gas flows, pregnancy using flowmeter

Base disiloxane flow is 80sccm, oxygen flow 50sccm, opens radio-frequency power supply, power 200W, after making gas ionization

It forms a film in substrate surface, 5 μm of deposit silicon oxide.

Film layer is obtained in ABS substrate surface after above-mentioned processing, appearance is silvery white in color, with electrodeposited chromium film outward appearance phase

Seemingly.Through detecting, the microhardness of the film layer reaches 1300HV;CSAA salt mist experiment rear surface film layer is unchanged within 48 hours;100 grams

Substrate is had no after the lower 2000 paper tapes friction of load.

Technical solution of the present invention is described in detail in embodiment described above, it should be understood that the above is only

For specific embodiments of the present invention, it is not intended to restrict the invention, all any modifications made in spirit of the invention,

Supplement or similar fashion substitution etc., should all be included in the protection scope of the present invention.

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