Application of fluorocarbon plasma technology



为了解决环境污染的问题,达到清洁生产的目的,等离子体表面处理技术引起了人们的注意� �等离子体是气固液三态以外物质存在的又一种广泛存在的基本形态� �在一定条件下,如采取加热,外加电场、激光照射等手段,使分子离解和电离,形成自由电子和离子� �当电离产生的带电粒子密度达到一定的数值时,电离气体变成由带电粒子和中性粒子组成的集合体,成为等离子体� Plasma…

为了解决环境污染的问题,达到清洁生产的目的,等离子体表面处理技术引起了人们的注意� �等离子体是气固液三态以外物质存在的又一种广泛存在的基本形态� �在一定条件下,如采取加热,外加电场、激光照射等手段,使分子离解和电离,形成自由电子和离子� �当电离产生的带电粒子密度达到一定的数值时,电离气体变成由带电粒子和中性粒子组成的集合体,成为等离子体� Plasma contains a variety of high-energy active particles such as various ions, excited molecules, free radicals and photons. The energy of the plasma can act on the material surface through the collision of radiation, neutral particle flow and ion flow, so that the material surface can be modified. sex �</p

等离子体内部电子温度很高,而气体粒子(离子、中性粒子等)温度却可能很低,这种状态的等离子体称为低温等离子体� The use of low-temperature plasma to modify materials has the following outstanding advantages: it only modifies the surface of the material without damaging the material itself, and can retain the original physical and mechanical properties of the material to a large extent; plasma treatment can use various Gases, even gases that are not reactive in nature like inert gases, can also be used as reaction atmosphere; plasma treatment is a dry process, which only produces little pollution and toxic waste. Unlike traditional chemical treatment, which can cause problems such as solvent residues, it is A new energy-saving, water-saving and environmentally friendly new technology �</p

利用氟碳化合物进行等离子体处理,引入了含氟基团,获得低能表面,从而使材料获得各种特殊的性能,应用于各个方面,是材料改性的一个重要手段。

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1. Application of fluorine-containing gas low-temperature plasma technology in the textile industry</p

等离子体处理与纺织印染企业传统的湿处理工艺比较,等离子体处理技术作为一种有效的表面处理技术,是一种极具发展前途的清洁生产技术� Research on the application of plasma processing technology in textiles at home and abroad mainly focuses on the following aspects: improving the spinning performance of wool fiber; improving the dyeing and printing performance of fiber; improving the anti-felting performance of wool; and the deepening effect of dyed fabrics. ; Improve the bonding force and interface strength between fiber and polymer matrix; enhance the pre-treatment effect of fabrics, etc. The atmosphere used is mostly oxygen, nitrogen, air, argon and other gases �</p

对织物进行耐久性拒水拒油多功能整理,国内外报道较多的是以有机氟树脂进行处理。利用等离子体处理,引入了含氟基团,进行耐久性拒水拒油多功能整理,在这方面的研究还不是很多。

使用含氟气体等离子体处理可以提高多种纤维的拒水拒油性能� Yasuda used CF4 plasma to treat some common fiber fabrics such as polyester, nylon, vinylon, cotton, nylon, wool and silk. After treatment, the contact angle of the fabric increased to varying degrees, the surface tension decreased, and the fabric had good Water and oil repellency �有人利用含氟单体在棉织物、腈纶织物上进行等离子体聚合,使织物获得良好的防水效果� �而棉织物的柔软性、保水率、颜色变化、手感、透气性等都优于使用商用Scotchgad防水防污剂涂层的织物� �</p

There are a variety of gases that can be used as plasma treatment atmosphere, including CF4, C2F4, C3F6, mixed gases of CF4 and H2, etc. These gases can improve the water-repellent properties of fabrics, and the water-repellent properties vary with the type of fluorocarbon used. Different, processing time and power size vary �采用不同气体和不同操作条件处理不同织物,织物表面的含氟量有明显不同,引入的含氟基团也有所不同� �采用CF4作为气氛处理尼龙,表面氟元素含量为1-2%;以C3F6为气氛,表面氟元素含量为2.3-7.8%� Through X-ray photoelectron spectroscopy (XPS), it was observed that CF4 plasma treatment produces fluorination on the fiber surface and introduces fluorine-containing groups. Analysis of the Cls spectrum shows that -C-O-C-, -CF, -CF2 and -CF3 groups increased, while -COH and -COOH groups decreased �对不同织物,引入的主要基团也有不同,对聚酯、尼龙、维尼纶和棉织物主要引入-CF2基团,而天然蛋白质纤维羊毛和蚕丝则表现为强-CF吸收� �且C3F6处理效果优于CF4� �</p

处理效果的耐久性是评价处理效果优劣的重要指标之一� Some people reported that fabrics after plasma treatment have a time effect, that is, the hydrophilic properties obtained will gradually decline after a period of time. However, polyester fabrics were treated with CF4 plasma and found that even if the treated materials were stored for 150 days, no F/ There is a significant change in C, but there is no significant change in its water repellency. �研究发现使用气体的结构是织物处理效果耐久性的重要影响因素� �织物使用不饱和结构的气体时,耐久性较饱和结构的气体差� �原因可能是不饱和结构的气体进行等离子体处理时容易发生聚合,而聚合物与织物表面结合不是非常牢固� �</p

等离子体处理后获得的拒水性经过水洗和烘干处理It will weaken after washing, because the fluorine-containing groups on the fiber surface are prone to flipping after the fabric is washed, and the surface tension increases, causing the fabric’s water-repellent performance to decrease. High-temperature drying after washing will help restore the water-repellent performance.

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2. Fluorine-containing monomer plasma treatment of other materials</p

涤纶薄膜(PET),聚丙烯(PP)等是现在广泛使用的材料� �使用含氟单体等离子体处理这些高分子材料可获得特殊性能,获得更广泛的用途� J.Piglowski et al. used C6F14 plasma to treat PET films and used them as biological treatment materials. After plasma treatment, the material did not cause any toxic reactions, did not affect its biocompatibility, and could improve its anticoagulation. performance �有人报道在膜材料上进行等离子体聚合,得到一层含氟薄膜,可用于分离氧气和氮气� �采用C2F6和H2混合气体为气氛,当混合气体中C2F6比例增加时,氧气的渗透系数和膜的选择性都得到提高� The ink cartridge nozzle of a traditional inkjet printer has a coating containing polyimide, which is easily wetted by ink and affects the printing effect. Some people use fluorine-containing monomers as the atmosphere for plasma treatment to obtain water and oil repellency. surface, which improves the shortcomings of traditional ink cartridges and has applied for a number of patents. Using CF4/CH4 plasma to treat the surface of the material can also obtain flame retardant properties. �XPS研究表明,经甲烷等离子体处理可得到一层高度交联的聚合碳膜� �甲烷等离子体的沉积速率越高,聚合膜的厚度愈厚,愈有利于阻燃� �施来顺的研究也证实聚丙烯膜经甲烷等离子体处理后,燃烧速率普通降低,由此证实了高度交联作用的碳层对等离子体改性聚合膜的表面所起的阻燃作用� �</p

SigurdurSigurdsson等人用CF4等离子体处理PET和PP,处理后表面能降为2-20mJ/m2� �水和丙酮洗涤对处理后表面的疏水性能影响不大,说明处理表面较为稳定� �XPS表明疏水性能随着表面上非极性基团-CF2-,-CF3,和-CH2-CF2-的增加而增大� Someone used CF4CH4/CF4 plasma to modify the surface of PET, and found that different molar ratios of fluorocarbon mixed gases have different mechanisms of action, and divided them into three regions. Region 1 (0-83.3% CF4) is the plasma polymerization region, and region Plasma polymerization plays a major role in area 2 (83.3-96.2%CF4), etching plays a minor role, and etching and fluorinated grafting play a major role in area 3 (96.2-100%CF4). �</p

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3. Conclusion</p

等离子体技术能清洁、快速、高效的改变各种材料的表面性能,在纺织行业和高分子材料领域内有着重要的应用价值� �使用不同的氟碳化合物进行低温等离子体处理,可以获得特殊的低能表面,用于各种不同的用途� �但目前低温等离子体技术应用于工业,仍存在很多问题,如等离子体通常在真空中产生,给大规模应用带来了困难� �且氟碳化合物低温等离子体进行表面改性的反应机理尚未明确,限制了其进一步应用� �随着等离子体技术的完善,利用的氟碳化合物进行低温等离子体处理将得到更广泛的应用�

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