摘要
润湿性是材料表面的重要特征之一。影响材料表面润湿性的主要因素有:材料表面能、表面粗糙度以及表面微细结构,其中低表面能材料是制备超疏水性的基本条件,表面粗糙度和表面微细结构是决定性因素。寻求和制备高表面自由能或低表面自由能的固体表面成为制备超亲水和超疏水的前提条件。
本文以季铵盐型离子液体为研究对象,利用自由基聚合方法在固体硅片表面制备了微纳米结构的聚离子液体刷,对硅片表面润湿性进行了改性。
1.对离子液体的种类、物理化学性质及其应用研究进展进行了综述,简要介绍了常见的活性自由基聚合方法在材料改性中的应用。
2.合成了季铵型离子液体单体烯丙基三乙基六氟磷酸铵,利用表面引发反向原子转移自由基聚合(Surface initiate reverse atom transfer radical polymerization)方法,以CuCl_2/Bpy/AIBN作为催化体系,将其接枝于硅片表面,制得了聚合季铵型离子液体刷。利用凝胶渗透色谱仪(GPC)、椭圆偏光仪、静态接触角测定仪、傅里叶变换衰减红外光谱(ATR-FTIR)、X射线光电子能谱(XPS)、原子力显微镜(AFM)对聚合物分子量,聚合物膜等进行了表征。结果表明,聚合离子液体膜表面的润湿性与离子液体的种类及取代基碳链长度密切相关。
3.通过氮氧自由基聚合法,在硅片表面成功聚合了ADMBA-Cl离子液体。结果表明,此种离子液体修饰的硅片表现出亲水性,通过氮氧自由基聚合法在硅片表面制备的聚离子液体薄膜与原子转移自由基聚合法制得的薄膜,表面形貌有很大不同,后者空隙较大,表面呈现均匀而致密的刷型,称之为聚合物刷,而前者表面空隙非常小,表面致密而且平整,可以将其称为聚合物膜。
4.通过表面引发原子转移自由基聚合或表面引发反向原子转移自由基聚合,将ATEA-PF_6,VBTEA-PF_6,ADMBA-PF_6,和VBDMBA-PF_6四种季铵型离子液体,自组装在硅片表面。结果表明,聚合离子液体刷表面的静态水接触角因离子液体种类的不同而不同。
Wettability is an important feature of surface. The main factors influencing the surface wettability are surface energy, surface roughness, and surface micro-nano structure, in which low surface energy is the basic conditions for preparing super-hydrophobic surface, surface roughness and surface micro-nano structure are decisive factors.
In this thesis, some quaternary ammonium ionic liquid brushes have been successfully grafted by surface-initiated radical polymerizations on single crystal silicon surface, their surface wettability was discussed in detail.
Part one: Types, physical and chemical properties, and relative application investigation advances of ionic liquids including several living radical polymerization were reviewed.
Part two: Quaternary ammonium poly(ionic liquid) brushes have successfully been grafted onto silicon surface by surface initiate reverse atom transfer radical polymerization with CuCl_2/Bpy/AIBN as catalytic system and N-allyl-N,N,N-triethyl ammonium hexafluorophosphate as monomer. Surface properties of the polymer film and the polymer molecular weight are characterized by the ellipsometry,static water contact angle measurement , fourier transform infrared spectroscopy(ATR-FTIR) , X-ray photoelectron spectroscopy(XPS), atomic force microscope(AFM) and gel permeation chromatography (GPC). The results showed that the surface wettability of the poly(ionic liquid) films was closely related to the type of ionic liquids and length of the substitutes.
Part three: poly(N-Allyl-N,N-dimethylbenzenaminium chloride, ADMBA-Cl) film was successfully grafted on silicon surface by NMP. The silicon surface modified with this ionic liquid showed hydrophilic. Compared with the film prepared by atomic transfer radical polymerization, this fim was more dense, smooth and homogeneous.
Part four: Four kinds of quaternary ammonium ionic liquids monomers, allyltriethylamine hexafluorophosphate(ATEA-PF_6), (p-vinylbenzyl)triethylammonium hexafluorophosphate (VBTEA-PF_6), N-allyl-N,N-dimethyl-N-benzenammonium hexafluorophosphat(eADMBA-PF_6) and (p-vinylbenzyl)- N,N- dimethylbenzenaminium hexafluorophosphate(VBDMBA-PF_6) were synthesized and grafted on silicon surface The results indicated that the surface wettability of the films was closely related to the structures of the ionic liquids.
引文
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