不同有机单体等离子体聚合的对比研究

采用等离子体聚合的方法对正丙醇和丙烯醇进行了聚合,成功地在Si基体上得到了有机高分子薄膜,利用FT-IR,XPS研究了薄膜的结构,表明薄膜呈现出一种嵌段的高分子薄膜结构,利用AFM研究了薄膜的表面形貌并且测量了表面粗糙度,研究表明,等离子体聚合后薄膜表面十分平整,平均粗糙度在2 nm以内,利用测量薄膜表面接触角的方法计算了材料的表面能以及临界表面自由能,并且进行了讨论分析.     

射频等离子体聚合SiOx薄膜的研究

在射频等离子体放电条件下，以六甲基二硅氧烷（Hexamethyldisilone，HMDSO）为单体，氧气为反应气体，在PET薄膜及载玻片上聚合SiOx薄膜。通过红外光谱（FTIR）分析了工作压强、功率、单体氧气比、聚合时间等对聚合薄膜的结构和沉积速度的影响；通过扫描电子显微镜（SEM）观察了薄膜的表面形貌；通过表面轮廓仪测试了薄膜厚度，计算了沉积速率并对薄膜的均匀性做了研究。在38％恒温水浴箱中进行的水蒸汽阻隔实验表明，PET薄膜的阻隔性能得到有效的提高。     

大气等离子体枪制备类金刚石薄膜

大气下,采用DBD等离子体枪为等离子体聚合装置,以甲烷为单体,氩气为工作气体,在载玻片和单晶硅片上沉积类金刚石薄膜(DLC).考察了基片预处理、内电极形状、进气方式、以及等离子体炬喷口和基材的距离对DLC薄膜沉积的影响.通过傅立叶变换红外光谱(FTIR)分析聚合膜结构并探索可能的沉积机理;表面轮廓仪测定了成膜速率;并对薄膜进行了机械性能测量.     

等离子体聚合沉积聚烯丙胺薄膜改性聚酯及体外血小板粘附研究

采用脉冲和连续波方式沉积等离子体聚烯丙胺薄膜改性聚酯(PET)材料表面,并进一步在等离子体聚烯丙胺薄膜表面固定肝素分子.利用衰减全反射红外光谱、X射线光电子能谱和接触角测试等离子体聚烯丙胺薄膜的元素成分、组成和表面能,采用对三氟甲基苯甲醛衍生法和甲苯胺蓝法分别检测了等离子体聚烯丙胺薄膜表面的伯胺基浓度和固定肝素分子的聚烯丙胺薄膜表面的肝素浓度.实验结果表明,脉冲等离子体聚合薄膜PPAa-P表面的伯胺基浓度为1.4%,而连续波等离子体聚合薄膜PPAa-C表面伯胺基浓度只有0.71%.等离子体聚烯丙胺薄膜改性的PET的表面能增加,其中PPAa-P改性的PET表面的表面能的极性分量增加较大.脉冲等离子体聚烯丙胺薄膜表面固定的肝素浓度为4.07μg/cm2,为连续波等离子体聚烯丙胺薄膜表面固定肝素浓度2.23μg/cm2的1.8倍.体外血小板粘附实验结果表明,表面肝素化的PET表面有较低数量的血小板粘附和激活,尤其是在固定肝素分子的脉冲等离子体聚烯丙胺薄膜改性的PET表面表现出更好的抗凝血性.     

等离子体合成胺基生物功能薄膜的研究

采用高气压脉冲DBD放电等离子体,以丙烯胺为聚合单体,氩气为辅助气体,合成含胺基薄膜.利用各种测量方法对功能薄膜的结构、成分以及表面形貌进行洲试表征.讨论了不同等离子体放电参数对放电沉积薄膜的影响.通过体外细胞培养的方式研究了胺基生物功能薄膜对细胞黏附以及细胞生长的作用.结果表明:高气压脉冲DBD放电等离子体能够有效地聚合含胺基的薄膜,其合成的胺基功能薄膜能较好地促进细胞在其表面的黏附和生长.     

等离子体聚合胺基功能薄膜及其生物性能研究

本文采用射频(13.56MHz)等离子体技术,以丙烯胺(allylamine)为聚合单体,氩气为辅助气体,进行了合成含胺基生物功能薄膜的研究.利用接触角测定仪(WCA),傅里叶变换红外光谱(FTIR),X-射线光电子能谱(XPS)对功能薄膜的结构、成分进行测试表征.同时,也通过体外细胞培养的方式研究了胺基生物功能薄膜对细胞黏附以及细胞生长的作用,并在倒置显微镜下观察细胞的黏附以及生长情况.研究了不同等离子体参数如功率、工作气压、放电模式、占空比等对聚合功能薄膜表面结构成分、功能团含量以及生物性能的影响.测试结果表明,射频等离子聚合的胺基功能薄膜具有良好的生物相容性,能较好地促进细胞在其表面的黏附和生长.     

高气压脉冲DBD等离子体合成胺基功能薄膜及其性能研究

采用高气压脉冲DBD等离子体,以丙烯胺(allylamine)为聚合单体,氩气为辅助气体,合成胺基薄膜.利用接触角测定仪(WCA),傅立叶变换红外光谱(FTIR),原子力显微镜(AFM)对功能薄膜的结构、成分以及形貌进行测试表征.讨论了不同等离子体放电参数,如:气压、占空比、时间和功率对放电沉积薄膜的影响.结论是:高气压脉冲DBD等离子体放电能够有效地聚合含胺基的薄膜,气压、占空比、时间和功率对沉积薄膜有较大的影响.     

氢化微晶硅薄膜的两因素优化及高速沉积

采用甚高频等离子体辅助化学气相沉积技术(VHF-PECVD)分别对薄膜沉积参数进行了功率密度-沉积气压和硅烷浓度-气体总流量两因素优化.主要研究沉积参数对薄膜沉积速率和结晶状况的影响,结果表明:高沉积压强下,功率密度的提高对微晶硅薄膜(μc-Si∶H)沉积速率的影响减弱,硅烷浓度和气体总流量影响作用相对增强,高硅烷浓度有利于材料的利用,最终在高压强(600Pa)条件下,使微晶硅薄膜的沉积速率提升到2.1nm·s-1.同时,利用分步沉积法对薄膜的纵向结构均匀性进行了初步研究.     

等离子体聚合掺有苯环的超薄有机硅膜

用化学气相沉积方法制备了超薄有机硅膜.研究了等离子体聚合工艺过程中,工艺条件对膜的特性和沉积速率的影响.结果表明沉积掺有苯环的有机硅膜增强了膜的强度和耐腐蚀性能.最近研制的膜已成功地用于一些工程中.     

射频功率对微晶硅薄膜微结构和光电性能的影响

采用射频等离子体增强化学气相沉积(rf-PECVD)技术,在玻璃和硅衬底上沉积微晶硅(μc-Si:H)薄膜。利用拉曼光谱、AFM和电导率测试对不同射频功率下沉积的薄膜的结构特性及光电性能进行分析。研究表明:随着射频功率的增加,薄膜的晶化率和沉积速率也随之增加,而当射频功率增加到一定的程度,晶化率和沉积速率反而减小。薄膜的暗电导率与晶化率的变化情况相对应。     

Kontrollierte Abscheidung und Alterung von Plasmapolymerschichten

Controlled deposition and ageing of plasma‐polymerized films A combined analytical approach using surface analytical methods as ESCA, ToF‐ SIMS and XAS is demonstrated to be successfull in the chemical characterisation of plasma polymerised films. Elements as well as functional groups can be identified and determined (semi‐)quantitatively. Correlations between deposition parameters and film chemistry can be established thus enabeling a controlled deposition. Ageing phenomena due to air exposure can be investigated more in detail because the spectrometers are combined with a plasma deposition chamber in a way that freshly deposited samples can be investigated without any air exposure which are, subsequently, exposed to air. Selected examples are presented considering plasma polymerised films made from ethylene‐, allylamine and allyl alcohol.     

丙烯酸、丙烯醇、乙烯基咪唑三元共聚物的合成

通过沉淀聚合的方法,采用偶氮二异丁基腈为引发剂,将乙烯基咪唑、丙烯酸、丙烯醇三元共聚,制备了一种具有类似于纤溶酶生物活性的新型高分子。探讨了合成条件对聚合过程、黏度及分子量的影响,并对利用红外光谱(IR)和核磁共振(NMR)对该共聚物进行了结构表征。纤维蛋白平板实验证实该共聚物能溶解血栓。     

Plasma polymer coatings to aid retinal pigment epithelial growth for transplantation in the treatment of age related macular degeneration

Subretinal transplantation of functioning retinal pigment epithelial (RPE) cells grown on a synthetic substrate is a potential treatment for age-related macular degeneration (AMD), a common cause of irreversible vision loss in developed countries. Plasma polymers give the opportunity to tailor the surface chemistry of the artificial substrate whilst maintaining the bulk properties. In this study, plasma polymers with different functionalities were investigated in terms of their effect on RPE attachment and growth. Plasma polymers of acrylic acid (AC), allyl amine (AM) and allyl alcohol (AL) were fabricated and characterised using X-ray photoelectron spectroscopy (XPS) and water contact angle measurements. Octadiene (OD) hydrocarbon films and tissue culture polystyrene were used as controls. Wettability varied from hydrophobic OD to relatively hydrophilic AC. XPS demonstrated four very different surfaces with the expected functionalities. Attachment, proliferation and morphological examination of an RPE cell line and primary RPE cells were investigated. Both cell types grew on all surfaces, with the exception of OD, although the proliferation rate of primary cells was low. Good epithelial morphology was also demonstrated. Plasma polymerised films show potential as cell carrier surfaces for RPE cells in the treatment of AMD.     

含氮化合物的等离子共聚研究

报道了含氮化合物如吡咯（Ｐyr)、吡啶（Ｐd)、四氢吡咯（Ｐyd)和六氢吡啶（Ｐpd)等离子（Plasma)聚合研究结果,它们具有相对不同的聚合行为。同时不研究了催化剂Ｉ２对Ｐlasma聚合的加速作用,可使吡咯Ｐlasma聚合速率提高４０％－６０％。     

Interface molecular engineering of carbon-fiber composites

Adhesion of carbon fibers to epoxy and related resins is a complex subject requiring a fundamental understanding of: (a) the nature of the adhesive characteristics of the fiber; (b) the mechanisms involved; and (c) an appropriate quantification of adhesion. This paper discusses the application of plasma co-polymerization of acrylic acid/hexane, allyl alcohol/hexane and allylamine/octadiene, for the controlled functionalization of untreated type A carbon fiber through the deposition of thin, conformal coatings. The single-fiber fragmentation test has been used to estimate the influence of these pretreatments. The conventional data reduction technique and cumulative stress transfer function (CSTF) have been used as a measure of adhesion. The surface free energy of the coatings of allyl alcohol/octadiene deposited on glass plates, has also been estimated from the contact angle of polar and non-polar liquids. Hydrocarbon coatings resulted in a lower degree of adhesion than the parent untreated fiber. Increasing the concentrations of acrylic acid and allylamine promoted adhesion. This was attributed to the formation of covalent bonds between functional groups on the fibers and epoxy groups. The incorporation of allyl alcohol was less effective, because only dipole–dipole interactions were available. Contact angle measurements indicated that the polar component of surface free energy increased with the hydroxyl group concentration, despite no quantifiable increase in adhesion. The CSTF methodology has been shown to provide a precise estimate of adhesion.     

Immobilization of laccase and tyrosinase on untreated and plasma-treated cellulosic and polyamide membranes

Laccase and tyrosinase were immobilized by adsorption and covalent attachment onto microfiltration membranes made of cellulosic and polyamide material. Amine, hydroxyl and carboxylic functional groups for covalent attachment were generated by plasma polymerization of allylamine, allyl alcohol and acrylic acid using mild plasma parameters. Mass analysis of the modified membranes, surface tension and FTIR-ATR spectra were used to show the presence of stable plasma polymer on the membrane surface. It was shown that untreated and plasma treated cellulosic membranes were unsuitable for laccase and tyrosinase immobilization. Both, immobilization of laccase onto polyamide membrane modified with AlNH₂ and adsorption on the untreated membrane at pH 5.2 gave satisfactory and comparable results with better operational stability in 10 consecutive batch processes for covalently bound enzyme. In the case of tyrosinase, adsorption of the enzyme on the untreated PA at pH 7.0 was as effective as covalent binding onto PA-AlNH₂ (in pH 7.0). Operational stability was tested in the presence of diphenolic substrate, which exhibits strong suicide inactivation towards the enzyme. It was shown that immobilized tyrosinase seems to be exceptionally stable in the presence of diphenolic substrate.     

Catalytic properties of polyvinylpyridine complexes of palladium

The catalytic activity of poly-2-vinylpyridine-Pd(II) and poly-4-vinylpyridine-Pd(II) complexes was studied with respect to hydrogenation of allyl alcohol. The reaction order for allyl alcohol, hydrogenation rate and activation energy were determined. Observation of the specific rate of allyl alcohol reduction indicates that the order of activity of the catalysts under study is: P4VP-Pd(0) > P2VP-Pd(0) > P4VP-Pd(II) > P2VP-Pd(II) > Pd black. Polyvinylpyridine complexes of palladium promote the selective hydrogenation of allyl alcohol to propanol with 86–89% product yield. The influence of the structure of the polymer complexes on their catalytic activity is discussed.     

醋酸乙烯细乳液聚合动力学

用十二烷基硫酸钠(SDS)为乳化剂,十六醇(CA)为难溶助剂,以偶氮二异丁腈(AIBN)引发醋酸乙烯酯(VAc)进行细乳液聚合。在聚合体系中预先引入了聚合物,研究了聚合物、温度、引发剂浓度对细乳液转化率的影响,得出聚合物的引入可以显著加快聚合反应速率,聚合物用量宜控制在单体用量的2%,反应的表观活化能为38.6 kJ/mol,聚合速率与引发剂浓度的0.24次方成正比。     

Study of the effect of process parameters for n-heptylamine plasma polymerization on final layer properties

Plasma polymerization processes are widely used to chemically functionalize surfaces, which properties can be tuned by different operating variables. In this study, thin amine-containing polymer layers were produced on solid substrates in a custom-made cylindrical plasma polymerization reactor by radio frequency glow discharges of n-heptylamine vapours. Carefully planned experiments were conducted to evaluate the importance of four different process parameters on the chemical composition and thickness of the resulting films. The parameters investigated were: 1) deposition time, 2) power of the glow discharge, 3) distance between the electrodes, and 4) monomer pressure. Possible interactions between these variables were investigated through the use of statistical analyses (i.e., factorial design). This study reveals that n-heptylamine plasma polymer (HApp) layer thickness is influenced by the power of the glow discharge and the deposition time, as assessed by surface plasmon resonance and atomic force microscopy step height measurements. Also, the atomic ratio of nitrogen to carbon atoms on the treated surfaces is mainly influenced by the power of the glow discharge, as revealed by X-ray photoelectron spectroscopy. Quartz crystal microbalance analysis also confirmed that HApp layers are stable when immersed in aqueous solution.