碳氟等离子体处理PET表面动力学的研究Ⅳ: 静、动态接触角 及变角XPS方法的 应用

利用静、动态接触角及变角XPS来研究碳氟(CF~4/CH~4)气体等离子体处理PET表面的浸水行为,结果表明碳氟等离子体处理的PET浸水后,其表面的憎水性下降。通过PET表面的接触角及F/C比的测定,计算出表面动力学衰减常数k,三种测试方法得到的k值都可以用来表征碳氟等离子体处理PET的表面动力学行为,其中混合气体的k值最小。从而证明混合气体等离子体的改性效果更有利于保持其表面的憎水性。     

碳氟等离子体处理PET表面动力学的研究Ⅳ: 静、动态接触角 及变角XPS方法的 应用

利用静、动态接触角及变角XPS来研究碳氟(CF~4/CH~4)气体等离子体处理PET表面的浸水行为,结果表明碳氟等离子体处理的PET浸水后,其表面的憎水性下降。通过PET表面的接触角及F/C比的测定,计算出表面动力学衰减常数k,三种测试方法得到的k值都可以用来表征碳氟等离子体处理PET的表面动力学行为,其中混合气体的k值最小。从而证明混合气体等离子体的改性效果更有利于保持其表面的憎水性。     

碳氟等离子体改性PET表面的反应机制的研究

利用CF₄与cH₄/CF₄等离子体来处理涤沦膜(PET),讨论了不同摩尔比的碳氟等离子体改性PET表面的作用机制.利用变角x光电子能谱(XPS)和接触角测试技术研究了改性后PET表面的结构和性质.结果表明,碳氟等离子体的处理可以显著地改善PET表面的憎水性.不同摩尔比的碳氟混合气体的作用机制不同,其中碳氟混合气体等离子体以聚合为主,在PET表面形成均匀的改性层;而纯CF₄气体则以刻蚀为主,含氟基团主要分布在PET表面.     

无机-有机复合聚合物:材料研究的一个新领域

无机-有机复合聚合物特别是类分子筛聚合物、类多层钙钛矿和仿生物材料的合成及其应用研究成为近几年来一个热门的研究领域。我们瞄准了这一前沿领域并合成和表征了以下四个系列具有纳米孔洞的分子笼和一维、二维或三维的新型无机聚合物:(1)带有纳米尺寸空腔和孔状结构的新型过渡金属和稀土金属聚合物;(2)含有螺旋链的一维链状聚合物;(3)具有石墨形态层状结构和优异导电性能的聚合物;(4)以强金属-金属相互作用为核心、有机分子为稳定外壳的纳米线聚合物。本文总结这四个系列化合物的合成结构和特性。     

用哈克流变仪模拟D3F反应挤出阴离子开环聚合反应

采用哈克流变仪模拟1,3,5-三甲基-1,3,5-三(3′,3′,3′-三氟丙基)环三硅氧烷(D3F)阴离子开环聚合的反应挤出试验.通过凝胶渗透色谱法(GPC)测定其绝对分子量,并通过红外光谱(FT-IR)和核磁共振氢谱(1H-NMR)表征其结构.研究表明:在促进剂乙酸乙酯作用下,120 ℃下反应4 min可得到数均分子量为2.45×105的氟硅聚合物,反应温度、时间对制备氟硅聚合物有一定的影响.     

新型含磷和氟聚芳醚的制备、表征及性能

通过分子设计, 成功合成了一种含有三苯基膦结构的二氟单体--4,4’-二氟二苯苯磷氧(BFPPO). 在碱催化条件下, BFPPO与2-双-(4-羟苯基)六氟丙烷(六氟双酚A)缩聚得到一种新型含三苯基膦结构的聚芳醚材料(6F-PAEPO). 使用FTIR,1H NMR, 31P NMR, 和16F NMR等表征手段确定了聚合物的结构, 聚合物表现出良好的热稳定性、有机可溶性、机械性能和光透过性能, 其中聚合物的玻璃化转变温度高达211℃, 空气气氛和氮气气氛下5%热失重温度分别为512℃和523℃, 聚合物薄膜的最大光透过率超过80%. 尤其, 聚合物由于主链中三苯基磷氧结构的存在, 表现出了优异的阻燃性能, 有限氧指数(LOI)达到39.9%.     

P(VdF-HFP)型聚合物电解质的结构和导电性研究

制备了以偏氟乙烯与六氟丙烯共聚物[P(VdF-HFP)]为基质的聚合物电解质,并测定了该类电解质的电导率。讨论了锂盐浓度、增塑剂配比、纳米SiO_2粉末掺入等对离子电导率的影响。结果表明:以P(VdF-HFP)为基质的电解质室温电导率最高达到2.81×10~(-3)S/cm。利用红外、扫描电镜、X射线衍射分析对聚合物电解质的结构和性能进行了表征,探讨了聚合物电解质膜的各组分间相互作用的规律。     

含三苯基膦聚醚醚酮酮的结构与性能

以双[4-(对氟苯甲酰基)苯基]苯基氧化膦和对苯二酚(HQ)为单体, 合成了新型主链含三苯基膦结构的聚醚醚酮酮, 并对聚合物的结构和性能进行了表征.     

乙烯基三甲基硅烷等离子体聚合物膜的结构与性能

采用外部电极电容耦合高频等离子体装置对乙烯基三甲基硅烷(VTMS)进行等离子体聚合。用IR、XPS、PGC/MS、X-ray、ESR和元素分析等方法对聚合物结构进行表征,并推断聚合反应历程。应用TG研究聚合物的热性能。通过X-ray证实聚合物为非晶结构。在无添加气体存在时聚合,XPS测试结果表明产物中有氧嵌入,且聚合物的C/Si比总的说来比单体的C/Si比低。TG的测试结果表明聚合物膜具有优良的热稳定性。     

直流负偏压对类金刚石薄膜结构的影响

在不同的直流负偏压下利用直流射频等离子体辅助化学气相沉积技术在单晶硅表面沉积得到了类金刚石薄膜,用拉曼光谱、红外光谱和原子力显微镜对薄膜的结构和形貌进行了表征.结果表明:无偏压时,沉积得到的薄膜呈现类聚合物结构且表面比较粗糙,而叠加了偏压后,薄膜表现出类金刚石薄膜的结构特征,随着偏压的增大,膜中的氢含量和sp3碳含量均逐渐减小,且薄膜的表面粗糙度逐渐减小.     

Stabilization of plasma-polymerized allylamine films by ethanol extraction

The effect of ethanol extraction on plasma-polymerized allylamine (PPAA) films was investigated by measuring their thickness change using surface plasmon resonance (SPR) spectroscopy and optical waveguide spectroscopy (OWS). It was found that much of the freshly deposited PPAA films is lost upon ethanol treatment. The decrease in PPAA thickness is related to the plasma input power, the monomer vapor pressure, and the thickness of the deposited films. Despite the relatively high loss in film thickness, the densities of the amine groups in the extracted PPAA are comparable to those of fresh films, as seen by Fourier transform infrared (FT-IR) spectroscopy. The results of this study are of specific importance with respect to the biomedical application of plasma-polymerized functional thin films, in which the stability of a plasma polymer in contact with aqueous media is essential.     

Deposition of π-Conjugated Polycyanate Ester Thin Films and Their Dielectric Properties

Two kinds of novel π-conjugated polycyanate esters, namely the plasma-polymerized 4-methoxyphenol cyanate ester (PPMPCE) and the plasma-polymerized 4-phenylphenol cyanate ester (PPPPCE), were successfully prepared by plasma polymerization for the first time. The structure and compositions of both plasma polycyanate esters were investigated by Fourier Transform Infrared (FT-IR), X-ray Photoelectron Spectroscopy (XPS) and UV–Visible Absorption Spectra (UV–Vis). The results show that extensively conjugated C=N double bonds were formed in the plasma-deposited cyanate ester thin films, the plasma polymerization of both monomers proceeded mainly via the opening of π-bonds of the O–C≡N functional groups which are further on being formed into a large π-conjugated system, this unique process is noticeably different from the conventional thermal polymerization reaction of cyanate ester monomers. Further dielectric measurement shows that PPPPCE thin film gives a lower dielectric constant comparing to that of the PPMPCE film, and the dielectric constant of both plasma deposited thin films decreased with an increase in measurement frequency.     

Plasma polymerization of aniline on different surface functionalized substrates

The plasma polymerization of aniline on different surface functionlized low-density polyethylene (LDPE) substrates was investigated, and the resulting polymer was characterized by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, and atomic force microscopy. The results showed that the structure of plasma-polymerized polyaniline was rather different from polyaniline synthesized by conventional chemical and electrochemical methods. This difference may be due to extensive coupling reactions and cross-linking reactions during the plasma polymerization process. The use of acrylic acid graft copolymerized LDPE substrate significantly enhanced the adhesion of the polyaniline to the substrate over that observed with pristine LDPE. The plasma polymerized polyaniline can be rendered electrically conductive if the polymerization is carried out on a polystyrenesulfonic acid-coated LDPE substrate. Conductivity can also be induced by acid protonation of the polyaniline by HClO(4). The reaction of the plasma-polymerized polyaniline with viologen grafted on the substrate under UV irradiation and with AuCl(3) and Pd(NO(3))(2) in acid solutions was also investigated.     

Vacuum lithography—A completely dry lithography using plasma processing

The purpose of this paper is to describe a thoroughly dry lithography using plasma polymerization and plasma etching. The new lithography is named vacuum lithography because all processes are performed at reduced pressures. Resist films were formed in bell-jar-type and argon-flow-type reactors. The controllability of plasma polymerization is discussed with respect to the type of reactor and gas mixture. A pattern was delineated in the resist using an electron beam, and it was developed by plasma etching with a mixture of argon and oxygen. It was found that the quality of the plasma-polymerized resist depends strongly on the polymer structure and on the plasma etching conditions. In this experiment, the recorded values of sensitivity and value of plasma-polymerized methyl methacrylate were 700 µC/cm² and 1, respectively.     

Control of attachment of bovine serum albumin to pulse plasma-polymerized maleic anhydride by variation of pulse conditions

This letter describes how the irreversible attachment of bovine serum albumin (BSA) to films of plasma-polymerized maleic anhydride can be measured by an indirect antibody-binding assay and how this attachment appears to be strongly affected by the polymerization conditions. Surface plasmon resonance (SPR) was used to follow the binding of the antibody, anti-bovine serum albumin (aBSA), to protein-modified plasma-polymerized maleic anhydride films. It was found that BSA could be irreversibly bound to polymers made under pulse plasma conditions, but BSA did not bind to polymers made under continuous wave conditions. Moreover, the degree of antibody binding, which is directly related to the quantity of BSA on the polymer, correlated with the plasma duty cycle (t(on)/t(on) + t(off)): lower duty cycle pulse plasma conditions gave greater BSA attachment. We speculate that BSA is being covalently bound to the polymer via the reaction of amine groups on lysine residues in BSA with the retained anhydride group functionality in the polymer.     

等离子体聚合及其聚合物的应用

本文着重综述了烃,含氮、氧的有机化合物,碳氟化合物以及有机硅化合物的等离子体聚合。同时还系统地介绍了等离子体聚合物在制备反渗透膜、分离膜、材料表面的涂层等方面的国内外的最新研究成果。     

H2 plasma development of X-ray imaged patterns on plasma-polymerized resists

An X-ray imaged pattern on a plasma-polymerized film was successfully developed by H₂ plasma etching. Plasma-polymerized MMA and 6FBMA were formed by using an inductively coupled argon flow type reactor. An X-ray imaged pattern on the film was attained through a knife-cut window of a gold plate. The X-ray was generated from a Cu target at 20 kV and main wavelength 1.54 Å. The pattern development was performed using a tubular type reactor with parallel plate electrodes. The quality of plasma-polymerized resists in an X-ray lithography was evaluated by comparing it with the conventional polymer in the dry and wet process, and the minimum dose rate for a visible pattern fabrication was measured to be 4.1 J/cm² for both resists in H₂ plasma etching development.     

Gold particles containing plasma-polymerized styrene as an X-ray absorber

Gold particles containing plasma-polymerized styrene film were formed simultaneously by plasma polymerization and evaporation using an inductively coupled argon gas flow type reactor. Gold was used as the evaporated metal and styrene as the monomer. The plasma etching characteristics of the film were evaluated by O₂ and CO₂ plasmas using a reactor with parallel-plate electrodes. A structure of lines and spaces of 4m width was successfully fabricated in the film on Si wafer by CO₂ plasma etching through a mask pattern of plasma-polymerized resist. A self-developed pattern was obtained through the X-ray mask with polyimide substrate by synchrotron radiation. The molecular structure and atomic composition of the film were investigated by ESCA and TEM.     

Fundamental aspect and behavior of saturated fluorocarbons in glow discharge in absence of potential source of hydrogen

The glow discharge of a series of saturated fluorocarbons, C_nF_2n+2 (n = 1, 2, 4, 6, and 8), was studied with glass substrates which do not contain any hydrogen. It was found that the deposition rate was a function of the F/C ratio of the starting fluorocarbons. That is, fluorocarbons with higher F/C ratio, such as CF₄ and C₂F₆, hardly polymerized, while fluorocarbons with lower F/C ratio, such as C₈F₁₈, polymerized as well as C₂F₄. After plasma exposure, the surface of glass substrate was characterized by measurements of water contact angle, water droplet rolling-off angle, and ESCA. Although all saturated fluorocarbon plasmas could alter the surface more hydrophobic than before, the deposited materials from fluorocarbons with higher F/C were not stable. Also, in plasmas with high F/C fluorocarbons, i.e., CF₄ and C₂F₆, sputtering of the electrode material was observed. © 1992 John Wiley & Sons, Inc.     

Characterization of diffusion-controlled mass transport through nanoporous and nanothin films plasma polymerized on a sputtered platinum electrode

We demonstrate the diffusion mode of various redox chemical species through a plasma-polymerized nanothin coating with nanometer-sized pores on a sputtered platinum (Pt) electrode. In this work, hexamethyldisiloxane plasma-polymerized films (PPFs) were added onto the sputtered platinum film, both of which were sequentially deposited in the same vacuum chamber. Results of atomic force microscopy, X-ray photoelectron spectroscopy, and electrochemical studies showed that the PPF provided the platinum electrode with a coating with a complete surface coverage. Sub-nanometer-sized pores (less than 1 nm) responsible for a highly crosslinked polymer network in the PPF coatings offered diffusivity-controlled permeation of redox molecules (i.e., size-exclusivity) rather than solubility-controlled permeation (i.e., chemoselectivity). Consequently, variation of the plasma power could give control over the size of the nanometer-sized cavities.