反射吸收红外光谱法研究铝表面硅烷试剂膜的结构与性能

采用反射吸收红外光谱法（RA－IR）研究了铝金属表面涂覆乙炮基三乙氧基硅烷（VS），环氧基三乙氧基硅烷（GS）和γ－氨丙基三乙氧基硅烷（γ-APS）溶液成膜后结构及膜与金属表面之间结合状态，比较并探讨了不同处理工艺条件下硅烷溶液在金属铝材上成膜后膜的特性。以指导硅烷用作金属表面处理新技术的优化和实用化处理过程。     

表面硅烷化铜箔的电化学腐蚀与防护研究

用γ-氨丙基三甲氧基硅烷(γ-APS)溶液对铜箔表面硅烷化处理,采用动电位极化和电化学交流阻抗研究不同pH的γ-氨丙基三甲氧基硅烷溶液自组装铜箔电极在0.1 mol.L^-1NaCl溶液的腐蚀防护效果,采用扫描电子显微镜观察γ-氨丙基三甲氧基硅烷自组装膜的表面形貌.结果表明,γ-氨丙基三甲氧基硅烷自组装铜箔有较好的腐蚀防护效果,其中pH=7的γ-氨丙基三甲氧基硅烷溶液自组装膜的抗腐蚀效果最佳.     

Ar/O2低温等离子体处理对高密度聚乙烯-玻璃粘接性能的影响

Ar／O2低温等离子体处理的高密度聚乙烯(HDPE)膜，和硅烷化玻璃进行粘接。借助X光电子能谱仪(XPS)和衰减全反射红外光谱(ATP-FTIR)对Ar／O2等离子体处理的HDPE膜和硅烷化玻璃进行表面结构分析。研究不同等离子体处理时间、成层温度和成层时间对HDPE／APS-玻璃粘接效果的影响，考察HDPE膜的亲水性与其粘接性之间的关系，寻找HDPE／APS-玻璃最佳粘接条件。结果表明，在本实验条件下，实现了HDPE膜与玻璃之间的粘接，HDPE／APS-玻璃剥离粘接强度高达51．2N／cm。     

钼酸盐封闭后处理的热镀锌钢板硅烷膜的耐蚀性

为进一步增强硅烷膜的耐蚀性, 将硅烷化热镀锌钢板用钼酸盐溶液进行封闭后处理, 并采用扫描电子显微镜(SEM)、中性盐雾(NSS)实验、盐水全浸实验和电化学技术研究了所得复合膜层的表面形貌和耐蚀性能. 结果表明: 经钼酸盐溶液封闭处理后, 硅烷膜的孔隙被填充, 在锌层表面形成了由硅烷膜和钼酸盐转化膜构成的连续完整致密的复合膜; 复合膜的耐蚀性能明显提高, 且与钼酸盐溶液的封闭时间有关, 封闭60 s时所形成的复合膜的耐蚀性最佳. 在5%(w, 质量分数)NaCl溶液中的电化学测量结果表明: 硅烷化热镀锌钢板经钼酸盐溶液封闭处理后, 同时抑制了腐蚀过程中的阳极和阴极反应, 但主要是抑制阴极反应, 导致腐蚀电流密度明显减小, 发挥了单一硅烷膜和单一钼酸盐转化膜腐蚀防护的协同效应, 腐蚀防护效率高达99.1%; 随浸泡时间延长, 试样低频扩散阻抗先增大后减小, 表明膜层具有一定的“自愈”能力, 其耐蚀性优于常规铬酸盐钝化膜.     

微米/纳米结构对氟硅烷修饰氧化铝表面疏水性能的影响

以多孔氧化铝膜为基板,用NaOH溶液进行化学腐蚀,控制适当的条件,得到氧化铝微米/纳米表面结构.用氟硅烷分别修饰光滑氧化铝膜、多孔氧化铝膜及其微米/纳米结构表面,进行接触角测试、XPS成分分析和SEM结构表征.结果表明,氟硅烷修饰的微米/纳米结构表面对水的接触角(149°±2°)比光滑表面(101°±1°)和纳米孔洞结构表面(141°±2°)都高.     

用CuCl直接合成三乙氧基硅烷的研究

对氯化亚铜催化剂进行了预处理及在溶剂中硅粉与气态醇反应合成三乙氧基硅烷进行了研究，讨论了反应温度、氯化亚铜用量、硅粉粒度、乙醇流量及不同预处理温度对反应的影响，优化了工艺条件。发现低温处理下三乙氧基硅烷的选择性可达到96．5％，首次提出三乙氧基硅烷反应机理。     

氟硅烷自组装单分子膜的制备及其摩擦学性能

利用分子自组装技术制备了全氟辛酰胺丙基硅烷单分子膜,用X射线光电子能谱(XPS)对组装膜的表面元素进行了表征;接触角测试表明,该组装膜具有很好的疏水疏油性,其对水的接触角高达105°,对正十六烷的接触角为50°.摩擦磨损实验结果表明,全氟辛酰胺丙基硅烷自组装单分子膜可以大大降低基片的摩擦系数,使载玻片的摩擦系数从0.85左右降低到0.14左右,而且低负荷下具有很好的耐磨性.     

过渡金属表面有机官能团硅烷膜的研究——镍电极表面γ-氨丙基三甲氧基硅烷膜的结构

在镍电极表面制备了γ-氨丙基三甲摒在硅烷膜并对其形成和结构进行了研究 。镍电极表面有机官能团硅烷膜的X射线光电子能谱（XPS）结果表明氮、硅等元素 在电极表面的存在，并且氨基在膜中有若干种存在方式，包括自由氨基和质子化的 氨基。通过对表面增强拉曼散射光谱（SERS）谱图的分析，发现与电极表面作用的 吸附基团硅醇羟基和氨基发生了竞争吸附，它们及其邻近基团的拉曼谱几随着电位 的负称除了相对强度发生变化以外，还发生了一定的位移，这缘于吸咐基团吸附的 量和吸附取向随电极电位发生了变化并形成的更为复杂的界面结构；氨基不同存在 方式之间也会随之发生转变，这一结果与X射线光电子能谱分析的结果相符合。原 子力显微镜（AFM）结果表明镍电极表面的有机官能团硅烷膜呈现为一种较规则的 多孔结构。     

氟硅烷自组装单分子膜的制备及其摩擦学性能

利用分子自组装技术制备了全氟辛酰胺丙基硅烷单分子膜,用X射线光电子能谱(XPS)对组装膜的表面元素进行了表征;接触角测试表明,该组装膜具有很好的疏水-疏油性,其对水的接触角高达105°,对正十六烷的接触角为50°.摩擦磨损实验结果表明,全氟辛酰胺丙基硅烷自组装单分子膜可以大大降低基片的摩擦系数,使载玻片的摩擦系数从0.85左右降低到0.14左右,而且低负荷下具有很好的耐磨性.     

多孔硅球的活化和硅烷化

经甲烷磺酸水溶液活化处理的多孔硅球与γ－氨丙基三乙氧基硅烷的反应能力较浓盐酶活化方法有显著提高；多孔硅球与γ－氨丙基三乙氧基硅烷的反应由两个步骤组成，即先室温反应然后再回流；用改进方法制备的氨丙基硅烷化多孔硅球固定化胰凝乳蛋白酶时，其酶活力满足选择催化ＤＬ－苯丙氨酸甲酯水解的需要，相同反应条件下，多孔硅球比表面积越大，氨丙基硅烷化产物氨基含量越高。     

Effect of deposition parameters on the wettability and microstructure of superhydrophobic films with hierarchical micro-nano structures

Superhydrophobic films with hierarchical micro-nano structures were deposited on glass substrates by solution immersion method from a solution containing cobalt chloride, urea and cetyl trimethyl ammonium bromide (CTAB). Subsequently the films were hydrophobized with a low surface energy material like octadecanoic acid under ambient conditions resulting in superhydrophobic surfaces with water contact angle (WCA) of about 168° and contact angle hysteresis of 1°. The effect of deposition parameters such as solution composition, temperature, deposition time and alkanoic acid treatment on surface morphology and wettability of the films was studied. Mechanism of formation of cobalt chloride carbonate hydroxide film is discussed. Addition of CTAB to the solution resulted in a change in the surface morphology of the deposited films with flower-like structures. The wettability of films obtained under different process conditions was correlated to surface roughness using Wenzel and Cassie models.     

金核银壳纳米粒子薄膜的制备及SERS活性研究

采用柠檬酸化学还原法制备金溶胶, 通过自组装技术在石英片表面制备金纳米粒子薄膜, 在银增强剂混合溶液中反应获得金核银壳纳米粒子薄膜. 用紫外-可见吸收光谱仪和原子力显微镜(AFM)研究了不同条件下制备的金核银壳纳米粒子薄膜的光谱特性和表面形貌, 并以结晶紫为探针分子测量了金核银壳纳米粒子薄膜的表面增强拉曼光谱(SERS). 结果表明, 金纳米粒子薄膜的分布、银增强剂反应时间的长短对金核银壳纳米粒子薄膜的形成均有重要影响. 制备过程中, 可以通过控制反应条件获得一定粒径的、具有良好表面增强拉曼散射活性的金核银壳纳米粒子薄膜.     

Nanostructure formation in polymer thin films influenced by humidity

The influence of relative humidity (RH) during the film preparation on the surface morphology and on the material distribution of the resulting technical polymer blend films consisting of poly (methyl methacrylate) (PMMA) and poly (vinyl butyral) (PVB) is investigated by atomic force microscopy. Both pure polymers and polymer blends with different compositions of PVB/PMMA dissolved in tetrahydrofuran (THF) were used. Polymer films prepared under dry conditions (RH < 20%) are compared with those that have the same polymer composition but were prepared under increased humidity conditions (RH > 80%). The films consisting of the pure polymers showed a nonporous surface morphology for low‐humidity preparation conditions, whereas high‐humidity preparation conditions lead to porous PVB and PMMA films, respectively. These pores are explained as the result of a breath figure formation. In the case of the polymer blend films containing both polymers, porous or phase‐separated surface structures were observed even at low‐humidity conditions. A superposition of the effects of phase separation and breath figure formation is observed in the case of polymer blend films prepared under high‐humidity conditions. Atomic force microscopy (AFM) images taken before and after the treatment with ethanol as a selective solvent for PVB indicate that PMMA is deposited on top of a PVB layer in the case of the low‐humidity preparation process whereas for high‐humidity conditions the silicon substrate is covered with a PMMA film. Copyright © 2006 John Wiley & Sons, Ltd.     

类金刚石碳薄膜对碳膜导电性能的影响

以聚酰亚胺薄膜为原料,经炭化形成碳膜;进而在碳膜表面制备了类金刚石碳(DLC)薄膜,研究了制备条件对碳膜导电性能的影响.采用扫描电镜分析了薄膜的表面形貌和微观结构;采用X射线衍射仪分析了薄膜的晶体结构.结果表明,DLC薄膜的电阻率随着沉积时间的延长先减小后增加;当沉积时间达到3 h时,相应DLC薄膜的电阻率达到最小值5.66×10-5Ω.m.     

Surface properties and swelling behaviour of hyperbranched polyester films in aqueous media

Thin films of hydroxyl (POH) and carboxyl (PCOOH) terminated aromatic hyperbranched polyesters (HBPs) were prepared by spin coating on silicon wafers and subsequently annealed above their glass transition temperature (T_g). The surface properties and the swelling behaviour of these films in aqueous buffer solutions were studied as a function of annealing time using contact angle measurements and ellipsometry. Non-annealed films were hydrophilic with surface free energies of 51 mJ/m² for POH and 49 mJ/m² for PCOOH, respectively. The swelling behaviour of the polymer films in buffer solution with pH 7.4 was described in terms of changes of the thickness and effective refractive index of the swollen layer. Under identical conditions a lower water uptake was found for hydroxyl terminated HBPs (POH) which were annealed more then 2 h. The lower water uptake correlates with the surface properties of the films. The annealed films were less hydrophilic. Their surface free energy was 38 mJ/m² independent of the annealing. Films of carboxyl terminated HBPs (PCOOH) showed similar surface properties after annealing. However, these films were unstable under the same conditions in aqueous solutions. Stable PCOOH films were obtained by additional covalent binding to the substrate using an epoxy silane as a coupling agent.     

Supramolecular structure of polylactides: Influence of the crystallization parameters on the structure of film samples

The supramolecular formations and structure of the surface of polylactide films were studied. Atomic force and optical microscopy techniques were used to examine the spherulite growth processes and the influence of the sample preparation conditions on the surface parameters of polylactide films. Isothermal crystallization runs produced a number of samples differing in the structure of the supramolecular formations and in the surface roughness characteristics.     

Controlling wrinkles and assembly patterns in dried graphene oxide films using lyotropic graphene oxide liquid crystals

We fabricated graphene oxide (GO) films on glass substrates by blade coating a lyotropic GO liquid crystal dispersion. Substrate temperature and blading speed were precisely controlled to manipulate the surface morphologies of GO films. The temperature and blade speed influenced the drying rate of film and the amount GO dispersion supplied. By controlling these parameters, film-thickness modulation and three types of surface wrinkle patterns were selectively achieved. We also plotted the wrinkle patterns diagram as functions of the film fabrication conditions. The films exhibited different optical anisotropies depending on wrinkle patterns. GO films with controlled wrinkles can be used as electrodes for supercapacitor applications owing to the large surface areas.     

An atomic-force microscopy study of the formation of vinyl and acryl graft polymers on a polypropylene film surface

Changes in the surface structure of oriented polypropylene (PP) films in conditions of graft copolymerization of acrylamide, vinylpyridine, and styrene on a PP surface preliminary subjected to plasmochemical activation in oxygen plasma or in a plasma-electrolyte solution system are investigated by atomic-force microscopy. It is shown that the latter soft conditions of activation are superior to the hard conditions with oxygen plasma in retaining original lamellar structure of oriented PP films. It is established that the subsequent graft copolymerization of the vinyl and acryl monomers on the PP surface yields amorphous phases of respective polymers.     

Surface structural evolution in iron oxide thin films

Ordered iron oxide ultrathin films were fabricated on a single-crystal Mo(110) substrate under ultrahigh vacuum conditions by either depositing Fe in ambient oxygen or oxidizing preprepared Fe(110) films. The surface structure and electronic structure of the iron oxide films were investigated by various surface analytical techniques. The results indicate surface structural transformations from metastable FeO(111) and O-terminated Fe(2)O(3)(0001) to Fe(3)O(4)(111) films, respectively. The former depends strongly on the oxygen pressure and substrate temperature, and the latter relies mostly upon the annealing temperature. Our experimental observations are helpful in understanding the mechanisms of surface structural evolution in iron oxides. The model surfaces of Fe-oxide films, particularly O-terminated surfaces, can be used for further investigation in chemical reactions (e.g., in catalysis).     

Influence of substrate nature and growth conditions on the morphology of thin DMOAP films

We report some preliminary results on the morphology of thin N,N -dimethyl- n -octadecyl-3-aminopropyltrimethoxysilyl chloride (DMOAP) films. When deposited on a glass substrate, DMOAP forms a mono- or multi-layer structure parallel to the substrate. The surface topography of the film is probed by atomic force microscopy. In general, the free surface of such a film is not flat and smooth. Islands and holes are formed on the free surface of the films when a sufficiently flat substrate is used. The thin film surface topography depends strongly on the nature of the bare substrate, the curing conditions, and the immersion time of the substrate in the DMOAP solution. The film is always rougher than the bare substrate used. Annealing roughens the surface of the alkoxysilane thin films deposited on a glass substrate. For films on glass plates covered with an indium tin oxide layer, annealing has minor effects. The surface topography affects the microstructure of homeotropic smectic samples.