多晶铑表面上碳氧共存体系的研究

用紫外光电子能谱（ＵＰＳ）和俄歇电子能谱（ＡＥＳ）对碳氧共存的多晶铑表面及ＣＯ、Ｏ_２、Ｃ_２Ｈ_４在该表面上的吸附进行了研究，发现铑表面上共存的表面碳和表面氧存在相互作用，由于表面氧的存在，外来吸附物如ＣＯ、Ｏ_２、Ｃ_２Ｈ_４等可以覆盖在表面碳上面，使表面碳占据表面位抑制其它物种吸附的屏蔽效应消失。该表面具有氧化性，可以把吸附的乙烯氧化。     

表面扩散的Monte Carlo初探

利用ＭｏｎｔｅＣａｒｌｏ方法模拟了理想表面和分形表面上的扩散过程；通过模拟可以发现，表面扩散系数不仅与表面浓度有关，而且还与扩散的时间、表面的几何形貌等有关。在表面覆盖度比较高时，表面扩散系数有一极大值。与理想表面相比，分形表面会使扩散系数减小。     

溶胶凝胶法制备仿生超疏水性薄膜

通过溶胶-凝胶(Sol-Gel)法和自组装(Self-assembled)制备了具有超疏水性的薄膜, 水滴在该薄膜上的平衡静态接触角为155°～157°, 滑动角为3°～5°. 通过扫描电子显微镜(SEM)观察薄膜微观表面, 发现该薄膜表面分布了双层结构(Binary structure)的微纳米粗糙度的微凸体, 上表层微米微凸体的平均直径为0. 2 μm, 下表层纳米微凸体的平均直径约为13 nm, 其分布与荷叶表面的结构极其相似. 用X射线光电子能谱(XPS)对薄膜表面元素进行了成分分析, 结果表明, 其表面存在大量的F, Cl等元素, 它能显著降低薄膜表面的表面能. 薄膜超疏水性的原因可能是, 通过硅片经溶胶粒子表面制备的薄膜具有合适的表面粗糙度, 再经过全氟辛基三氯甲硅烷(FOTMS)化学修饰后, 薄膜表面能进一步降低, 这两个条件的有机结合就使得薄膜产生了超疏水性.     

氧等离子体改性聚乙烯表面的疏水性过回复机制

用200 W射频容性耦合氧等离子体处理低密度聚乙烯(LDPE)表面1 min, 研究了老化温度及时间对LDPE表面成分、 形貌和润湿性的影响. 扫描电子显微镜结果表明, 等离子体改性LDPE表面出现纳米凸点织构, 在60和90 ℃老化24 h后纳米凸点织构特征基本保持稳定. X射线光电子能谱分析表明, 等离子体改性LDPE表面经60 ℃老化24 h后, C—C含量由76.9%增至83.0%, C—O, CO和O—CO含量分别由16.4%, 2.2%和4.5%降至13.1%, 1.9%和2.0%. 经90 ℃老化24 h后, C—C含量较60 ℃老化表面增至84.1%, C—O含量分别降至10.1%, CO和O—CO含量分别增至3.1%和2.7%. 等离子体改性LDPE表面接触角由97.2°降至42.3°, 经60 ℃老化24 h后接触角增至95.9°, 经90 ℃老化24 h后接触角增至104.2°, 等离子体改性LDPE表面发生“疏水性过回复”. 根据含有粗糙因子的接触角随时间演变模型, 得到了具有纳米凸点织构LDPE表面在不同老化温度下的可移动极性基团所占面积分数(\begin{array}{c}{f}_m^p\end{array})、 固定极性基团所占面积分数(\begin{array}{c}{f}_{\mathit{im}}^p\end{array})和特征时间常数(τ)3个成分重构参数, 解释了“疏水性过回复”现象.     

聚醚硅油表面迁移行为对聚苯乙烯表面极性的影响

利用变角衰减全反射傅立叶变换红外光谱(ATR-FTIR)法和接触角,分析了聚醚硅油在聚苯乙烯共混物薄膜表面的选择性富集行为及对其表面结构和表面极性的影响,认为接触介质的表面性质是影响共混物中各组分产生选择性迁移扩散的重要影响因素.强极性介质的诱导作用可以在共混物表面层中产生剧烈变化的浓度梯度,而弱极性介质所产生的表面浓度梯度比较缓和.     

The effect of surface microtopography of poly(dimethylsiloxane) on protein adsorption, platelet and cell adhesion

Chemical homogeneous poly(dimethylsiloxane) (PDMS) surface with dot-like protrusion pattern was used to investigate the individual effect of surface microtopography on protein adsorption and subsequent biological responses. Fibrinogen (Fg) and fibronectin (Fn) were chosen as model proteins due to their effect on platelet and cell adhesion, respectively. Fg labeled with ¹²⁵I and fluorescein isothiocyanate (FITC) was used to study its adsorption on flat and patterned surfaces. Patterned surface has a 46% increase in the adsorption of Fg when compared with flat surface. However, the surface area of the patterned surface was only 8% larger than that of the flat surface. Therefore, the increase in the surface area was not the only factor responsible for the increase in protein adsorption. Clear fluorescent pattern was visualized on patterned surface, indicating that adsorbed Fg regularly distributed and adsorbed most on the flanks and valleys of the protrusions. Such distribution and local enrichment of Fg presumably caused the specific location of platelets adhered from platelet-rich plasma (PRP) and flowing whole blood (FWB) on patterned surface. Furthermore, the different combination of surface topography and pre-adsorbed Fn could influence the adhesion of L929 cells. The flat surface with pre-adsorbed Fn was the optimum substrate while the virgin patterned surface was the poor substrate in terms of L929 cells spread.     

Chain structures of surface hydroxyl groups formed via line oxygen vacancies on TiO2(110) surfaces studied using noncontact atomic force microscopy

Structures of surface hydroxyl groups arranged on a reduced TiO2(110) surface that had line oxygen vacancies were studied using noncontact atomic force microscopy (NC-AFM). NC-AFM results revealed that by increasing the density of oxygen vacancies on the TiO2(110) surface, line oxygen vacancies were formed by removal of oxygen atoms in a bridge oxygen row on the TiO2(110) surface. After the TiO2(110) surface with the line oxygen vacancies was exposed to water, the surface showed hydroxyl chain structures that were composed of hydroxyl groups linearly arranged in a form of two rows on the line oxygen vacancies and on a neighboring bridge oxygen row. In-situ NC-AFM measurements of these surfaces exposed to water at room temperature revealed that hydroxyl chain structures were formed at the line oxygen vacancy. Annealing above 500 K was sufficient to remove the hydroxyl chain structures on the TiO2(110) surface and allowed line oxygen vacancies to reappear on the surface. The line oxygen vacancies are active sites for water dissociation. In conclusion, the formation of the hydroxyl chain structure suggests that the surface hydroxyl groups on a TiO2(110) surface can be controlled by preparing oxygen vacancy structures on the surface.     

三氧化钼-二氧化硅的制备方法与表面结构、表面酸性的关系

用共沉淀法和浸渍法制备样品. 测定了样品的表面酸性. 通过XRD, XPS、IR和激光喇曼光谱测定了样品的结构、MoO3的表面浓度和酸位类型. 结果表明, 两系列样品的表面结构、酸性变化的规律、MoO3的表面化学状态都与制备方法密切相关.在用共沉淀法制备的样品中, MoO3以两种不同的化学形态存在在表面上, 它们对表面酸性的影响然不同.     

H2分子在LaFeO3表面吸附的第一性原理研究

基于密度泛函理论的第一性原理方法,通过计算表面能确定La Fe O_3(010)表面为最稳定的吸附表面,研究了H_2分子在La Fe O_3(010)表面的吸附性质。La Fe O_3(010)表面存在La O和Fe O_2两种终止表面,但吸附主要发生在Fe O_2终止表面,由于La Fe O_3(010)表面弛豫的影响,使得凹凸不平的表面层增加了表面原子与H原子的接触面积,表面晶胞的纵向体积增加约2.5%,有利于H原子向晶体内扩散。研究发现,H_2分子在La Fe O_3(010)表面主要存在3种化学吸附方式:第一种吸附发生在O-O桥位,2个H原子分别吸附在2个O原子上,形成2个-OH基,这是最佳吸附位置,此时H原子与表面O原子的作用主要是H1s与O_2p轨道杂化作用的结果,H-O之间为典型的共价键。H_2分子的解离能垒为1.542 e V,说明表面需要一定的热条件,H_2分子才会发生解离吸附;第二种吸附发生在Fe-O桥位,1个H原子吸附在O原子上形成1个-OH基,另一个H原子吸附在Fe原子上形成金属键;第三种吸附发生在O顶位,2个H原子吸附在同一个O原子上,形成H_2O分子,此时H_2O分子与表面形成物理吸附,H_2O分子逃离表面后容易形成氧空位。此外,H_2分子在La Fe O_3(010)表面还可以发生物理吸附。     

Ar^＋, He^＋，S^＋离子轰击n-InP单晶表面的机理研究

通过X射线光电子能谱和低能电子衍射实验研究了10～180 eV的Ar＋、 He＋、S＋离子轰击n-InP（100）表面, 发现S＋离子轰击可以产生In-S组分,减轻离子轰击对表面的物理损伤.对于Ar＋离子轰击后的表面,经过S＋离子处理和加热过程以后,表面损伤得到了修复,最终得到了2×2的InP表面,进一步验证了S＋离子对InP表面的修复作用.     

O2和CN在铜活化闪锌矿(110)表面的吸附

采用基于密度泛函理论(DFT)的平面波赝势法模拟了O₂和CN分子在铜活化闪锌矿(110)表面的吸附. 结果表明: 铜活化后闪锌矿表面的铜原子3d轨道处于费米能级附近, 增强了闪锌矿表面的活性. 未活化闪锌矿表面不能吸附O₂, 活化后闪锌矿表面的铜原子和硫原子提供电子填入氧的反键π_2p^*轨道从而形成吸附键. CN分子吸附模拟表明, 铜活化增强了CN分子与闪锌矿表面的吸附作用. Cu原子d轨道与C原子反键p轨道作用形成反馈π键, 同时C原子s轨道与Cu原子sp轨道作用形成共价键; CN分子中N原子与闪锌矿表面S原子发生相互作用.     

Surface acidity and basicity of functionalized silica particles

Tetraethoxysilane has been co-hydrolyzed with functionalized organosilanes in a modified Stöber process to produce silica particles with amino, carboxylate or dihydroimidazole groups on the surface. The effects of reaction conditions and the loading of the functionalized organosilane on particle size was examined by TEM. Fluorescence spectroscopy of the surface amino groups covalently modified with fluorescamine, and the surface carboxylate groups with 4-bromomethyl-6,7-dimethoxycoumarin, demonstrated that these functional groups were accessible for further reaction. Changes in surface acidity and basicity caused by the presence of functional groups (amine, dihydroimidazole, carboxylate) on the particle surface were determined using an indicator titration technique. Particles with surface imidazole and amine groups and particles with surface carboxylate groups have enhanced basicity and acidity, respectively. Dihydroimidazole-modified silica had greater surface basicity than the amine-modified silica. The effect on basicity and acidity increases as the amount of added functionalized silane increases. However, this increase is nonlinear with respect to the increase in added functionalized silane. Particles with both surface dihydroimidazole and carboxylate groups demonstrated reduced surface basicity and acidity.     

溶菌酶蛋白在聚合物防污膜表面的吸附

采用分子动力学模拟方法比较了溶菌酶蛋白在两种典型聚合物防污材料聚乙二醇(PEG)和聚二甲基硅氧烷(PDMS)表面的吸附行为,在微观上探讨了聚合物膜表面性质对蛋白质吸附的影响.根据蛋白质与聚合物膜之间的相互作用、能量变化及表面水化层分子的动力学行为,解释了PEG防污涂层相对于PDMS表面具有更佳防污效果的原因:(1)相比PDMS涂层,蛋白质与PEG涂层的结合能量较低,使其结合更加疏松;(2)蛋白质吸附到材料表面要克服表面水化层分子引起的能障,PEG表面与水分子之间结合紧密,结合水难于脱附,造成蛋白质在其表面的吸附需要克服更高的能量,不利于蛋白质的吸附.     

Surface phases and nanostructures on silicon surface

The paper gives definitions of conventional terms related to silicon surface science, such as surface, surfaced phase, adatoms, “in phase” and “on phase” atoms. The formation methods of surface phases are illustrated as well as their role in physical processes on the surface. The influence of surface phases on diffusion, desorption, adsorption, and phase interface formation at the silicon surface is described.     

溶菌酶蛋白在聚合物防污膜表面的吸附

采用分子动力学模拟方法比较了溶菌酶蛋白在两种典型聚合物防污材料聚乙二醇(PEG)和聚二甲基硅氧烷(PDMS)表面的吸附行为, 在微观上探讨了聚合物膜表面性质对蛋白质吸附的影响. 根据蛋白质与聚合物膜之间的相互作用、能量变化及表面水化层分子的动力学行为, 解释了PEG防污涂层相对于PDMS表面具有更佳防污效果的原因: (1) 相比PDMS涂层, 蛋白质与PEG涂层的结合能量较低, 使其结合更加疏松; (2) 蛋白质吸附到材料表面要克服表面水化层分子引起的能障, PEG表面与水分子之间结合紧密, 结合水难于脱附, 造成蛋白质在其表面的吸附需要克服更高的能量, 不利于蛋白质的吸附.     

Spatial Effect of C?H Dipoles on the Electron Affinity of Diamond (100)‐2×1 Adsorbed with Organic Molecules

Cycloaddition of allyl organics on the dimer rows of a clean C(100)‐2×1 diamond surface can be used for the controlled functionalization of such a surface. Sticking probability measurements confirm that appreciable uptake of acetylene and butadiene occur on the clean diamond surface at room temperature. The change in electron affinity of the surface as a function of the coverage of the organic molecules is investigated with periodic DFT calculations. The presence of C? H dipoles on these adsorbates modify the surface charge density and gives rise to an induced dipolar layer that modifies the electrostatic potential outside the surface. There is a significant reduction of up to 2.5 eV in electron affinity following the chemisorption of ethylene. Therefore, the adsorbed molecules play the same role as surface hydrogen in inducing the NEA condition on the clean diamond. The change in electron affinity does not scale linearly with the coverage of the organic molecules, because the spatial profile of the C? H dipoles as well as the orientation of the molecules on the surface have a predominant effect on the surface charge density.     

The effect of iron and copper impurities on the wettability of sphalerite (110) surface

The effect of impurities in the zinc sulfide mineral sphalerite on surface wettability has been investigated theoretically to shed light on previously reported conflicting results on sphalerite flotation. The effect of iron and copper impurities on the sphalerite (110) surface energy and on the water adsorption energy was calculated with the semi-empirical method modified symmetrically orthogonalized intermediate neglect of differential overlap (MSINDO) using the cyclic cluster model. The effect of impurities or dopants on surface energies is small but significant. The surface energy increases with increasing surface iron concentration while the opposite effect is reported for increasing copper concentration. The effect on adsorption energies is much more pronounced with water clearly preferring to adsorb on an iron site followed by a zinc site, and copper site least favorable. The theoretical results indicate that a sphalerite (110) surface containing iron is more hydrophilic than the undoped zinc sulfide surface. In agreement with the literature, the surface containing copper (either naturally or by activation) is more hydrophobic than the undoped surface.     

Non-specific and specific interactions on functionalized polymer surface studied by FT-SPR

Fourier transform surface plasmon resonance (FT-SPR) was utilized to study specific and non-specific interactions between proteins and a biotinylated polymer film by monitoring adsorptions of streptavidin (SAv) and bovine serum albumin (BSA) on the polymer films. The biotinylated polymer, poly(lactide-co-2,2-dihydroxymethyl-propylene carbonate-graft-biotin) [P(LA-co-DHC/biotin)], was prepared by ring-opening copolymerization of lactide and a OH-bearing cyclic carbonate monomer, followed by biotinylation of the OH groups. The copolymer was coated onto the FT-SPR chip and vacuum-dried, hydrated at 70°C, and treated with a blocking agent respectively to achieve different surface status. The FT-SPR results showed that the vacuum-dried film had the most BSA adsorption; hydration treatment led to migration of the biotin moieties from inner film to surface and thus resulted in less BSA adsorption; blocking layer on the polymer surface saturated the active sites for physical and chemical adsorptions on the surface and thus weakened the BSA adsorption. Adsorption of SAv displayed similar polymer-surface-status dependence, i.e., more adsorption on vacuum-dried surface, less adsorption on hydrated surface and the least adsorption on blocked surface. Compared with BSA, SAv showed more enhanced adsorptions on P(LA-co-DHC/biotin) surface because of the specific interaction of biotin moieties in the polymer with SAv molecules, especially on the blocked surface. The above semi-quantified results further indicate that the FT-SPR system is suitable for investigating interactions between polymer surface and bio-molecules.     

端基功能化聚合物的表面性能

综述了端基功能化聚合物表面结构与性能的最新研究进展.聚合物端基功能化是实现聚合物表面改性的一种有效技术.通过端基功能化可以精确控制聚合物表面功能基团的种类和数量,从而影响聚合物表面的化学结构与性能.重点论述了功能化端基在聚合物表面的离析现象和产生这一现象的原因,以及功能化端基对聚合物表面分子运动能力的影响.本文还介绍了近年来用于研究端基功能化聚合物表面的表征新技术,如SFG、NR、SSIMS等.对端基功能化聚合物表面的环境响应性也进行了阐述.指出了利用不同功能化端基可以有效地控制聚合物表面的亲疏水性.并对端基功能化聚合物的应用进行了展望.     

Effect of SDBS solution on the surface potential properties of the Zhaozhuang coal

It is of great significance to study the effect of surfactants on the coal surface potential for effective dust suppression in mining faces. The effect of different concentrations of sodium dodecyl benzene sulfonate (SDBS) solution on the surface potential of the Zhaozhuang coal was measured by atomic force microscopy (AFM). The experimental results show that the SDBS solution has significant influence on the surface potential of the Zhaozhuang coal. The electrical characteristics of the coal surface at the nanometer scale are different from those of macroscopic or the mesoscopic level. The surface potential of coal is basically a normal distribution, showing certain electrical characteristics. The mean value of the surface potential of the Zhaozhuang coal is increased with the increase in concentration of the SDBS solution; when the concentration of the SDBS solution is 0.3%, the mean value of surface potential is 5.59 mv, which is about two times of the mean value of the surface potential without SDBS solution added. With the increase of the concentration of the SDBS solution, the maximum value of the surface potential of the Zhaozhuang coal increases, and the minimum value decreases. It shows that the SDBS solution has a significant effect on the potential distribution law and the magnitude of the coal surface. Subsequently, on the basis of the constructed Zhaozhuang coal macromolecule model, xtb and Multiwfn simulation software were used to calculate the molecular surface electrostatic potential value and electron density value of the Zhaozhuang coal molecules after adding water molecules. The variation law for the electrostatic potential surface of the molecule was obtained after adding numbers of water molecules to the surface of the coal molecule. The simulation results show that the area proportion of absolute molecular surface electrostatic potential greater than 10 kcal/mol is increased with the growth in the number of water molecules, while the area proportion of absolute molecular surface electrostatic potential less than 10 kcal/mol is decreased. Because of the free state O─H bond polarity of water molecules, the charges on the molecular surface are rearranged in order to change the electron density on the surface of coal molecules, which affects the overall electrostatic potential of the configuration.