垂悬液滴用于表面单分子膜研究的理论计算

建立了用于表面单分子膜研究的垂悬液滴球体模型,所此模型,计算了表面活性剂荧光分子的偶极矩强度分布,分子密度分布以及荧光强强度分布。计算结果和罗丹明Ｂ表面活性剂分子的实验图像作了分析比较。     

表面活性剂对气-液界面纳米颗粒吸附规律的影响

通过测定及分析纳米颗粒和表面活性剂-纳米颗粒复配体系在自由吸附过程与动态收缩过程中表面张力的变化,总结了纳米颗粒在气-液界面的吸附排布规律以及表面活性剂对其吸附规律的影响.实验结果表明,自由吸附过程中,随矿化度增加、阳离子活性剂浓度增加,平衡表面张力降低,这与颗粒吸附密度增加及颗粒润湿性改变有关.浓度低于临界胶束浓度(CMC)时,阳离子活性剂体系与混合体系的表面张力差异证明了阳离子活性剂可以通过静电作用吸附于纳米颗粒表面,进而部分溶解于水相;而阴离子活性剂与纳米颗粒相互作用力较弱,对表面张力影响较小.纳米颗粒体系在液滴收缩过程中,表面张力从自由吸附平衡态进一步降低大约9 m N/m,说明自由吸附过程中纳米颗粒不能达到紧密排布;同时表面张力呈现为缓慢降低、快速降低和达到平衡三部分,表面压缩模量可达70 m N/m,满足了液膜Gibbs稳定准则,这将有助于提高泡沫或者乳液稳定性.纳米颗粒-表面活性剂体系在液滴收缩过程中表面张力降低值随活性剂浓度增加而减小;表面压缩模量由高到低依次为:纳米颗粒>阳离子活性剂-纳米颗粒>阴离子-纳米颗粒>表面活性剂.     

倾斜粗糙壁面上含不溶性活性剂溶液的动力学特性

针对倾斜随机粗糙壁面上含不溶性活性剂溶液的流动过程, 采用润滑理论建立了液膜厚度和浓度的时空演化模型, 通过PDECOL程序数值求解得到了液膜流/液滴铺展的动力学特性及壁面结构参数的影响. 研究表明: 在重力分量和Marangoni效应共同作用下, 液膜流/液滴铺展速度加快, 液膜边缘和液滴中心出现毛细隆起, 液膜/液滴底部出现凹陷, 同时受粗糙壁面影响, 液膜表面变形更显著. 增加壁面倾角θ具有使重力分量和Marangoni效应增强, 导致隆起和凹陷程度均有所增加的作用. 增大壁面高度D可使液膜流/液滴铺展速度加快, 表面变形放大. 而壁面波数k₀则使液膜流/液滴铺展过程减缓, 抑制隆起和凹陷产生. 与液膜流相比, D和k₀对液滴铺展速度的影响相对较小. 关键词： 随机粗糙壁面 液膜 Marangoni效应 倾斜流动     

分子束外延生长Si/GaP(111)异质结的界面特性

本文研究了分子束外延(MBE)生长的n-N型Si/GaP(111)异质结的界面特性。采用C-V法测量Si/GaP(111)异质结的表观载流子浓度分布n(x),从中导出了异质界面的导带失配值和界面电荷密度。实验结果表明,n-N型Si/GaP(111)是一种弱整流结构。导带失配△E_c=0.10eV,界面电荷密度σ_i=8.8×10¹⁰cm^-2。通过表现载流子浓度n(x)的理论计算曲线与实验曲线符合较好,说明了实验结果的可靠性 关键词：     

自辐射场下UN2分子的光谱研究

对铀原子和氮原子分别使用相对论有效原子实势和6-311+G(d)基组, 采用优选的密度泛函B3P86方法, 研究了铀本身产生自辐射场(-0.005–0.005 a.u.)作用下UN₂基态分子的能隙E_g和谐振频率ν. 结果表明: UN₂分子在自辐射场中反对称伸缩振动频率ν₃(σ_g)和对称伸缩振动频率σ₁(σ_g)与实验值1051.1 cm^-1和1008.3 cm^-1 基本符合; E_g随自辐射场场强的增大而趋于减少, 占据轨道的电子容易被激发至空轨道而形成激发态; UN₂分子在自辐射场中趋于不稳定, N₂, O₂等更容易扩散到表面内层而腐蚀铀表面, 加剧了铀在自辐射场中的腐蚀.     

利用1H NMR探究混合离子型/非离子型表面活性剂临界胶束浓度降低的实质

利用¹H NMR技术研究了离子/非离子表面活性剂形成的二元混合体系,结果显示表面活性剂的混合导致各组分的临界胶束浓度（CMC）均比各自纯溶液有所降低,用吸附平衡理论清楚地解释了这个现象.通过定量分析,发现不同的表面活性剂混合使得其组分CMC降低的程度各异,可以理解为它们吸附于界面单分子吸附层上的分子之间相互作用的不同（相吸或相斥）引起的.由此揭示了"协同效应"的实质,可以为选择适当的表面活性剂类型和混合比例以达到预期的性能提供有力的参考.     

苯并咪唑苝与金属Ag的界面电子结构研究

利用同步辐射光电子能谱实验技术考察了苯并咪唑苝(BZP)和Ag的界面形成过程与电子结构.单层覆盖度以下时，BZP分子与Ag有弱相互作用，在有机分子禁带中出现明显界面反应态，结合能位于0.9eV.单层铺满后，BZP分子呈现三维岛式生长，且与Ag的相互作用逐渐减弱，同时最高占据分子轨道由于终态效应逐渐向高结合能方向位移至体相结合能位置(2.3eV). Ag衬底上BZP分子的生长导致样品表面功函数减小，表明形成了表面偶极势(Δ=0.3eV)，且电子从有机分子向金属Ag偏移.最后，考察了BZP/Ag 关键词： 有机-金属界面 电子结构 光电子能谱 同步辐射     

C2H2,C2H4与K在Ru(1010)表面上共吸附的UPS研究

利用紫外光电子谱(UPS)对乙烯(C₂H₄)和乙炔(C₂H₂)气体在Ru(1010)表面的吸附及与K的共吸附进行了研究,实验结果表明:当衬底温度超过200K,乙烯即发生脱氢反应后,σ_CH和σ_CC能级均向高结合能方向移动.在室温下,σ_CH和σ_CC能级位置与乙炔在Ru(1010)表面的吸附时的分子能级完全一致.乙烯发生脱氢反应后的主要产 关键词： 乙烯 乙炔 钾 Ru(1010)表面     

部分相干厄米-双曲正弦-高斯光束通过湍流大气传输的平均光强分布演化和角扩展

推导出部分相干厄米-双曲正弦-高斯(H-ShG)光束通过湍流大气的平均光强和角扩展的解析表示式,并用以研究了部分相干H-ShG光束在湍流中的平均光强分布演化和角扩展. 结果表明,折射率结构常数C²_n的增加和空间相关长度σ₀的减小都会加速演化过程. 引入相对角扩展来定量描述光束抗拒湍流的能力. 空间相关长度σ₀,束腰宽度w₀和双曲 关键词： 平均光强分布演化 角扩展 湍流大气 部分相干厄米-双曲正弦-高斯(H-ShG)光束     

界面活性剂对Fe3O4磁性与穆斯堡尔谱的影响

测量了不同颗粒尺寸Fe₃O₄覆盖界面活性剂前后磁性、红外谱以及穆斯堡尔谱。实验结果表明界面活性剂与Fe₃O₄微粒表面为化学吸附,覆盖界面活性剂后在相同磁场下磁化强度有所下降,穆斯堡尔谱变得弥散,随着颗粒尺寸变小,穆斯堡尔谱内场减小,谱线变得更为弥散,实验结果可以用表面各向异性的理论进行解释。 关键词：     

Preparation and the optical nonlinearity of surface chemistry improved titania nanoparticles in poly(methyl methacrylate)-titania hybrid thin films

With 800-nm, 120-fs laser pulses, optical nonlinearity has been studied in a series of thin films containing poly(methyl methacrylate) (PMMA), filled with surfactant acetylacetone (Acac) capped TiO₂ nanoparticles, which were synthesized by a simple in situ sol-gel/polymerization process, assisted by spin coating and multi-step baking. The resulting nanohybrid thin films have highly optical transparency and demonstrate a unique nonlinear optical (NLO) response. The highest nonlinear refractive index (n₂) is observed up to 6.55 × 10⁻² cm² GW⁻¹ in the nanohybrid thin film of 60 wt% Ti(OBu)₄ in PMMA, with a negligible two-photon absorption (TPA), as confirmed by the Z-scan technique. The titanium precursor loading combined with the nature of the capping molecules are used to influence the ability of nanoparticles to nonlinear optical response. Indeed, the ligands at the nanoparticles’ surface can not only control the extent of the interaction between the organic molecules and the embedded nanoparticles but also influence the optical nonlinearities of nanoparticles.     

Molecular simulation of C60 adsorption onto a TiO2 rutile (1 1 0) surface

A Monte Carlo molecular simulation study is presented on the adsorption and growth of C₆₀ films on the surface of the (1 1 0) face of rutile. Simulations are performed for a temperature of 600 K using atomistic models both for the fullerene molecules and the TiO₂ surface. It is found in this work that C₆₀ is adsorbed preferably in an ordered arrangement along the surface depressions over the exposed undercoordinated Ti cations. At low densities adsorption occurs preferably at alternate rows, with locations in consecutive rows being occupied appreciably only at higher C₆₀ densities. At low densities, the fullerene molecules tend to aggregate into islands in the surface plane. Additional layers of C₆₀ form only as the density increases, and do so before a monolayer is completed in all consecutive rows. Full monolayer capacity obtained at the highest densities is about 0.9 C₆₀ molecules per nm², but this is only achieved by completing the packing of molecules in interstices at a slightly upper level. The fraction of the molecules that lie closest to the surface only amounts to 0.6 molecules per nm².     

Establishment of equivalent circuits from electrochemical impedance spectroscopy study of corrosion inhibition of steel by pyrazine in sulphuric acidic solution

This paper describes the use of the electrochemical impedance spectroscopy technique (EIS) in order to study the corrosion inhibition process of steel in 0.5 M H₂SO₄ solution at the open circuit potential (OCP). Diethyl pyrazine-2,3-dicarboxylate (Prz) as a non-ionic surfactant (NS) inhibitor has been examined. The Nyquist diagrams consisted of a capacitive semicircle at high frequencies followed by a well-defined inductive loop at low frequency values. The impedance measurements were interpreted according to suitable equivalent circuits. The results obtained showed that the Prz is a good inhibitor. The inhibition efficiency increases with an increase in the surfactant concentration to attain 80% at the 5 × 10⁻³M. Prz is adsorbed on the steel surface according to a Langmuir isotherm adsorption model.     

Positioning of cationic silver nanoparticle by using AFM lithography and electrostatic interaction

One-dimensional metal lines of silver nanoparticles with a nano-sized width were generated onto silicon surface by using a nano-level lithography technique, field induced oxidation (FIO) by AFM, on self-assembled monolayer-modified Si wafers. This FIO technique provided SiO₂ lines a width of less than 100 nm. Short-time immersion of partially anodized silicon surface which is covered by a cationic silanol surfactant ((CH₃O)₃SiCH₂CH₂CH₂N(CH₃)₃⁺Cl⁻)-monolayer into quaternary ammonium (HSCH₂CH₂N(CH₃)₃⁺Br⁻)-covered silver nanoparticles readily and reproducibly gave nano-metal lines of silver onto silicon wafers. Hydrophilicity of the whole wafer surface was indispensable for homogeneously wetting the anodized SiO₂ area with a nanodimensional width.     

Surface area per molecule in lipid/C12E n membranes as seen by fluorescence resonance energy transfer

Fluorescence resonance energy transfer (FRET) from NBD-PE to rhodamine-PE has been used to measure the average area occupied by surfactant molecules in lipid bilayers. The Foerster radius has been determined from the spectral overlap of donor fluorescence and acceptor absorption (R ₀=4.6 nm). The results of steady-state as well as of time-resolved investigations have been compared. The analysis of time-resolved fluorescence data by means of nonexponential decay functions yields an average area per lipid of 0.65 nm² in pure POPC bilayers. The area per surfactant in two-component C₁₂E _n /POPC-membranes (n=2, 4, 6) has been determined and compared with the results of X-ray investigations. The surfactant head group seems to adapt a predominantly disordered confirmation within the bilayer.     

Theoretical study on adsorption of Au and hydrated Au cations on clean Si(1 1 1) surface

To model the adsorption of Au⁺ cation in aqueous solution on the semiconductor surface, the interactions of Au⁺ and hydrated Au⁺ cations with clean Si(1 1 1) surface were investigated by using hybrid density functional theory (B3LYP) and Møller-Plesset second-order perturbation (MP2) methods. Si(1 1 1) surface was described with Si₇H₁₁, Si₁₁H₁₇ and Si₂₂H₂₁ clusters. The effect of the basis set superposition error (BSSE) was taken into account by applying the counterpoise correction. The calculated results indicated that the binding energies between hydrated Au⁺ cations and clean Si(1 1 1) surface are large, suggesting a strong interaction between hydrated Au⁺ cations and the semiconductor surface. The bonding nature of the chemical adsorption of Au⁺ to Si surface can be classified as partial covalent as well as ionic bonding. As the number of water molecules increases, the water molecules form hydrogen bond network with one another and only one water molecule binds directly to the Au⁺ cation. The Au⁺ cation in aqueous solution will safely attach to the clean Si(1 1 1) surface.     

Mid-infrared polarization spectroscopy of C2H2: Non-intrusive spatial-resolved measurements of polyatomic hydrocarbon molecules for combustion diagnostics

Polarization spectroscopy in the mid-infrared (IRPS) has been applied to the detection of acetylene molecules making use of the asymmetric C-H stretching vibration at around 3 μm. The infrared laser pulses were produced through difference frequency generation in a LiNbO₃ crystal pumped by a Nd:YAG and dye laser system. By directly probing the ro-vibrational transitions with IRPS, sensitive detection of molecules with otherwise inaccessible electronic states was realized with high temporal and spatial resolution by using a pulsed laser and a cross-beam geometry. Detection sensitivities of 2 × 10¹³ molecules/cm³ (10 ppm in 70 mbar gas mixture) of C₂H₂ were achieved using the P(1 1) line of the (0 1 0(1 1)⁰)-(0 0 0 0⁰ 0⁰) band. The dependence of the IRPS signal on the pump laser fluence, acetylene mole fraction, and buffer gas pressure of Ar, N₂, H₂, and CO₂ has been studied experimentally. The investigation demonstrates the quantitative nature of IRPS for sensitive detection of polyatomic IR active molecules. In order to fully demonstrate the technique for combustion applications, nascent acetylene molecules were measured in a low pressure methane/oxygen flame.     

A novel one-step synthesis of mesostructured silica-pillared clay with highly ordered gallery organic-inorganic hybrid frame

A new class of organic-inorganic hybrid mesostructured silica-pillared clay (HSPC) has been prepared through the surfactant directed assembly of organosilica in the galleries of montmorillonite. The surfactant templates were removed from the pores by solvent-extraction. The products were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), nitrogen adsorption-desorption measurements, solid-state ²⁹Si and ¹³C NMR, and Fourier-transform infrared (FT-IR) spectra. XRD patterns indicated a regular interstratifications of the clay layers for HSPCs. Depending on loading of phenyl groups, HSPCs had BET surface areas of 395-602 m² g⁻¹, pore volumes of 0.34-0.79 cm³g⁻¹, and the framework pore sizes in the supermicropore to small mesopore range (1.3-2.6 nm). HSPCs were hydrophobic and acidic. The number of silanol groups on the surface of HSPC materials has been titrated by a surface reaction with hexamethyldisilazane, followed by quantification of the liberated NH₃. Based on this method extracted HPCHs have high silanol numbers, a very important feature with respect to the amount of catalytic sites that can eventually be grafted onto the surface.     

Protonated dye-surfactant ion pair formation between neutral red and anionic surfactants in aqueous submicellar solutions

Spectral and surface tension behavior of aqueous neutral red in the presence of sodium dodecyl sulfate (SDS), sodium dodecyl benzene sulfonate (SDBS) and sodium dodecyl sulfonate (SDSN) have been studied to understand the nature of the interactions in their submicellar concentration ranges. The variations in spectra and surface tension with variation in the concentrations of the surfactants suggest the formation of a 1:1 close-packed dye-surfactant ion pair, HNR⁺S⁻ between the acid form, HNR⁺ of the dye and the surfactant anion at very low concentrations of the surfactant below critical micelle concentration (cmc) of the pure surfactant. The dye-surfactant ion pair behaves like a nonionic surfactant having higher efficiency and lower cmc than that of the corresponding pure anionic surfactant. The ion pairs are adsorbed on the air/water interface at very low concentrations of the surfactant. As the concentration of the surfactant increases and the ion pairs form micelles of their own, the dye in the ion pair is protonated to form H₂NR²⁺S⁻. As the cmc of the pure surfactant is approached, the protonation equilibrium gradually reverses and pure surfactant ions gradually replace the ion pairs at the interface. Finally, a homogeneous monolayer of pure surfactant anions exists at the air/water interface and the dye remain solubilized in pure micelles above the cmc of the pure surfactant. The equilibrium constants, K_c for the close-packed protonated dye-surfactant ion pair (PDSIP) formation have been determined at varying pH. The submicellar interaction has been found to be stronger with SDS than SDBS. The plots of logarithm of K_c vs. pH have been found to be quite linear which consolidates the assumption of formation of the species, H₂NR²⁺S⁻. The interaction is driven by enthalpy as well as entropy.     

Surface reaction kinetics in oxygen nonstoichiometry re-equilibration of BaTiO3−δ

We report the (bare) surface redox-reaction rate constant that was determined, along with the chemical diffusivity , by a conductivity relaxation technique on Al-doped single crystal and undoped polycrystal BaTiO_3−δ as a function of oxygen activity in its range of −16≤log a_O2≤0 at elevated temperatures of 800–1100 °C. It takes a value in the range of −4<log( /cm s⁻¹)≤−1, which is even larger than that of the oxides that are considered best as oxygen membranes. It has been found that the surface reaction step grows more rate controlling as the electronic transference number gets smaller or the electronic stoichiometric composition (δ≈0) is approached. The oxygen potential drop due to the surface reaction was estimated by an oxygen concentration cell technique. The oxygen potential drop grows larger as the stoichiometric composition is approached, that is in accord with the variation of against oxygen activity.