介电失配度对沸石电流变液界面极化的影响

利用介电谱方法研究了NaA沸石/硅油和NaA沸石/煤油两种电流变液的介电行为, 测量发现两体系在10⁵ Hz处均出现明显的弛豫现象. 采用单弛豫Cole-Cole函数拟合各体系的介电参数, 结果表明在相同体积分数条件下硅油体系具有较大的介电增量(?ε), 且两体系的介电增量与体积分数(φ)均服从?ε＝4ε_mφ的函数关系. 通过计算和分析粒子与介质间介电失配程度, 阐明了油介质的介电常数(ε_m)对于沸石电流变液界面极化强度的贡献. 此外研究了吸附水对沸石电流变液界面极化的影响, 结果发现水的吸附对于体系的?ε值没有影响, 但明显降低了弛豫时间, 证明吸附水对沸石电流变液的界面极化率具有增强作用.     

反渗透膜UTC-70在水溶液中的介电谱及其解析

根据平面层状体系介电弛豫理论研究了反渗透膜UTC-70在各种浓度氯化钠和氯化钾溶液中的介电弛豫行为.利用计算机拟合的方法得到膜/溶液体系的介电参数,并由此计算得到了UTC-70膜相和水溶液相的相参数,获得了反映反渗透膜UTC-70荷电情况的信息及其与电解质溶液浓度的关系,介电解析的结果解释了介电弛豫的产生机制.     

非导电微球悬浊系的介电谱——弛豫机制的考察和界面信息的解析

研究了不同浓度电解质溶液中聚苯乙烯微球悬浊液的介电谱, 发现在40 Hz～110 MHz频率范围内出现了两个明显的弛豫. 在介电模型基础上对弛豫原因的理论分析结果表明, 千赫兹频域出现的弛豫是由粒子附近双电层中对离子的扩散所致, 兆赫兹附近出现的弛豫源于空间电荷在固/液界面的累积. 应用Hanai方法计算出体系内部的相参数, 获得了微球/溶液界面的电信息, 并给出了合理解释. 理论计算结果验证了模型和方法的适用性. 实验采用透析法调制样品, 有效地防止了体系内部粒子二次团聚的发生.     

平面结构非均匀体系的介电驰豫─—组成相的数目与电导对弛豫的影响

非均匀体系在０．１ｋＨｚ～１０ＭＨｚ频率范围显示出显著的介电弛豫,为了弄清介电弛豫的原因以及该弛豫与非均匀体系界面数目的关系,本文从介电的观点在理论及实验两方面讨论了典型的非均匀体系的例子：膜／溶液体系。特别地,对频率域的介电弛豫谱与组成相的结构及浓度的关系进行了分析,并在Ｍａｘｗｅｌｌ－Ｗａｇｎｅｒ机理的基础上现象论地解释了弛豫的原因。非均匀体系的介电弛豫性质具有下列特征：（１）介电弛豫数目等于体系内界面种类的数目;（２）特征弛豫频率紧密地依存于溶液相的电导。     

离子交换树脂悬浊液的介电弛豫谱研究

研究了D354阴离子交换树脂分散在不同浓度KCl溶液中的悬浊液的频率域介电谱,发现在测量频率为106～107 Hz处出现了显著的介电弛豫现象,得出了介电常数、电导率以及弛豫时间随KCl溶液浓度的特异的变化关系,理论分析表明,该弛豫是一个以界面极化为主的非单一极化机制的弛豫过程,进而利用Maxwell-Wagner界面极化理论和双电层性质解释了该体系的特异介电行为,得到了树脂悬浊液在外加交变电场下的离子迁移和聚集信息,并确定了该树脂在静态平衡下双电层中对离子的相对离子强度.     

PS-PBA粒子分散系的介电弛豫谱解析——同、反离子对弛豫的影响及表界面电参数的计算

制备了近纳米级的聚苯乙烯-丙烯酸丁酯(PS-PBA)复合微球粒子,并在40Hz～110×106Hz的宽频范围测量了该粒子分散在9种电解质中时的介电弛豫谱,发现了与PS微球粒子分散系不同的特异介电弛豫:低频弛豫对反离子种类具有敏感性而高频弛豫则与电解质种类几乎无关;根据Shilov-Dukhin模型和M-W-O模型分别分析了高、低频率的弛豫机制,并通过对介电谱的Cole-Cole拟合获得了各体系的介电参数.进一步利用Hanai方法由介电参数计算获得了所有体系的相参数;详细分析了体系的内部参数受PS-PBA微球自身结构以及电解质种类影响的原因;讨论了离子扩散系数对介电参数的影响,从而得出了低、高频的弛豫特征时间分别由同离子的扩散系数和反离子的扩散系数所决定之结论.最后,结合Grosse宽频介电理论计算了粒子表面的以及双电层的主要电参数,并分析了电解质种类差异对这些电参数的影响.     

非导电球型粒子悬浮液宽频介电谱——薄双电层理论的计算机模拟

以Shilov等提出的带有紧密层表面电导率的非导电球型粒子悬浮液宽频介电弛豫的薄双电层理论为基础, 从电动力学角度解释了粒子分散系两种典型介电弛豫(高频和低频弛豫)的机制. 在此基础上, 利用Mathcad程序将该理论定量程序化并建立了粒子/水相分散系介电谱参数与体系内部相参数的关系. 进而利用该程序模拟了溶液浓度、Zeta电位以及分散粒子半径等内相参数对两种弛豫的影响, 结合该理论阐述了不同环境下这两种弛豫的变化规律, 从而为今后更好地利用这两种弛豫表征纳米至毫米级球形粒子分散系的各相电及界面性质提供了有价值的参考.     

NaA沸石离子交换过程的介电弛豫谱研究

在40 Hz~110 MHz频率段对不同Ca²⁺交换度的NaA沸石堆积体系进行了介电测量, 并利用Cole-Cole公式及Hanai方法对介电参数和相参数进行拟合与解析. 结果表明, 随着Ca²⁺交换度的不断增高, 堆积体系的介电增量、弛豫频率、弛豫分布系数以及粒子的电导率均有不同程度的降低, 而粒子的介电常数保持不变. 通过综合分析弛豫变化规律与离子交换度的内在联系发现, 离子交换后Ca²⁺选择六元环占位, 同时六元环和八元环位置的相邻2个Na⁺被置换; 占据六元环的Ca²⁺与八元环位置的Na⁺对沸石粒子的极化贡献等价; Ca²⁺的进入导致沸石孔道内微观电场多样化.     

球壳粒子悬浮系模型化研究——内部相参数对介电谱影响的数值模拟

在Hanai理论基础上对球壳粒子悬浮系的介电模型进行了模拟研究,通过用C++的复数类对理论公式的程序化,建立了介电谱的介电参数与体系内部相参数的关系.所得的解析解可方便地模拟介电弛豫谱依不同相参数的变化曲线,计算并分析了内部参数对介电谱的模式以及介电参数的影响因素.     

膜对物质吸附和释放的介电谱研究——弛豫机制和扩散动力学

对壳聚糖膜吸附和缓释水杨酸过程的介电监测显示: 伴随着吸附或释放的进行, 相应膜/溶液体系的介电谱也发生规律性变化. 通过对这一变化的系统分析, 对介电弛豫产生的机制提出了新的看法, 确认了吸附或缓释行为引起的溶液中的浓差极化是介电弛豫产生的根本原因, 进而由浓差极化层电导率梯度、厚度与介电谱弛豫强度之间的理论关系解释了体系介电谱随时间等因素变化的原因. 这一弛豫机制的确立, 有望为建立获得吸附或释放过程体系各相的动态变化参数的理论方法、从而实现介电谱方法对药物控制释放过程的实时监测开辟一个新的途径.     

Dielectric analysis on phase transition and micelle shape of polyoxyethylene trisiloxane surfactant in dilute aqueous solution

The cloudy Silwet L-77 aqueous solution on the concentration range from 0.5%to 50%was investigated by dielectric relaxation spectroscopy.The concentration dependence of phase microstructure was confirmed by means of analyzing the dielectric parameters of bulk solution.The relaxation behavior was assigned to the interfacial polarization between the micelle and the medium,and the relaxation distribution parameter was used to figure the shape transition from sphere to ellipsoid with the concentration increasing.The synchronous reduction of permittivity and conductivity indicated the formation of the lamellar phase. As compensation,the quantity of the surfactant liquid phase gradually decreased,whose shape constantly kept ellipsoidal.     

Dielectric Spectroscopy Study on Vesicles of CTAB/SDBS System

IntroductionWhen the cationic and anionic surfactants in which the total carbon number is equal to or greater than 20 are mixed, then the vesicles can form spontaneously due to the strong interactions or by sonication1. Vesicle is of bilayer structure containing a closed aqueous room, resembling the structure of a real cell. So it seems to be imperative to study the membrane mimicry system like vesicle in order to understand the structure and functions of real cells further. In addition, it ca…     

自探针荧光法研究十二烷基苯磺酸钠与TritonX-100相互作用

采用荧光光谱法研究了十二烷基苯磺酸钠（SDBS）与非离子表面活性剂TritonX-100混合体系在水溶液中聚集体的性质。 发现在浓度与荧光强度的关系曲线上存在2个转折点,分别对应于混合体系的临界胶团浓度和胶团形状发生转变的浓度。 通过混合胶团相互作用关系,计算了SDBS与TritonX-100的相互作用参数βM,说明SDBS以其自身所带生色基团苯磺酸与TritonX-100发生了协调效应且存在着较强的相互作用。     

Assemblies of amphiphilic compounds over rigid polymers: 2. Interaction of sodium dodecylbenzenesulfonate with chitosan-scleraldehyde gels

Gels based on chitosan cross-linked with scleraldehyde were prepared. The swelling behavior due to pH variation and to equilibration with solutions of sodium dodecylbenzene-sulfonate (SDBS) or sodium p-toluenesulfonate (p-STS) was investigated. Binding isotherms and the solubilization of Sudan III by gels equilibrated with SDBS were also determined. Gel collapse was at a SDBS concentration one order of magnitude smaller than the critical micelle concentration and was accompanied by moderately cooperative binding with K equal to 4120 M⁻¹. Binding of p-STS, which is characterized by a similar value of K but much smaller cooperativity parameter, was not accompanied by gel collapse. The formation of micelle-like aggregates of SDBS within the gel is discussed in terms of recent theoretical and experimental results.     

硅胶与高岭土的润湿性及荧光和驱油研究

利用Washburn方程测量固体粉末的润湿性,研究了十二烷基苯磺酸钠(SDBS)水溶液在硅胶及高岭土两种固体粉末表面上的接触角,用荧光猝灭法测定了SDBS在水溶液里的胶束平均聚集数。并由此探讨了十二烷基苯磺酸钠水溶液在固体粉末表面的润湿性,表面活性剂的临界胶束浓度(CMC)与表面含油粉末脱油率的关系。     

Dielectric relaxation spectroscopy of aqueous micellar electrolyte solutions: A novel application to infer Dukhin number and zeta potential of a micelle

The complex permittivities of aqueous SDS solutions, with and without the addition of sodium chloride (NaCl), are measured in the frequency range from 200 MHz to 14 GHz. The SDS concentrations are chosen such that the SDS molecules aggregate to micelles. In this frequency range, the measured spectra allow for the identification of two different relaxation processes. That is, the relaxation of the water molecules at frequencies above 1 GHz and the micellar relaxation at frequencies lower than 1 GHz. It is found that the addition of NaCl to the system mostly affects the micellar relaxation process. In detail, the time constant as well as the amplitude of the relaxation decrease by adding NaCl. These effects are attributed to the change in the solution conductivity that changes the properties of the micelle's electrical double layer. We also extract the Dukhin number of the micelles as a function of surfactant and electrolyte content from the measurements. The Dukhin number is a dimensionless group that describes the influence of the surface conductivity on a phenomena. A regression between Dukhin numbers and free sodium ions is found so that all data collapses on a single curve independent of the surfactant concentration. The surface conductivity is a manifestation of the electrical double layer and we use the Bikerman equation to infer the zeta potential of the micelles. Comparison to literature data shows very good agreement and proves that dielectric relaxation spectroscopy can be engaged to infer the zeta potential of micelles. Abbreviations: CMC critical micelle concentration, DRS dielectric relaxation spectroscopy, EDL electrical double layer     

共振光散射方法研究钙存在下十二烷基苯磺酸钠的聚集行为

利用共振光散射技术在不引入探针的条件下,建立了室温下直接测定十二烷基苯磺酸钠(SDBS)的临界胶束浓度(CMC)的方法.研究发现:在室温下,SDBS水溶液的共振光散射强度(RLS)随SDBS浓度的增加而增强;且当SDBS接近其临界胶束浓度时,RLS强度增强显著,共振光散射峰分别位于330和396 nm.396 nm处的RLS强度与SDBS浓度关系曲线呈S型曲线,本文将曲线突升起点处两条切线的交点对应的SDBS浓度,确定为SDBS的临界胶束浓度(CMC),这与荧光芘探针和电导率等方法测定结果基本一致.并利用此方法分别研究了Ca2+浓度对SDBS及其SDBS-聚乙二醇辛基苯基醚(OP)复配体系聚集行为的影响.结果表明,SDBS与OP以1∶ 3复配时,增强了体系的抗钙能力.     

Dielectric Properties of Apolar Micelle Solutions Containing Solubilized Water

Varying amounts of water have been solubilized in a micelle solution of sodium di-2-pentyl–sulfoscuccinate in benzene and the complex permittivity has been observed in the range 200 KHz to 10 MHz. Part of a dielectric dispersion is seen, which extends to higher frequencies with a broad distribution of relaxation times. Due to association processes, the static dielectric increment is found to vary non-linearly with hydrated micelle concentration and with the amount of solubilized water, whereas a linear variation with micelle concentration is found if no water is added. These effects are explained on the assumption that part of the solubilized water increases the dipole moment of the micelle. Additionally, at higher water concentrations, a sudden increase in the conductivity of the solution is observed, which is taken to indicate a conformational change of the solubilized micelle.     

Dielectric Analysis on the Microscopic Characteristics of the Cloudy Silwet L-77 Solution

Dielectric relaxation spectra of the cloudy Silwet L-77 solutions were investigated from 40 Hz to 110 MHz. A striking Maxwell-Wagner relaxation was observed at about 10⁶ Hz, which was assigned to the interfacial polarization between the micelle particle (L₁) and the continuous water (W). Based on the concentration and the temperature dependence of the dielectric increment and the low-frequency conductivity (σ _l ), the critical data and the corresponding micellar structures of the Silwet L-77 solutions under cloudy state were clarified. Furthermore, the viscosity evolution in the W-L₁ region was confirmed according to an anomalous lower temperature dependence of σ _l .      

一个高粘弹的阴离子蠕虫胶束体系

以频率扫描和稳态剪切实验研究了140 mmol·L^-1羧酸盐gemini 表面活性剂(C₁₄Φ₂C₁₄)在100 mmol·L^-1 NaBr 条件下溶液的流变行为. 在低剪切频率时, 溶液呈现出具有单一松弛时间特性的Maxwell 流体行为.通过活的高分子模型(living polymer model)分析,C₁₄Φ₂C₁₄体系在25℃ 时形成了很长的蠕虫胶束(3.6-6.8μm). 冷冻透射电镜也观察到蠕虫胶束的形成. 这些胶束相互缠绕, 形成了很黏稠的溶液(零剪切粘度高达1.10×10⁴ Pa·s), 外观呈现胶状. 随着温度升高至70℃, 体系的相对粘度仍旧保持很高(1.8×10⁴), 这在阴离子表面活性剂蠕虫胶束溶液中是很少见的. 体系的流动活化能(E_a)约为(141±5) kJ·mol^-1. 利用动态光散射测定了C₁₄Φ₂C₁₄聚集体的尺寸分布, 证实了这个表面活性剂在5-10 mmol·L^-1的低浓度时生成了约100 nm的大聚集体, 这些大聚集体随着表面活性剂浓度的增加很容易转化成棒状直至蠕虫胶束.