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Polymerization in non-aqueous lyotropic liquid crystals: Influence of the unsaturation site 非水溶性液晶中的聚合:不饱和位点的影响
Pub Date : 1993-01-18 Epub Date: 2001-10-15 DOI: 10.1016/0166-6622(93)80005-Z
Stig E. Friberg , Bing Yu , Ahsan U. Ahmed , Gregory A. Campbell

Two surfactants, bis[2-(dodecyloxycarbonyl)ethyl](p-vinylbenzoyl)methylammonium chloride (SI) and bis[2-(10-undecenoyloxycarbonyl)ethyl](p-methylbenzoyl)methylammonium chloride (SII) were synthesized and copolymerized with polar and non-polar monomers to form regularly layered structures.

The results showed a pronounced difference between the two surfactants. SI with the double bond close to the polar group accepted a large number of monomers, in contrast to the behavior of SII. For SI the polymerization changed the conformation of the p-vinylbenzoyl group depending on the location of the added monomer while copolymerization of the monomers with SII gave no significant change.

A comparison with earlier results from bis[2-(10-undecenoyloxycarbonyl)ethyl](p-vinylbenzoyl)methylammonium chloride provided proof of copolymerization of all the groups.

合成了双[2-(十二烷基氧羰基)乙基](对乙烯基苯甲酰)甲基氯化铵(SI)和双[2-(10-十一烷基氧羰基)乙基](对甲基苯甲酰)甲基氯化铵(SII)两种表面活性剂,并与极性和非极性单体共聚形成规则的层状结构。结果表明两种表面活性剂之间有明显的差异。具有靠近极性基团的双键的SI接受了大量的单体,与SII的行为相反。对于SI,聚合改变了对乙烯基苯甲酰基团的构象,这取决于添加的单体的位置,而单体与SII的共聚没有明显的变化。与先前的[2-(10-十一烯氧羰基)乙基](对乙烯基苯甲酰)甲基氯化铵的结果进行比较,证明了所有基团的共聚。
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引用次数: 9
On the stability of concentrates. Non-aqueous dispersions 精矿稳定性研究。非水乳液
Pub Date : 1993-01-18 Epub Date: 2001-10-15 DOI: 10.1016/0166-6622(93)80008-4
E. Ruckenstein

It is demonstrated that the depth of the potential well between two colloidal particles which interact via van der Waals interactions can be minimized if they are covered with a shell of adsorbed surfactant molecules whose Hamaker constant is near to that or the liquid medium. This result is used to explain some experimental observations (I. Sushumna, R.P. Gupta and E. Ruckenstein, J. Mater. Res., 7 (1992) 2884) which indicate that long-chain fatty acids with an alkyl side chain of 5–10 carbon atoms located far from the head group of the surfactant lead to lower paste viscosities than those without side chains or with longer side alkyl chains. It is also suggested that, in concentrated suspensions, the collective interactions when the pair interaction is attractive can lead to an effective repulsion component between two neighboring particles, and that this effect may contribute to the stability of the concentrated dispersions.

结果表明,在两个通过范德华相互作用相互作用的胶体粒子表面覆盖一层Hamaker常数接近的表面活性剂分子或液体介质,可以使它们之间的势阱深度最小化。这个结果被用来解释一些实验观察(I. Sushumna, R.P. Gupta和E. Ruckenstein, J. Mater)。Res., 7(1992) 2884)表明,与没有侧链或侧烷基链较长的脂肪酸相比,具有5-10个碳原子的烷基侧链的长链脂肪酸,其膏体粘度较低,且远离表面活性剂的头基团。研究还表明,在浓悬浮液中,当对相互作用具有吸引力时,集体相互作用会导致两个相邻粒子之间产生有效的排斥分量,这种效应可能有助于浓悬浮液的稳定性。
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引用次数: 12
Micelle dissociation kinetics study by dynamic surface tension of micellar solutions 胶束解离动力学的动态表面张力研究
Pub Date : 1993-01-18 Epub Date: 2001-10-15 DOI: 10.1016/0166-6622(93)80006-2
V.B. Fainerman, A.V. Makievski

The dynamic surface of sodium tetradecylsulphate and sodium bexadecylsulphate solutions in water and also in Triton X-100 solutions was measured by the maximum bubble-pressure method, using modern computerized instrumentation, for a wide range of surface lifetimes (from 0.001 to 10 s), temperatures (from 30 to 80°C) and surfactant concentrations (from 1 to 200 CMC). On the basis of a previously suggested adsorption kinetics theory for micellar solutions of ionogenic surfactants (V.B. Fainerman, Colloids Surfaces, 62 (1992) 333) a method was developed for the calculation of the micellar dissociation rate constant k. For the surfactants studied, k increases with increasing concentration. Moreover, for ionic surfactants the dependence of k on concentration (C) becomes more striking for C> (10–30) CMC. This can be explained by a micelle shape transition and by a strengthening of the intermolecular repulsion in micelles. In solutions of the ionic surfactants the constant k increasing with increasing temperature, whereas in Triton X-100 solutions a temperature dependence is absent. This phenomenon is associated with the different nature of the molecular interactions for ionogenic and non-ionogenic surfactants in micelles. The k values, obtained from results of dynamic surface tension measurements, are in satisfactory agreement with the results of a study of the relaxation of micellar solutions published previously.

采用现代计算机化仪器,采用最大气泡压力法测量了十四烷基硫酸钠和十六烷基硫酸钠溶液在水和Triton X-100溶液中的动态表面,其表面寿命范围从0.001到10秒,温度范围从30到80°C,表面活性剂浓度范围从1到200 CMC。在先前提出的离子源表面活性剂胶束溶液吸附动力学理论的基础上(V.B. Fainerman, Colloids Surfaces, 62(1992) 333),开发了一种计算胶束解离速率常数k的方法。对于所研究的表面活性剂,k随着浓度的增加而增加。此外,对于离子表面活性剂,k对浓度(C)的依赖性对C>更为明显;CMC(10 - 30)。这可以用胶束形状的转变和胶束中分子间排斥的加强来解释。在离子表面活性剂溶液中,k常数随温度的升高而增加,而在Triton X-100溶液中则不存在温度依赖性。这种现象与胶束中离子性和非离子性表面活性剂分子相互作用的不同性质有关。从动态表面张力测量结果中得到的k值与先前发表的胶束溶液弛豫研究结果一致。
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引用次数: 16
Contact angle kinetics of human albumin solutions at solid surfaces 人白蛋白溶液在固体表面的接触角动力学
Pub Date : 1993-01-18 Epub Date: 2001-10-15 DOI: 10.1016/0166-6622(93)80001-V
R. Miller , S. Treppo , A. Voigt , W. Zingg , A.W. Neumann

Contact angle kinetics of sessile drops of albumin solution on hydrophilic acetal and hydrophobic FC 721 surfaces were measured using axisymmetric drop shape analysis. Young's equation is used to calculate the solid/liquid interfacial tension from measured contact angles and surface tensions as a function of time. The change in solid/liquid interfacial tension is a result of protein adsorption. It indicates that at the hydrophilic acetal surface the albumin molecules, interact only weakly, whereas the interaction with the hydrophobic FC 721 surface is quite strong.

采用轴对称液滴形态分析方法,测定了白蛋白溶液在亲水性缩醛和疏水性FC 721表面上的固滴接触角动力学。杨氏方程用于从测量的接触角和表面张力作为时间的函数来计算固/液界面张力。固/液界面张力的变化是蛋白质吸附的结果。结果表明,在亲水性缩醛表面,白蛋白分子的相互作用较弱,而与疏水性FC 721表面的相互作用较强。
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引用次数: 33
Open circuit potential measurements with Ti/TiO2 electrodes Ti/TiO2电极开路电位测量
Pub Date : 1993-01-18 Epub Date: 2001-10-15 DOI: 10.1016/0166-6622(93)80003-X
Marcelo J. Avena, Osvaldo R. Cámara, Carlos P. De Pauli

The open circuit potential (OCP) vs pH response of Ti/TiO2 electrodes prepared by thermal and electrochemical oxidation of metallic titanium was measured in KNO3 aqueous solutions in order to establish whether the slopes of the OCP-pH curves can be used as a measure of the variation of surface potential (ψo) of TiO2 with the pH of the aqueous solution. For comparison purposes, ψo—pH slopes were also evaluated from surface charge-pH data obtained by acid-base potentiometric titrations of TiO2 dispersions.

Ti/TiO2 electrodes showed a linear OCP-pH response in the range of ph 5–10 with slopes of −0.039 ± 0.005 V ph−1. The OCP-pH dependence of Ti/TiO2 electrodes was lower than that predicted thermodynamically. According to the triple-layer model, used to describe the oxide/aqueous solution interface, the OCP-pH slopes obtained for Ti/TiO2 electrodes cannot be identified with the variation of ψo with the pH. Calculations with this model indicated that neither the single nor the double extrapolation methods used to evaluate the intrinsic ionization constant of oxide surface sites render realistic values of these parameters for the TiO2 surface.

The analysis of surface charge—pH data and the use of the triple-layer model to predict experimental values indicated that the ψo—pH slopes of TiO2 surfaces must be greater (in absolute magnitude) than 0.041 V pH−1.

测定了金属钛热氧化和电化学氧化制备的Ti/TiO2电极在KNO3水溶液中的开路电位(OCP)与pH响应,以确定OCP-pH曲线的斜率是否可以作为TiO2表面电位(ψo)随水溶液pH变化的指标。为了比较起见,我们还从TiO2分散体的酸碱电位滴定得到的表面电荷- ph数据中评估了ψ - ph斜率。Ti/TiO2电极在ph 5 ~ 10范围内呈线性OCP-pH响应,斜率为−0.039±0.005 V ph−1。Ti/TiO2电极的OCP-pH依赖性低于热力学预测。根据描述氧化物/水溶液界面的三层模型,得到的Ti/TiO2电极的OCP-pH斜率不能用ψo随ph的变化来识别。该模型的计算表明,用于评估氧化物表面位置的本征电离常数的单外推法和双外推法都不能给出TiO2表面这些参数的真实值。通过对表面电荷- pH数据的分析和利用三层模型对实验值的预测表明,TiO2表面的ψ - pH斜率必须大于(绝对值)0.041 V pH−1。
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引用次数: 30
Science and technology of carbon black 炭黑科技
Pub Date : 1993-01-18 Epub Date: 2001-10-15 DOI: 10.1016/0166-6622(93)80011-4
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引用次数: 0
The adsorption of phosphamidon on the surface of antimony(V) phosphate: A thermodynamic study 磷酸锑(V)表面吸附磷酰胺的热力学研究
Pub Date : 1993-01-18 Epub Date: 2001-10-15 DOI: 10.1016/0166-6622(93)80007-3
K.G. Varshney, A.A. Khan, Upma Gupta, S.M. Maheshwari

The thermodynamics of the adsorption of phosphamidon on antimony(V) phosphate cation exchanger has been studied at 30, 45 and 50°C and the thermodynamic equilibrium constant (K0), standard free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°) have been calculated to predict its adsorption behaviour. All the data are adequately represented by the Freundlich isotherms.

研究了磷酸锑(V)阳离子交换剂在30℃、45℃和50℃下吸附磷酰胺的热力学,并计算了热力学平衡常数K0、标准自由能变(ΔG°)、焓变(ΔH°)和熵变(ΔS°)来预测其吸附行为。所有的数据都可以用Freundlich等温线充分表示。
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引用次数: 6
Zeolite '93 沸石93
Pub Date : 1993-01-18 Epub Date: 2001-10-15 DOI: 10.1016/0166-6622(93)80010-D
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引用次数: 0
Relaxation of adsorption layers at solution/air interfaces using axisymmetric drop-shape analysis 利用轴对称液滴形状分析溶液/空气界面吸附层的松弛
Pub Date : 1993-01-18 Epub Date: 2001-10-15 DOI: 10.1016/0166-6622(93)80002-W
R. Miller , R. Sedev , K.-H. Schano , C. Ng , A.W. Neumann

Axisymmetric drop-shape analysis is used to investigate the relaxation of surfactant adsorption layers after transient interfacial area changes, e.g. square-pulse or step-type disturbances. The response functions for sodium dodecyl sulfate solutions of different origin and for sodium tetradecyl sulfate are measured and interpreted in terms of a diffusion-controlled matter-exchange model. For both surfactant systems the data can be explained by considering small amounts of surface-active contaminations.

采用轴对称液滴形状分析研究了表面活性剂吸附层在瞬态界面面积变化(如方波或阶跃扰动)后的弛豫。测量了不同来源的十二烷基硫酸钠溶液和十四烷基硫酸钠溶液的响应函数,并用扩散控制的物质交换模型解释了响应函数。对于这两种表面活性剂体系,数据可以通过考虑少量表面活性污染来解释。
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引用次数: 67
Dissolution of solid particles in liquids: A reaction—diffusion model 固体颗粒在液体中的溶解:一个反应-扩散模型
Pub Date : 1993-01-18 Epub Date: 2001-10-15 DOI: 10.1016/0166-6622(93)80004-Y
Jyh-Ping Hsu, Bo-Tau Liu

The dissolution of solid particles in liquids involves the dissociation of solute molecules through a surface reaction and the subsequent diffusion of these molecules toward the bulk liquid phase. The conventional analysis is mainly based upon extreme cases, i.e. the rate of dissolution is either controlled by surface reaction or by molecular diffusion. Here, the analysis is generalized so that the diffusional resistance and the resistance for the surface reaction are considered simultaneously. Also, the effect of the variation of the solute concentration in the bulk liquid phase on dissolution is taken into account. The applicability of the present model is justified by analyzing the experimental results for the dissolution or human enamel powder in water. The evaporation of a water drop in air and the dissolution of 2-naphthol in water are also discussed. It is concluded that neglecting the effect of the surface reaction in the dissolution kinetics may lead to a significant deviation between experimental data and theoretical calculation.

固体颗粒在液体中的溶解包括溶质分子通过表面反应解离和随后这些分子向散装液相的扩散。传统的分析主要基于极端情况,即溶解速率要么由表面反应控制,要么由分子扩散控制。在此,对分析进行了推广,同时考虑了扩散阻力和表面反应阻力。同时,考虑了体积液相中溶质浓度的变化对溶解的影响。通过对人牙釉质粉末在水中溶解的实验结果分析,证明了该模型的适用性。还讨论了水滴在空气中的蒸发和2-萘酚在水中的溶解。结果表明,忽略表面反应对溶解动力学的影响可能导致实验数据与理论计算存在较大偏差。
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引用次数: 9
期刊
Colloids and Surfaces
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