Interfacial Properties of Aqueous Nonionic Fluorocarbon Surfactant Solutions

The equilibrium, dynamic surface tensions, and surface dilatational elasticity of aqueous solutions of nonionic fluorocarbon surfactant are reported. The critical micellar concentration, CMC (0.023 mM) and equilibrium surface tension (24.6 m N . m^?1) at CMC were measured by Wilhelmy plate method for aqueous solution of C₈F₁₇SO₂N(C₃H₇)(C₂H₄O)_nH (n=20), abbreviated as EF122A. The surface tension decay is slower for C₈F₁₇SO₂N(C₃H₇)(C₂H₄O)_nH (n=10) system, abbreviated as EF122B compared to the EF122A system over short time region, which indicates the slow transport of the surfactant molecules to the surface. The relaxation time for surface tension decay is estimated by fitting a series of exponentials to the dynamic surface tension data and it decreases with temperature for EF122A. Slow exchange of monomers between bulk and interface is reflected in the high elasticity value of the air‐liquid interface for EF122B compared with EF122A within measured frequency window (0.125–1.25 Hz).     

Dependence of Surface Tension of Near-boiling Non-associated Liquids on Their Molar Volume and Some Critical Constants

Abstract

The equation proposed for near-boiling non-associated liquids describes a new functional dependence of their surface tension on such physico-chemical characteristics as: critical volume, critical temperature and molar volume at the temperatures which are near their normal boiling points. It is shown that, in the case of some low-boiling liquids, possessing small molecules, this equation can be used for the adequate calculation of surface tension at different temperatures in the liquid phase.     

Some Physical Properties of Binary Liquid Systems: (2-Butanone + n-Propionic Acid or n-Butyric Acid)

Abstract

Density, viscosity and surface tension of two binary liquid systems: 2-butanone + n-propionic acid, 2-butanone + n-butyric acid have been determined at 20, 30 and 40°C, over the whole compositional range. The excess values of molar volume, viscosity, Gibbs free energy for the activation of flow and surface tension were evaluated. These excess values were fitted to a Redlich-Kister type of equation. The Grunberg-Nissan parameter, d, was also calculated. The binary viscosity data were fitted to the models of McAllister, Heric, Auslander and Teja and Rice. Surface tension data were fitted to the models of Zihao and Jufu, Rice and Teja, and an empirical two-constant model proposed in this study.     

Surface tension of pure liquid lanthanide and early actinide metals

A systematic theoretical study of the surface tension of liquid rare earth metals and early actinides is performed. An equation, based on the theoretical considerations suggested by Eyring, enables one to calculate the surface tension of elementary substances in a wide temperature range from melting to boiling points. The results of temperature-dependent surface tension calculations of a pure liquid terbium (1629–1880?K) are fitted as γ?=?845?0.1 (T???T _m) (mJ?m²), where the surface tension decreases linearly with temperature. The surface tension was also calculated, at melting points, for all the liquid rare earth metals from La to Lu and for the first six metals of the actinide series from Ac to Pu. It is observed that the lanthanides may be divided into three groups in accordance with their electronic structure. Mostly, the calculated results agree well with available experimental data.     

Synthesis of Highly Fluorinated Aryl N-Acylsulfamates and Evaluation of Their Surfactant Properties

Abstract

Reaction of highly fluorinated carboxylic acids with aroxysulfonylisocyanates in the presence of triethylamine allowed the preparation of the corresponding highly fluorinated aroxy-N-sulfonylsulfamates. The reaction proceeds with good yield in toluene at room temperature or more rapidly in the same solvent at 60 °C. Surface tension measurement at the air/water interface showed that these compounds constitute new excellent nonionic surfactants exhibiting high surface activity in the range of the best nonionic fluoro surfactants, already described in the literature. The critical micelle concentration (CMC) has been calculated from the surface tension measurements on surface aqueous solutions.     

Prediction of the surface tension of cesium in the whole liquid range

Surface tension is an important quantity, both as physical and technological features. We applied the general form of Lennard-Jones potential model, LJ (m-n), and some thermodynamic arguments in the Kirkwood and Buff equation to calculate the surface tension of liquid cesium. To find out the surface tension in a wide temperature range, only pVT data are required. By this method, we investigated the influence of the potential model on the surface tension. For two selected potential models [LJ (6–3) and LJ (8.5–4)], the values of the calculated surface tension and the predicted surface energy agree with the experimental values.     

The Thermocapillary Migrations of Drop and Fluid in Microgravity Environment

In this article, we consider that the geothermal gradient induces the surface tension gradient and the surface tension gradient induces longitudinal shear stress and fluid motion. The temperature gradient induces transfer of heat and matter. A theoretical solution of the velocity distribution of thin fluid film and the velocity of migration of oil are presented. Three experiments attest to the geothermal gradient is assuredly a driven force of the migration of oil. An experiment is mathematics simulation of migration of oil; the other two experiments are from literatures (Huang, C., Hu, L., & Kang, Q. (2005) Acta Mechanica Sinica, 37 (02), 232–237; Qiu, N. & Fang, J. (2003) Oil & Gas Geology, 24 (03), 210–214 [in Chinese].). All experiments show that under the action of an applied temperature difference the gradient of surface tension is formed. The consequence of variation of the surface tension due to a thermal gradient results in a tangential stress which, by viscous traction, causes the motion of neighboring fluid. The temperature difference and time control the migration velocity and distance. This also may effect accumulation and evolvement of oil/gas.     

Silicon-Modified Carbohydrate Surfactants V: The Wetting Behaviour of Low-Molecular-Weight Siloxane,Carbosilane, Silane and Polysilane Precursors on Low-Energy Surfaces

The surface tensions, wetting tensions, contact angles and solid/liquid interfacial tensions of defined siloxanes as well as those of analogous carbosilanes, polysilanes and neopentyl substituted silanes were determined. The wetting experiments were carried out on a glass plate coated with perfluoroalkyl methacrylate (FC 722^®). The siloxanes possess the lowest surface tensions. Due to the presence of oxygen atoms in the siloxane backbone, a donor–acceptor portion (γ^+/−_lv) of the surface tension of about 1–2 mN/m was determined. The solid/liquid interfacial tension also contains a donor–acceptor portion (γ^+/−_sl). Its value is almost identical to that of γ^+/−_lv. The γ^+/−_sl differences between individual molecules of the same surface tension are responsible for contact angle differences of up to 4°. © 1997 John Wiley & Sons, Ltd.     

1-烷基-3-甲基咪唑系列室温离子液体表面张力的研究

合成了系列1-烷基-3-甲基咪唑四氟硼酸盐([C_2～7mim]BF₄)及六氟磷酸盐([C_4～7mim]PF₆)室温离子液体, 并通过核磁氢谱、红外光谱、质谱等手段对其进行了结构表征; 采用Wilhelmy白金板法, 在293～338 K范围内测定了离子液体的表面张力, 测试结果显示, 同类离子液体表面张力γ随温度的升高而线性下降, 同种离子液体的表面张力呈现出较宽的变化范围, 如293 K下, 表面张力值从[C₂mim]BF₄的50.4 mJ/m²到[C₇mim]BF₄的36.1 mJ/m². 最后对离子液体的表面性能进行了讨论.     

Interaction Between GMAC-m-CS and Surfactants: Surface Tension and Conductivity Methods

Glycidyl trimethyl ammonium chloride-modified chitosan (GMAC-m-CS) was synthesized through nucleophilic substitution of GMAC on CS in isopropanol dispersed system, which was characterized by FTIR and ¹H NMR methods. The interaction between GMAC-m-CS and surface active ILs ?1-dodecyl (tetradecyl and hexadecyl)-3-methylimidazolium bromide (C_nmimBr, n = 12, 14, 16) was studied by surface tension and conductivity methods. The amount of C_nmimBr adsorbed on GMAC-m-CS increases first with raising temperature, and then decreases, which reaches the largest amount at 30°C. The amount increases with the increase of alkyl chain length. The surface tension reducing capabilities of GMAC-m-CS/C_nmimBr systems increase with temperature, however, decrease with the increase of GMAC-m-CS concentration. The aggregation processes of C₁₄mimBr in solutions without GMAC-m-CS and with high concentration of GMAC-m-CS were entropy driven; however, it is enthalpy driven in solutions with low concentration of GMAC-m-CS. Based on the analysis of properties of GMAC-m-CS/C_nmimBr, the interaction model of GMAC-m-CS/ILs was proposed.     

Non-monotonic behaviour with concentration of the surface tension of certain binary liquid alloys

The surface tension σ(c) of most liquid binary alloys usually varies with concentration c in a monotonic way between the values σ₁ and σ₂ of the two pure metals, and this behaviour is well explained by current models. Some alloys show deviations from this ideal behaviour. One of those is Fe–B. The surface tension of this liquid alloy shows a minimum at 17 atomic % B, which corresponds well with the composition of the eutectic point in the phase diagram, followed by a maximum at a concentration of 24 atomic % B or higher. The usual models for the surface tension of liquid binary alloys do not explain those exceptional features, and we propose that a model involving the concentration fluctuations in the liquid alloy has the proper ingredients to account for the features in Fe–B and similar alloys.     

Synthesis of Surfactants from Alkali Lignin for Enhanced Oil Recovery

With the cheap and abundant resource of alkali lignin as feedstock, surfactants for enhanced oil recovery were synthesized by amination and alkylation reaction of lignosulfonate. The effects of amination conditions, including the ratio of raw materials, amination reagent, temperature, and reaction time, on nitrogen contents and surface tension of the surfactants were investigated. The results showed that ethylenediamine was more suitable for amination, and the molar ratio of alkali lignin, ethylenediamine, and formaldehyde was 1:2:1.5 at 80°C for 5 hours. The structure of synthesized products was characterized by Fourier transform infrared spectrometry. The HLB value of synthesized product was 10. The interfacial tension between Daqing crude oil and synthetic water could be decreased to 10^?2 mN/m with synthesized surfactant and NaOH at 45°C. Moreover, the effects of molecular weight of surfactants on interfacial tension were also studied. The synthesized surfactant (M_w > 10,000) showed a better interfacial activity on Daqing crude oil.     

The wettability of polytetrafluoroethylene by aqueous solution of cetylpyridinium bromide and propanol mixtures

Measurements of advancing contact angles (θ) were carried out for aqueous solutions of cetylpyridinium bromide (CPBr) and propanol mixtures at constant CPBr concentration equal to 1 × 10⁻⁵, 1 × 10⁻⁴, 6 × 10⁻⁴, 1 × 10⁻³ M, respectively, on polytetrafluoroethylene (PTFE). The obtained results indicate that the wettability of PTFE by aqueous solutions of these mixtures depends on their composition and concentration. In contrast to Zisman, there is no linear dependence between the cos θ and surface tension of aqueous solutions of CPBr and propanol mixtures (γ_LV), but a linear relationship exists between the adhesion tension and the surface tension of aqueous solutions of CPBr and propanol mixtures which have a slope equal to −1, and between cos θ and the reciprocal of the surface tension of solution. The slope equal to −1 and the intercept on the cos θ axis close to −1 suggest that adsorption of CPBr and propanol mixtures and the orientation of their molecules at aqueous solution–air and PTFE–aqueous solution interfaces are the same. This also suggests that the work of solution adhesion to the PTFE surface does not depend on the concentration of propanol and CPBr. Extrapolation of the straight line to the point corresponding to the surface tension of solution, which completely spreads over the PTFE surface, gives the value of the critical surface tension of PTFE wetting equal to 24.84 mN/m. This value is higher than PTFE surface tension (20.24 mN/m) and the values of the critical surface tension of PTFE wetting determined by other investigators from the contact angle of nonpolar liquids (e.g. n-alkanes). The differences between the value of the critical surface tension obtained here and those which can be found in the literature were discussed on the basis of the simple thermodynamic rules. Using the measured values of the contact angles and Young equation the PTFE–aqueous solution interfacial tension was determined. The values of PTFE–aqueous solution interfacial tension were also calculated from Miller and co-workers equation in which the correction coefficient of nonideality of the surface monolayer was introduced. From comparison of the obtained values it appears that good agreement exists between the values of PTFE–solution interfacial tension calculated on the basis of Young and Miller and co-workers equations in the whole range of propanol concentration.     

Experiments and model for the surface tension of carbonated monoethanolamine aqueous solutions

The surface tension of carbonated monoethanolamine aqueous solutions from 293.15 to 323.15 K was measured by using an automatic surface tension-meter.A model applicable for the surface tension of MEA-CO2-water mixtures was proposed and the calculated results agreed well with the experiments.The influences of temperature,MEA concentration and CO2 loading were demonstrated on the basis of experiments and calculations.     

Prediction of critical temperature of n-alkanes and n-alkenes from surface tension vs. temperature data

 The surface tension versus temperature data of homologous series of n-alkanes and n-alkenes is analyzed. Critical temperatures are shown to be predicted from these data, with a very high precision, after some corrections are made. The corrections are shown to arise from the effect of the critical pressure on the extrapolated data to surface tension approaching zero. Received: 29 October 1996 Accepted: 13 December 1996     

The surface tension of aqueous polyvinylamine and copolymers with <Emphasis Type="Italic">N</Emphasis>-vinylformamide

 The surface tensions of aqueous poly(N-vinylformamide) (PNVF), polyvinylamine (PVAM), and PNVF–PVAM copolymers were measured as functions of pH. The nonionic PNVF gave a pH-independent surface tension of 68 mN/m. The surface tension of PVAM was pH dependent; at pH 10 it was 56 mN/m, whereas it was 71.5 mN/m at pH 3.5. The transition from higher to lower surface tension values occurred most dramatically between pH 8 and 9, reflecting the dissociation behavior of the amine groups. The copolymers showed intermediate behavior. Received: 20 August 2001 Accepted: 26 September 2001     

Behavior of the Surface Tension and the Viscosity in the Eutecticregion of the Liquid Feb alloy

Abstract

Thermodynamic and transport properties of pure liquid metals show interesting correlations near the melting temperature. This is well known for the case of the surface tension σ and the shear viscosity η In this paper we investigate the possible extension of these correlations to binary alloys, taking the FeB alloy as a case study. Based on literature data we analyze the variation of σ and η as a function of temperature and concentration in a deep eutectic region of the phase diagram of this alloy, as well as the possible correlations between those two quantities. Substantial differences with respect to the behavior in pure metals are found.     

Dynamic Surface Tension and Adsorption Mechanism of Surfactant Benzyltrimethylammonium Bromide at the Air/Water Interface

The air‐solution equilibrium tension, γ_c and dynamic surface tension, γ_t, of aqueous solutions of a novel ionic surfactant benzyltrimethylammonium bromide (BTAB) were measured by Wilhelmy method and Maximum bubble pressure method (MBPM), respectively. Adsorption equilibrium and mechanism of BTAB at the air‐solution interface were studied. The CMC was determined to be 0.11 mol/L. The results show that at the start, the adsorption process is controlled by a diffusion step. Toward the end, it changes to a mixed kinetic‐diffusion controlled mechanism with the adsorption activation energy of about 11.0 KJ/mol. Effects of temperature, inorganic salts, and alcohols on adsorption kinetics also are discussed.     

Understanding the Buoy Effect of Surface-Enriched Pt Complexes in Ionic Liquids: A Combined ARXPS and Pendant Drop Study**

Recently, we demonstrated that Pt catalyst complexes dissolved in the ionic liquid (IL) [C₄C₁Im][PF₆] can be deliberately enriched at the IL surface by introducing perfluorinated substituents, which act like buoys dragging the metal complex towards the surface. Herein, we extend our previous angle-resolved X-ray photoelectron spectroscopy (ARXPS) studies at complex concentrations between 30 and 5 %_mol down to 1 %_mol and present complementary surface tension pendant drop (PD) measurements under ultraclean vacuum conditions. This combination allows for connecting the microscopic information on the IL/gas interface derived from ARXPS with the macroscopic property surface tension. The surface enrichment of the Pt complexes is found to be most pronounced at 1 %_mol. It also displays a strong temperature dependence, which was not observed for 5 %_mol and above, where the surface is already saturated with the complex. The surface enrichment deduced from ARXPS is also reflected by the pronounced decrease in surface tension with increasing concentration of the catalyst. We furthermore observe by ARXPS and PD a much stronger surface affinity of the buoy-complex as compared to the free ligands in solution. Our results are highly interesting for an optimum design of IL-based catalyst systems with large contact areas to the surrounding reactant/product phase, such as in supported IL phase (SILP) catalysis.     

Studies on the Effects of Additional Components on Micellization of CTAB via Surface Tension Measurements

The effects of Tris-HCl buffer solution on the cmc of cetyltrimethylammonium bromide (CTAB) were studied by surface tension measurement. The result shows that the effect of the buffer solution depends on the interaction between CTAB and NaCl and the structure accelerants of water, Tris. A series of parameters, including the critical micelle concentration (cmc), the surface tension at cmc (γ_cmc), the adsorption efficiency (pC₂₀), and the effectiveness of surface tension reduction (∏_cmc) were obtained from the surface tension measurements in the presence of glycine with different concentration in the Tris-HCl buffer solution at 27°C. In addition, maximum surface excess concentration (Γ _max) and minimum surface area per molecule (A_min) at the air-water interface were estimated according to the Gibbs adsorption isotherm. The thermodynamic parameters (Δ C _p,m , Δ H _m,tr , Δ C _p,m,tr ) of micellization for CTAB in the absence and presence of glycine at different temperature were also been obtained.