多支链烷基苯磺酸钠水溶液的表面性质

用自制的四种高纯度多支链烷基苯磺酸钠,研究了支链结构对其表面性质的影响.结果表明,随支链烷基碳数增加,临界胶束浓度降低,标准吸附自由能DGadӨ更负;但是,饱和吸附量Γmax却随支链烷基碳数增加而减小,且临界胶束浓度时的表面张力γcmc随吸附量减小而降低,表现出与一般表面活性剂不同的变化趋势.从多支链烷基苯磺酸钠的分子结构特点,解释了随支链烷基碳数增加Γmax和γcmc的变化规律,探讨了分子的独占面积(as)对Γmax及γcmc的影响.     

Interfacial activity of a novel family of polymeric surfactants

A novel series of polymeric surfactants based on carboxy methyl cellulose and alkyl poly(etheroxy) acrylate were synthesized by ultrasonic irradiation. These polymeric surfactants have exhibit excellent surface activity due to their unique structure. The influences of salt, alcohol and alkali on the interfacial activity of these polymeric surfactants were studied by interfacial tensiometery, dynamic laser scattering (DLS), UV spectroscope and environmental scanning electrical microscope (ESEM). The surface tension and interfacial tension (IFT) properties change little with NaCl added. The formed micelles shrink, their size becomes smaller. Alcohols cause the IFT to decrease a little because a small amount of free chains present in solution. Under the influence of added alkali, the IFT of the polymeric surfactants, in aqueous solution, decreases so much that sometimes it is less than 10⁻² mN/m. Using data from the equivalent alkane scan, one cannot draw the conclusion that the action of alkali with the acidic components in crude oil leads to the ultra-low IFT. The analyses by UV, DLS and ESEM show that the micelles formed by polymeric surfactants could be disaggregated or destroyed sharply by the action of alkali. So the size of micelles decreases greatly and the number of free chains increases. That more polymeric surfactants molecules move to the interface of oil/water and rearrange at the interface of oil/water is believed to be the main reason of the ultra-low IFT (10⁻³ mN/m) that is obtained.     

LSmn系列表面化学性质与胶束化作用

通过表面张力的测定, 研究了十二烷基聚氧乙烯聚氧丙烯醚(LSmn)系列表面活性剂LS36、LS45、LS54在溶液表面吸附和形成胶束的热力学函数随温度的变化. 给出了它们在水溶液中的二组分相图.结果表明, LS36、LS45、LS54的表面活性都较高. 在25～50 ℃范围内, 临界胶束浓度(cmc)和平衡表面张力分别在4.44×10－6～17.3×10－6 mol•L－1和30.1～33.5 mN•m－1之间, 表面吸附和形成胶束的自由能分别在－40.0～－49.5 kJ•mol－1和－27.2～－33.1 kJ•mol－1之间.不论是在溶液表面吸附还是形成胶束均为熵驱动过程.其中LS36由于含具有亲水能力较强的聚氧乙烯基团(EO)成分较低, 因此不论其浊点还是其表面吸附和形成胶束的热力学函数均与LS45、LS54具有较大差异.     

Effect of Neck Formation on the Measurement of Dynamic Interfacial Tension in a Drop Volume Tensiometer

Dynamic interfacial tension values obtained by drop volume tensiometry will be affected under certain experimental conditions by the formation of a neck between the drop and the capillary tip. This phenomenon must be accounted for to obtain accurate values of interfacial tension. In this work, neck formation for a water–mineral oil system is studied under conditions where hydrodynamic effects can be neglected. A model originally developed for the determination of the surface tension of a suspended drop is modified for application to dynamic interfacial tensions of surfactant-containing liquids. The model relates apparent values of interfacial tension calculated from drops possessing necks to actual values. Experiments with Span 80 (sorbitan monooleate) and sodium dodecyl sulfate (SDS) surfactants in a mineral oil–water system are used to test the validity of the developed model. For the small tip diameter used, good agreement is obtained for Span 80 up to the critical micelle concentration, and for low concentrations of SDS, when the surfactant adsorption is diffusion-limited. In both cases, the neck diameter of the growing drop can be considered constant over the range of dynamic interfacial tensions tested.     

A theory of adsorption kinetics with time delay and its application to overshoot and oscillation in the surface tension of gelatin solution

A theory of adsorption kinetics with time delay [Ohshima et al. (1992) Colloid Polym. Sci. 270:707] is developed and applied to the surface tension of a polymer solution. It is found that the general appearance of the overshoot and oscillation in the time course of the surface tension of aqueous gelatin solution observed by Sato and Ueberreiter [(1979) Makromol. Chem. 180:829, 1107; (1979) Polym. Prepr. Am. Chem. Soc. Div. Polym. Chem. 20:907) can be explained by the present theory.     

Surfactants having polyfluoroalkyl chains. II. Syntheses of anionic surfactants having two polyfluoroalkyl chains including a trifluoromethyl group at each tail and their flocculation-redispersion ability for dispersed magnetite particles in water

Anionic surfactants having two polyfluoroalkyl chains per molecule, i.e. the sodium salt of bis(1H, 1H, 2H,2H-heptadeca-fluorodecyl)-2-sulfosuccinate, CF₃(CF₂)₇(CH₂)₂OCOCH₂CH(SO₃Na)COO(CH₂)₂(CF₂)₇CF₃, the sodium salt of bis(1H, 1H, 2H, 2H-tridecafluoro-octyl)-2-sulfosuccinate, CF₃(CF₂)₅(CH₂)₂OCOCH₂CH(SO₃Na)COO(CH₂)₂(CF₂)₅CF₃, and the sodium salt of bis(1H, 1H, 2H, 2H-nonafluorohexyl)-2-sulfosuccinate, CF₃(CF₂)₃(CH₂)₂OCOCH₂CH(SO₃Na)COO(CH₂)₂(CF₂)₃CF₃, have been prepared from maleic anhydride, the corresponding alcohols possessing a polyfluoroalkyl chain and sodium hydrogen sulfite. The flocculation and redispersion abilities of these surfactants for dispersed magnetic particles in water have been examined to investigate the effect of the chain length. It was found that this ability was enhanced by an increase in the chain length. The contact angles for water for pelleted surface-modified magnetite have been measured. In order to compare this ability and the contact angles, data for other fluorinated surfactant have been obtained. The Kraff point, the surface tension and the pNa of the aqueous surfactant solutions have also been measured.     

Dynamic surface tension of micellar solutions studied by the maximum bubble pressure method

A theoretical model for the dynamic surface tension of an air bubble expanding in micellar surfactant solution is proposed. The model accounts for the effect of expansion of the bubble surface during the adsorption of surfactant molecules (monomers) and the effect of disintegration of polydisperse micelles on the surfactant diffusion. Assuming small deviations from equilibrium and constant rate of expansion analytical expression for the surface tension and the subsurface concentration of monomers as a function of time is derived. The characteristic time of micellization is computed from the experimental data for two surfactants (sodium dodecyl sulfate and nonylphenol polyglycol ether) obtained by the maximum bubble pressure method.     

The influence of pH on phosphatidylcholine monolayer at the air/aqueous solution interface

The measurements of the interfacial tension at the air/aqueous subphase interface as the function of pH were performed. The interfacial tension of the air–aqueous subphase interface was divided into contributions of individuals. A simple model of the influence of pH on the phosphatidylcholine monolayer at the air/hydrophobic chains of phosphatidylcholine is presented. The contributions of additive phosphatidylcholine forms (both interfacial tension values and molecular area values) depend on pH. The interfacial tension values and the molecular areas values for LH⁺, LOH⁻ forms of phosphatidylcholine were calculated. The assumed model was verified experimentally.     

PREPARATION OF PERFLUOROOCTANOYL-MODIFIED POLY(VINYL-ALCOHOL)S AND THEIR ADSORPTION AT AN AIR-WATER INTERFACE

Perfluorooctanoyl modified poly(vinyl alcohol)s (FPVA) were prepared by means of substituting a small amountof hydroxyl groups on the backbone of poly(vinyl alcohol), for which the initial degree of polymerization is equal to 1750.The substitution extent, defined by the number of substituting units in a chain, for the four FPVA samples was in the range of0.5-5 perfluorooctanoyl groups per chain. The FPVA samples with the highest substitution extent still had good solubility inwater. It was shown by experimental measurement at 30.0±0.1℃ that the surface tension of the aqueous solution of thehighest substituted FPVA decreased to 16.6 mN/In at a higher concentration, e.g about 0.1 g/mL. Obviously,macromolecules of FPVA exhibit a very strong tendency to adsorb at the air-water interface, because the hydrophobicperfluorooctanoyl groups in FPVA have a very high surface activity as they are in small molecular fluorinated surfactants.The chain conformation of such a model polymer adsorbed on the air-water interface was also discussed.     

Effect of surface condition on liquid crystal photoalignment by light-induced azo dye adsorption phenomena

The effect of surface condition on the photoalignment of light-induced methyl red (MR) adsorption phenomena on various substrates based on azo dye-doped liquid crystals is investigated. The results show that the polar surface energy determines the initiation of MR adsorption phenomena. The surface polarity energy of different substrates, which are modulated by oxygen plasma treatment (OPT), is further examined using the sessile drop method. The results also indicate that the uniformity and efficiency of MR adsorption can be enhanced by OPT. Light intensity influences the MR adsorption rate. The uniformity of MR adsorption onto various substrates is analysed via polarised optical microscopy.