Exerowa D, Churaev N V, Kolarov T, Esipova N E, Panchev N, Zorin Z M
Institute of Physical Chemistry, Bulgarian Academy of Sciences, Sofia 1113, Bulgaria.
Adv Colloid Interface Sci. 2003 Jul 1;104:1-24. doi: 10.1016/s0001-8686(03)00033-2.
Foam films and wetting films on quartz, obtained from aqueous solutions of two different surfactants [cetyltrimethylammonium bromide (CTAB) and PEO-PPO-PEO triblock copolymer (F108)] with NaCl as a background electrolyte, are considered as convenient models to compare the properties of symmetric (free thin liquid films) and asymmetric (thin liquid films on solid substrate) films with the same air/solution interface. Microinterferometric methodology of assessment of foam and wetting films is used to allow precise determination of the film thickness. In the case of CTAB films, experimental data for the potential phi(0) of the diffuse electric layer at the solution/air interface and the potential phi(1) at the solution/quartz interface are used to analyze the stability of the films studied. A conclusion drawn is that electrostatic interaction forces stabilize both kinds of films studied. It is shown that with increasing CTAB concentration a charge reversal occurs at both the solution/air and solution/quartz interfaces that determines the stability/instability of the foam and wetting films. Concentration ranges where both types of films produce stable (equilibrium) films are found. There are also concentration ranges where the films either rupture or are metastable (quasi-equilibrium). The CTAB concentration ranges, which provide formation of unstable (rupturing and metastable) and stable films, are different for symmetric (foam) and asymmetric (wetting) thin liquid films. It is only at high CTAB concentrations (>2 x 10(-4) mol dm(-3)) that both cases render formation of stable equilibrium films. In the case of F108 films, the comparison of foam films and wetting films on quartz indicates film stability that is either electrostatic or steric in origin. On the basis of the effect of electrolyte concentration on film thickness, the transition from electrostatic to steric stabilization is demonstrated for both kinds of films. The critical electrolyte concentration at which this transition occurs is determined. Foam films are found to be always stable (equilibrium). Formation of either unstable (rupturing and metastable) or stable (equilibrium) wetting films on quartz is established depending on the solution composition. The effects are similar for both hydrophilic and hydrophobic quartz surfaces. The results obtained show certain similarity between foam and wetting films. In both cases, electrostatic forces below the critical electrolyte concentration, and above it steric forces govern film stability. Some specific properties of the wetting films are induced by the asymmetric boundary conditions as distinct from symmetric foam films.
以氯化钠为背景电解质,从两种不同表面活性剂(十六烷基三甲基溴化铵(CTAB)和聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物(F108))的水溶液中获得的石英上的泡沫膜和湿膜,被视为比较具有相同空气/溶液界面的对称(自由薄液膜)和不对称(固体基质上的薄液膜)膜性质的便捷模型。采用微干涉测量方法评估泡沫膜和湿膜,以精确测定膜厚度。对于CTAB膜,利用溶液/空气界面处扩散电层的电势φ(0)和溶液/石英界面处的电势φ(1)的实验数据来分析所研究膜的稳定性。得出的结论是,静电相互作用力使所研究的两种膜都稳定。结果表明,随着CTAB浓度的增加,溶液/空气和溶液/石英界面都会发生电荷反转,这决定了泡沫膜和湿膜的稳定性/不稳定性。发现了两种膜都能形成稳定(平衡)膜的浓度范围。也存在膜破裂或亚稳(准平衡)的浓度范围。对于对称(泡沫)和不对称(湿)薄液膜,提供不稳定(破裂和亚稳)和稳定膜形成的CTAB浓度范围不同。只有在高CTAB浓度(>2×10⁻⁴ mol dm⁻³)时,两种情况才会形成稳定的平衡膜。对于F108膜,石英上泡沫膜和湿膜的比较表明膜的稳定性源于静电或空间位阻。基于电解质浓度对膜厚度的影响,证明了两种膜都从静电稳定转变为空间位阻稳定。确定了发生这种转变的临界电解质浓度。发现泡沫膜总是稳定的(平衡的)。根据溶液组成,确定了在石英上形成不稳定(破裂和亚稳)或稳定(平衡)湿膜的情况。对于亲水和疏水石英表面,效果相似。所得结果表明泡沫膜和湿膜之间存在一定的相似性。在两种情况下,低于临界电解质浓度时静电力起作用,高于临界电解质浓度时空间位阻力决定膜的稳定性。与对称泡沫膜不同,不对称边界条件会导致湿膜具有一些特定性质。