全氟烷基表面活性剂吸附特性研究

doi:10.11949/0438-1157.20190868

摘要/Abstract

摘要：

针对全氟烷基季铵碘化物(Le-134)、全氟烷基磷酸酯(Le-107)和全氟烷基聚醚(Le-180)三种表面活性剂水溶液的平衡态表面张力和吸附动力特性进行了研究。临界胶束浓度的大小关系为Le-180 (15×10^-6) <Le-134 (40×10^-6) <Le-107 (150×10^-6)；饱和吸附量Г_max大小关系为 Le-107 <Le-134<Le-180。三种表面活性剂降低静态表面张力的效能接近，可将表面张力降低至20 mN/m以下。从亲疏水基、反离子的作用等方面对静态表面张力特性进行了分析。动态表面张力方面，Le-134降低表面张力的速度较快，Le-180次之，Le-107最慢。三种表面活性剂水溶液在低浓度时均属于扩散控制吸附；在高浓度时，吸附过程变化为混合动力控制吸附。研究了不同浓度下三种表面活性剂水溶液的表观扩散系数和吸附势垒的变化。结果表明吸附动力特性的变化主要原因可能是因为分子结构不同和胶束等对吸附过程产生了影响。

关键词: 表面活性剂, 静态表面张力, 动态表面张力, 吸附机理

Abstract:

Equilibrium surface tension and adsorption dynamic characteristics of perfluoroalkyl quaternary ammonium iodide (Le-134), perfluoroalkyl phosphate (Le-107) and perfluoroalkyl polyether (Le-180) were investigated. The relationship between the critical micelle concentration is Le-180 (15×10^-6) <Le-134 (40×10^-6) <Le-107 (150×10^-6); the saturation adsorption amount Γ_max is Le- 107 <Le-134 <Le-180. The effect of three kinds surfactants on reducing surface tension is similar, and the surface tension of surfactant aqueous solution can be reduced below 20 mN/m. Equilibrium surfaces tension characteristics were analyzed from the hydrophilic and hydrophobic groups and counterions. The dynamic surface tension (DST) of Le-134 drops fastest while Le-180 in second and Le-107 is the slowest. When the concentration of surfactant is relatively small, the adsorption is controlled by diffusion. Whereas the adsorption mechanism changes from diffusion controlled to barrier controlled at high concentrations. The variation of apparent diffusion coefficients (D_a) and adsorption barriers (E_a) of three aqueous surfactant solutions at different concentrations were investigated. It can be indicated that the variation of adsorption dynamics is mainly due to the difference in molecular structure and the influence of micelles on adsorption process.

Key words: surfactant, equilibrium surface tension, dynamic surface tension, adsorption mechanism

中图分类号:

TQ 423

龚志明, 王瑞祥, 邢美波. 全氟烷基表面活性剂吸附特性研究[J]. 化工学报, 2020, 71(4): 1754-1761.

Zhiming GONG, Ruixiang WANG, Meibo XING. Investigation on adsorption characteristics of perfluoroalkyl surfactants[J]. CIESC Journal, 2020, 71(4): 1754-1761.

图/表 8

表1 三种表面活性剂信息

Table 1 Information of three surfactants

名称	亲水基带电性质	分子式
全氟烷基季铵碘化物（Le-134）	阳离子	[C_nF₂_n₊₁C₂H₄]₄N⁺I^-
全氟烷基磷酸酯（Le-107）	阴离子	[C_nF₂_n₊₁C₂H₄]₃PO₄
全氟烷基聚醚（Le-180）	非离子	C_nF₂_n₊₁C₂H₄(C₂H₄O)_m

图1 白金板法测量表面张力原理示意图

Fig.1 Schematic of Wihelmy plate method measuring surface tension

图2 表面活性剂静态表面张力

Fig.2 Equilibrium surface tension of surfactants

表2 表面活性剂测试参数

Table 2 Information of three surfactants

试剂

CMC/

(mg/L)

π_CMC/

(mN/m)

pc₂₀

图3 不同浓度下表面活性剂的动态表面张力

Fig.3 Dynamic surface tension of various concentration surfactants

图4 不同浓度表面活性剂的ln(γt-γeq)-t曲线

Fig.4 ln(γt-γeq)-t curve of various concentration surfactants

图5 不同表面活性剂水溶液的表观扩散系数

Fig.5 Apparent diffusion coefficient of various surfactant solution

图6 不同表面活性剂水溶液的吸附势垒

Fig.6 Apparent absorption barrier of various surfactant solution

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