Ghavidel Nasim, Fatehi Pedram
Green Processes Research Centre and Chemical Engineering Department, Lakehead University, 955 Oliver Road, Thunder Bay, Ontario P7B5E1, Canada.
Langmuir. 2021 Mar 23;37(11):3346-3358. doi: 10.1021/acs.langmuir.0c03458. Epub 2021 Mar 5.
It is hypothesized that polymeric lignin surfactants have different affinities for stabilizing oil-water emulsions and that the emulsifying performance of these surfactants is highly affected by their adsorption performance at the oil-water interface. To validate this hypothesis, the adsorption performance of sulfethylated lignin (SEKL) surfactant at different oil-water interfaces was examined by assessing the contact angle, dynamic interfacial tension, and surface loading (Γ). Moreover, the interfacial adsorption kinetics of SEKL was comprehensively assessed in different oil-water systems to reveal the mechanisms of the SEKL adsorption at the interface. Also, the impacts of SEKL concentration and ionic strength on the performance of SEKL as an effective emulsifier for the emulsions were assessed. Furthermore, the droplet size and instability index of the emulsions were systematically correlated with the adsorption performance of SEKL at the interface of oil and water. For the first time, by implementing a modified Ward Toradai diffusion model, two distinct early stages of the adsorption of SEKL at the oil interface were identified. Interestingly, the second stage was the determining stage of adsorption with the diffusion-controlled mechanism when polymers reconfigured at the oil-water interface. Salt screening facilitated the clustering of SEKL upon charge repulsion elimination, which removed the energy barrier in the first stage of adsorption (Δ = 0), but it introduced a steric barrier upon the reconfiguration of polymers at the oil interfaces in the second stage of adsorption. In addition to the kinetics of adsorption, satisfactory correlations were observed between surface pressure (Δγ = γ - γ), surface loading (Γ) of polymers, and contact angle at oil interfaces on one hand and the oil droplet size and emulsion stability on the other hand.
据推测,聚合木质素表面活性剂在稳定油水乳液方面具有不同的亲和力,并且这些表面活性剂的乳化性能受其在油水界面的吸附性能影响很大。为了验证这一假设,通过评估接触角、动态界面张力和表面负荷(Γ),研究了磺乙基化木质素(SEKL)表面活性剂在不同油水界面的吸附性能。此外,还在不同的油水体系中全面评估了SEKL的界面吸附动力学,以揭示SEKL在界面处的吸附机制。同时,评估了SEKL浓度和离子强度对其作为乳液有效乳化剂性能的影响。此外,还系统地研究了乳液的液滴尺寸和不稳定指数与SEKL在油水界面吸附性能之间的关系。首次通过实施改进的沃德-托拉代扩散模型,确定了SEKL在油界面吸附的两个不同早期阶段。有趣的是,第二阶段是聚合物在油水界面重新构型时受扩散控制机制影响的吸附决定阶段。盐筛选通过消除电荷排斥促进了SEKL的聚集,这消除了吸附第一阶段的能量屏障(Δ = 0),但在吸附第二阶段聚合物在油界面重新构型时引入了空间位垒。除了吸附动力学外,一方面表面压力(Δγ = γ - γ)、聚合物的表面负荷(Γ)和油界面的接触角与另一方面油滴尺寸和乳液稳定性之间也存在令人满意的相关性。