Cain Department of Chemical Engineering, Louisiana State University, Baton Rouge, Louisiana 70803, United States.
Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, Delaware 19716, United States.
Langmuir. 2023 Apr 25;39(16):5917-5928. doi: 10.1021/acs.langmuir.3c00432. Epub 2023 Apr 13.
The adsorption of nonionic surfactants onto hydrophilic nanoparticles (NPs) is anticipated to increase their stability in aqueous medium. While nonionic surfactants show salinity- and temperature-dependent bulk phase behavior in water, the effects of these two solvent parameters on surfactant adsorption and self-assembly onto NPs are poorly understood. In this study, we combine adsorption isotherms, dispersion transmittance, and small-angle neutron scattering (SANS) to investigate the effects of salinity and temperature on the adsorption of pentaethylene glycol monododecyl ether (CE) surfactant on silica NPs. We find an increase in the amount of surfactant adsorbed onto the NPs with increasing temperature and salinity. Based on SANS measurements and corresponding analysis using computational reverse-engineering analysis of scattering experiments (CREASE), we show that the increase in salinity and temperature results in the aggregation of silica NPs. We further demonstrate the non-monotonic changes in viscosity for the CE-silica NP mixture with increasing temperature and salinity and correlate the observations to the aggregated state of NPs. The study provides a fundamental understanding of the configuration and phase transition of the surfactant-coated NPs and presents a strategy to manipulate the viscosity of such dispersion using temperature as a stimulus.
预计非离子表面活性剂吸附到亲水性纳米粒子(NPs)上将增加它们在水介质中的稳定性。虽然非离子表面活性剂在水中表现出盐度和温度依赖的体相行为,但这两个溶剂参数对表面活性剂吸附和自组装到 NPs 上的影响还了解甚少。在这项研究中,我们结合吸附等温线、分散透射率和小角中子散射(SANS)来研究盐度和温度对五乙二醇单十二醚(CE)表面活性剂在硅胶 NPs 上吸附的影响。我们发现随着温度和盐度的升高,吸附到 NPs 上的表面活性剂的量增加。基于 SANS 测量和使用散射实验的计算反向工程分析(CREASE)的对应分析,我们表明盐度和温度的增加导致硅胶 NPs 的聚集。我们进一步证明了 CE-硅胶 NP 混合物的粘度随温度和盐度的增加而呈非单调变化,并将观察结果与 NPs 的聚集状态相关联。该研究提供了对表面活性剂包覆 NPs 的构型和相变的基本理解,并提出了一种使用温度作为刺激来操纵此类分散体粘度的策略。