Despite the considerable advances of molecular-thermodynamic theory of micelle growth, agreement between theory and experiment has been achieved only in isolated cases. A general theory that can provide self-consistent quantitative description of the growth of wormlike micelles in mixed surfactant solutions, including the experimentally observed high peaks in viscosity and aggregation number, is still missing. As a step toward the creation of such theory, here we consider the simplest system – nonionic wormlike surfactant micelles from polyoxyethylene alkyl ethers, C_iE_j. Our goal is to construct a molecular-thermodynamic model that is in agreement with the available experimental data. For this goal, we systematized data for the micelle mean mass aggregation number, from which the micelle growth parameter was determined at various temperatures. None of the available models can give a quantitative description of these data. We constructed a new model, which is based on theoretical expressions for the interfacial-tension, headgroup-steric and chain-conformation components of micelle free energy, along with appropriate expressions for the parameters of the model, including their temperature and curvature dependencies. Special attention was paid to the surfactant chain-conformation free energy, for which a new more general formula was derived. As a result, relatively simple theoretical expressions are obtained. All parameters that enter these expressions are known, which facilitates the theoretical modeling of micelle growth for various nonionic surfactants in excellent agreement with the experiment. The constructed model can serve as a basis that can be further upgraded to obtain quantitative description of micelle growth in more complicated systems, including binary and ternary mixtures of nonionic, ionic and zwitterionic surfactants, which determines the viscosity and stability of various formulations in personal-care and house-hold detergency.

尽管胶束生长的分子热力学理论取得了长足的进步，但理论和实验之间只有在个别情况下才能达成共识。仍然缺少可提供蠕虫状胶束在混合表面活性剂溶液中的生长的自洽定量描述的通用理论，包括实验观察到的粘度和聚集数的高峰值。作为创建这种理论的步骤，我们在这里考虑最简单的系统-聚氧乙烯烷基醚C _i E _j的非离子蠕虫状表面活性剂胶束。我们的目标是构建与现有实验数据一致的分子热力学模型。为此，我们将胶束平均质量聚集数的数据系统化，从中确定胶束在不同温度下的生长参数。没有可用的模型可以对这些数据进行定量描述。我们构建了一个新模型，该模型基于胶束自由能的界面张力，头基空间和链构象成分的理论表达式，以及模型参数的适当表达式，包括它们的温度和曲率依赖性。特别注意了表面活性剂的链构象自由能，由此得出了一个新的更通用的公式。结果，获得了相对简单的理论表达式。输入这些表达式的所有参数都是已知的，这有助于对各种非离子表面活性剂的胶束生长进行理论建模，与实验极为吻合。构建的模型可以作为基础，可以进一步升级以获取更复杂系统中胶束生长的定量描述，包括非离子，离子和两性离子表面活性剂的二元和三元混合物，它决定了个人配方中各种配方的粘度和稳定性。护理和家庭清洁。