Since the first publications of large amplitude oscillatory shear (LAOS) responses of polymeric materials in the 1960s, different approaches have been developed to express, analyze, and interpret nonlinear viscoelastic behavior of materials. LAOS is currently recognized as one of the most powerful rheological techniques to characterize nonlinear viscoelasticity, as the amplitude and frequency of the employed deformation can be controlled, allowing researchers to tune the strength of flow and time scale independently. Additionally, in contrast to small amplitude oscillatory shear (SAOS) flow, LAOS is not limited to a perturbation about equilibrium. Such flexibility makes LAOS an attractive rheological protocol to mimic numerous industrial applications. Recently, there has been significant progress in the LAOS characterization of polymeric materials via different analysis techniques, including Fourier transform rheology, stress decomposition, Chebyshev coefficients, sequence of physical processes, and intrinsic nonlinearity. These advances have been achieved through utilization of modern commercial rheometers with high torque resolution and strong computational power, making the exploitation of these techniques possible in the recent decade. This increased accessibility has seen the number of LAOS publications dramatically increase in the past few years. The current surge in interest in the use of LAOS tests necessitates the search for appropriate measurement techniques to probe the nonlinear response of complex fluids. Although this area has been significantly investigated by many researchers who measured and reported LAOS data from a wide range of rheologically-complex materials, there is still one question that needs to be answered: which method of LAOS analysis is best for a specific polymeric system? In fact, the high volume of publications in the past decade provides us a unique opportunity for such a query to validate the efforts on the LAOS developments and compare the utility and sensitivity of these protocols. In this review, we highlight the history and fundamentals of each technique in chronological order. We present parameters and equations of each method that are indispensable for LAOS interpretation. We also present experimental work in LAOS characterization of polymeric materials, classified into four categories: (1) polymer solutions and melts, (2) polymer nanocomposites, (3) polymer blends, and (4) hydrogels. Indeed, the raison d’être of this review paper is that the nonlinear rheological properties of the mentioned polymeric systems are very sensitive to their microstructural features. In each section, the challenges and perspectives will be discussed to enhance understanding of the performance level of each method. This review offers inspiration for the interpretation of LAOS data to help rheologists and newcomers, and to contribute to current and future developments in the field.

自 1960 年代首次发表聚合物材料的大振幅振荡剪切 (LAOS) 响应以来，已经开发了不同的方法来表达、分析和解释材料的非线性粘弹性行为。LAOS 目前被认为是表征非线性粘弹性的最强大的流变技术之一，因为可以控制所采用变形的幅度和频率，从而使研究人员能够独立地调整流动强度和时间尺度。此外，与小振幅振荡剪切 (SAOS) 流相比，LAOS 不限于对平衡的扰动。这种灵活性使 LAOS 成为模拟众多工业应用的有吸引力的流变协议。最近，通过不同的分析技术，包括傅里叶变换流变学、应力分解、切比雪夫系数、物理过程序列和内在非线性，在聚合物材料的 LAOS 表征方面取得了重大进展。这些进步是通过使用具有高扭矩分辨率和强大计算能力的现代商用流变仪实现的，使得这些技术的开发在最近十年成为可能。这种增加的可访问性使 LAOS 出版物的数量在过去几年中急剧增加。当前对使用 LAOS 测试的兴趣激增，需要寻找合适的测量技术来探测复杂流体的非线性响应。尽管许多研究人员对这一领域进行了深入研究，他们测量并报告了来自各种流变复杂材料的 LAOS 数据，但仍有一个问题需要回答：哪种 LAOS 分析方法最适合特定的聚合物体系？事实上，过去十年的大量出版物为我们提供了一个独特的机会来进行这样的查询，以验证 LAOS 开发方面的努力并比较这些协议的实用性和敏感性。在这篇评论中，我们按时间顺序重点介绍了每种技术的历史和基础。我们提出了对 LAOS 解释必不可少的每种方法的参数和方程。我们还介绍了聚合物材料 LAOS 表征的实验工作，分为四类：（1）聚合物溶液和熔体，(2) 聚合物纳米复合材料，(3) 聚合物共混物，和 (4) 水凝胶。的确，这篇评论论文存在的理由是，上述聚合物系统的非线性流变特性对其微观结构特征非常敏感。在每个部分中，将讨论挑战和观点，以加深对每种方法的性能水平的理解。这篇综述为解释 LAOS 数据提供了灵感，以帮助流变学家和新手，并为该领域当前和未来的发展做出贡献。