Recently, the application of polymer-based composites at cryogenic conditions has become a hot topic, especially in aerospace fields. At cryogenic temperature, the polymer becomes more brittle, and the adverse effect of thermal stress induced by temperature is more remarkable. In this paper, the research development of thermoset and thermoplastic polymers for cryogenic applications are all reviewed. This review considers the literature concerning: (a) the cryogenic performance of modified thermoset polymers and the improving mechanisms of the reported modification methods; (b) the cryogenic application potential of some commercial thermoplastic polymers and the cryogenic performance of modified thermoplastic polymers; (c) the recent advance in the use of polymer for special cryogenic environment-liquid oxygen. This paper provides a comprehensive overview of the research development of the polymer for cryogenic application. Moreover, future research directions have been proposed to facilitate its practical applications in aerospace.

To select the appropriate polymer thin films for liquid oxygen composite hoses, the liquid oxygen compatibility and the cryogenic mechanical properties of four fluoropolymer films (PCTFE, ETFE, FEP and PFA) and two non-fluoropolymer films (PET and PI) before and after immersion in liquid oxygen for an extended time were investigated. The results indicated that the four fluoropolymers were compatible with liquid oxygen before and after immersion for 60 days, and the two non-fluoropolymers were not compatible with liquid oxygen. In addition, the cryogenic mechanical properties of these polymer films underwent changes with the immersion time, and the changes in the non-fluoropolymer films were more pronounced. The cryogenic mechanical properties of the two non-fluoropolymer films were always superior to those of the four fluoropolymer films during the immersion. Further analysis indicated that the fundamental reason for these changes in the cryogenic mechanical properties was the variation in the crystalline phase structure caused by the ultra-low temperature, which was not related to the strong oxidizing properties of the liquid oxygen. Analytical results can provide useful guidance on how to select the appropriate material combination to obtain a reasonable liquid oxygen composite hose structure.