Polymers

Fiber-reinforced polymer (FRP) composites are increasingly used in civil, marine, offshore, and energy infrastructure, where components routinely experience temperatures above ambient conditions. While the design of these components is largely driven by fiber-dominated characteristics, the deterioration of shear properties can lead to premature weakening and even failure. Thus, the performance and reliability of these systems depend intrinsically on the response of interlaminar shear characteristics, in-plane shear characteristics, and flexure-based shear characteristics to thermal loads ranging from uniform and monotonically increasing to cyclic and spike exposures. This paper presents a critical review of current knowledge of shear response in the presence of thermal exposure, with emphasis on temperature regimes that are below T_g in the vicinity of T_g and approaching T_d. Results show that thermal exposures cause matrix softening and microcracking, interphase degradation, and thermally induced residual stress redistribution that significantly reduces shear-based performance. Cyclic and short-duration spike/flash exposures result in accelerated damage through thermal fatigue; steep thermal gradients, including through the thickness; and localized interfacial failure loading to the onset of delamination or interlayer separation. Aspects such as layup/ply orientation, fiber volume fraction, degree of cure, and the availability and permeation of oxygen through the thickness can have significant effects. The review identifies key contradictions and ambiguities, pinpoints and prioritizes areas of critically needed research, and emphasizes the need for the development of true mechanistic models capable of predicting changes in shear performance characteristics over a range of thermal loading regimes.

In this work, rigid polyurethane materials were synthesized via a one-step polymerization method using isocyanate (MDI) and polyether polyol (4110S) as the main raw materials, with 1, 4-butanediol (BDO), 1, 6-hexanediol (HDO), diethylene glycol (DEG), and dipropylene glycol (DPG) as chain extenders. The influence of chain extender structure on the mechanical properties of rigid polyurethane was systematically investigated. The results indicate that when BDO was employed as a chain extender, the polyurethane exhibited the most uniform pore size distribution and the best mechanical properties. It was found that hydrogen bonding plays a dual role: on the one hand, it promotes microphase separation between soft and hard segments; on the other hand, it extends the molecular chains’ length, which hinders segment separation and consequently constrains its mechanical properties. Further analysis reveals that the influence of molecular chain length on mechanical properties outweighs that of polarity.

Phenyl-silicone rubber is the elastomer of choice for cryogenic and high-temperature static seals, yet quantitative links between thermo-oxidative aging and sealing reliability are still lacking. Here, sub-ambient (−70 °C to 25 °C) and room-temperature mechanical tests, compression set aging, SEM, FT-IR, and finite-element simulations are integrated to trace how aging translates into contact-pressure decay of an Omega-profile gasket. Compression set rises monotonically with time and temperature; an Arrhenius model derived from 80 to 140 °C data predicts 34 d (10% set) and 286 d (45% set) of storage life at 25 °C. SEM reveals a progressive shift from ductile dimple fracture to brittle, honeycomb porosity, while FT-IR confirms limited surface oxidation without bulk chain scission. Finite element analyses show that contact pressure always peaks at the two lateral necks; short-term aging increases in the shear modulus C₁₀ from 1.87 to 2.27 MPa, raising CPRESS by 8~21%, yet this benefit is ultimately offset by displacement loss from compression set (8.0 mm to 6.1 mm), yielding a net pressure reduction of 0.006 MPa. Critically, even under the most severe coupled condition (56 days aging with compression set), the predicted CPRESS remains above the 0.1 MPa leak-tightness criterion across the entire cryogenic service envelope. This framework provides deterministic boundaries for temperature, aging duration, and allowable preload relaxation, enabling risk-informed maintenance and replacement scheduling for safety-critical phenyl-silicone seals.