Fracture toughness is a key property of epoxy resins with a high glass transition temperature (T_g), used in carbon fiber/epoxy composites for aerospace applications. Conventional toughening methods rely on adding toughening agents, often compromising the processibility and thermal stability. This study introduces a simple self-toughening approach that enhances the fracture toughness without sacrificing other properties by controlling the cured epoxy network structure. Tetraglycidyl 4,4′-diaminodiphenylmethane (TGDDM) epoxy resin was cured using mixtures of structural isomeric curing agents, 3,3′- and 4,4′-diaminodiphenyl sulfone (3,3′- and 4,4′-DDS), at ratios of 7:3, 5:5, and 3:7. The optimal 7:3 ratio produced a resin with 30% higher fracture toughness compared to TGDDM/3,3′-DDS and 100% higher than the TGDDM/4,4′-DDS system. The T_g of the self-toughened resin ranged from 241 to 266 °C, which was intermediate between the T_g values of the TGDDM/3,3′-DDS and TGDDM/4,4′-DDS systems. This improvement is attributed to the higher crosslink density and reduced free volume of the epoxy network. These findings demonstrate that simply mixing isomeric curing agents enables self-toughening, providing a practical and efficient strategy to enhance the performance of high-T_g epoxy resins in advanced composite applications.

Epoxy-based composite materials, widely used in various industries such as coatings, adhesives, aerospace, electronics, and biomedical engineering, remain a topic of global interest due to their varying characteristics based on the base resin and curing agents used. This paper employs molecular dynamics simulation to examine the thermal and mechanical properties, as well as molecular behaviors, of epoxy systems cured with diglycidyl ether of bisphenol F as the base resin and aromatic amine curing agents, specifically the meta structure of 3,3′-diaminodiphenyl sulfone (3,3′-DDS) and the para structure of 4,4′-diaminodiphenyl sulfone (4,4′-DDS). The 3,3′-DDS system demonstrated a greater density and Young’s modulus than the 4,4′-DDS system. This tendency was analyzed based on differences in molecular fractional free volume and cohesive energy density (CED). The 4,4′-DDS system exhibits a higher glass transition temperature (T_g) compared to the 3,3′-DDS system, with values of 406.36 K and 431.22 K, respectively. To understand this behavior, we examined atomic-scale displacements at T_g through mean squared displacement analysis, which revealed that the onset of molecular motion occurs at a lower temperature in the 3,3′-DDS system. Molecular-level study reveals how the structural features of each curing agent appear in thermal and mechanical properties, offering important insights for epoxy system development.