Cure Kinetic Model, Heat of Reaction, and Glass Transition Temperature of AS4/3501-6 Graphite–Epoxy Prepregs

Abstract

A new isothermally-based, cure kinetic model for the carbon graphite–epoxy AS4/3501-6 prepreg is presented using an industrially supplied prepreg rather than the neat epoxy resin. A two-stage model is used: first, rate-controlled (autocatalytic); then diffusion-controlled. A Differential Scanning Calorimeter (DSC) is employed to investigate the prepreg’s cure kinetics using both isothermal and dynamic DSC scans, although only isothermal DSC scan data is used to fit the model’s parameters. A Thermogravimetric Analyzer (TGA) is used to determine the mass fraction of the epoxy resin in the prepreg. The coefficients are provided for a prepreg having 37.4% resin mass fraction; they must be re-evaluated for prepregs having significantly different resin mass fractions. The ultimate heat of reaction of the resin incorporated within the prepreg is measured as 433.7 J/g (based upon a linear baseline) or 422.7 J/g (based upon a specific-heat-corrected baseline) using dynamic DSC scans at 20°C/min. This value is 8–17% less than the reported 472–508 J/g for the neat 3501-6 epoxy also measured using dynamic DSC scans at 20°C/min. Important to manufacturing applications, dynamic DSC scans reveal that the prepreg’s ultimate heat of reaction is sensitive to scan rate. Finally, the prepreg’s carbon fiber and/or sizing appears to suppress the curing reaction and decrease the ultimate heat of reaction over that for the neat epoxy resin. The glass transition temperature Tg (°C) of partially-cured AS4/3501-6 prepregs is measured using DSC and is expressed as a function of degree of cure: Tg = 22.9 exp(2.16α) – markedly similar to 3501-6 neat resin Tg data measured earlier using a dynamic mechanical analyzer. The small specimen DSC thermal scans provide an effective means to measure the Tg of completely- or partially-cured prepregs. The Tg of the 100%-cured prepreg was experimentally determined to be 199°C, slightly higher than the 193°C reported for the 100%-cured neat epoxy resin. The AS4 fibers play little or no role in the degree-of-cure dependence of the AS4/3501-6 prepreg’s Tg. Recommended for general purpose structural applications, the AS4/3501-6 prepreg is composed of continuous, PAN-based, AS4C carbon (graphite) fibers and an amine-cured epoxy resin system. The epoxy resin, 3501-6, is a tetraglycidyl diamino diphenyl methane (TGDDM) with diaminodiphenylsulfone (DDS) catalyzed with boron trifluoride monoethylamine. 3501-6 was developed to operate in atemperature environment of up to 350°F (177°C).