Hydrolysis susceptibility and carbamate formation for a low moisture-absorbing,siloxane-modified cyanate ester resin matrix (TC410) material used for composite space applications

Siloxane-modified cyanate ester resins are ideal matrix materials for next-generation, high-precision composites used for radomes and satellite structures. They provide extremely low moisture uptake, excellent microcracking resistance, and protection from atomic radiation. However, cyanate ester resins have been shown to be susceptible to hydrolysis during cure, which may significantly impact both mechanical and thermal performance. In this investigation, we evaluate the cure kinetics and hydrolysis susceptibility of a siloxane-modified prepreg system (TC410/M55J). DSC tests verified that the E_a of polymerization for the TC410 system is 65 KJ/mol. Samples were also exposed to moisture during cure at several temperatures, and FTIR was used to follow changes in the carbonyl peak absorption intensity to compare the rate kinetics and activation energy for hydrolysis leading to carbamate formation (52 KJ/mol). DMA tests of composites exhibited significantly reduced Tg’s with increasing moisture levels during cure. TGA of these cured samples exhibited both a significant decrease in the onset of the thermal decomposition temperature as well as an increase in the relative degree of volatiles generated at low temperature. Flatwise tension strength tests showed a linear reduction in strength with decreasing Tg, at an equivalent trend to previous work on an M55J/RS3C system indicating a similar mechanism. However, the added margin provided from the higher initial FWT strength in the TC410 system allows for larger decreases in Tg before significant degradation occurs. Laminates manufactured on composite mandrels resulted in parts with larger decreases in the tool-side Tg of the part when compared to the bag-side Tg, with the differential depending on the initial moisture content of the tool. AFM was shown to selectively identify these carbamate-affected regions by showing that the recession behavior of these less cross-linked areas was greater than in areas where the resin was properly cured. Composites with increased carbamate formation resulted in increasing warpage of the part with elevated temperature exposure due to variations in stress relaxation. This effect should be considered when manufacturing precision, high-dimensional stability composite hardware.