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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 Ea 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.

Replicated composite optics is a promising technique to fabricate high-quality mirrors with reduced weight and processing time compared to conventional glass mirrors; however, the optical layer is organic and susceptible to environmentally-induced dimensional changes, specifically to moisture exposures. Generally, to enhance polymer stability, thermal curing is necessary to maximize the cure state. Because replications are bonded, thermal exposures generate residual stresses that degrade optical quality. In this paper, the cure state of a UV-cured epoxy with RT processing was varied by changing the photoinitiator (PI) concentration, and the replication stability was evaluated in different humidity environments by laser interferometry. Increasing the PI concentration transformed the epoxy microstructure from homogenous to a more phasic network, as evidenced by both DMA and AFM, resulting in significant changes to the Tg, modulus, and moisture absorption. When replications were exposed to moisture, they experienced initial swelling followed by stress relaxation to net-zero regardless of initial processing stress. Reduced PI concentrations exhibited higher moduli and shorter swelling periods, with dimensional changes as small as 35 nm and complete stress relaxation in days. TTS master curves describing stress relaxation behavior correlated well with the observed behavior in replicated mirror samples. Furthermore, it was shown that the relieved stress persisted through multiple humidity cycles between 100% to 0% RH. These results show that high-humidity conditioning treatments can be utilized to eliminate residual stress in as-fabricated replicated mirrors over just a few days, providing a viable manufacturing and processing route for highly precise and stable replicated composite mirrors.

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space Materials laboratory, The aerospace corporation, el segundo, ca, usa ABSTRACT Carbon fiber-reinforced composite replicated mirrors offer weight savings, higher stiffness, tailorable CTEs, higher thermal conductivities, and excellent damage tolerant mechanical properties in comparison to traditionally processed glass mirrors. These mirrors can also be rapidly manufactured by replicating the surface of a high-precision glass mandrel multiple times. The mold release coating used is critical and must be on the molecular scale, uniform, and exhibit low adhesion in order to produce high-fidelity replication. This study investigates the use of a self-assembled monolayer (SAM) as the mold release agent for the manufacture of replicated mirrors. We have synthesized and tested perfluoropolyether (PFPE) coatings formed on glass substrate via self-assembly. Ellipsometry, X-ray photoelectron spectroscopy, and atomic force microscopy were used to characterize the morphology, thickness uniformity and the chemical profile of the coatings. The release force necessary to remove the replicated surfaces from the mandrel is critical and was directly related to the surface distortion of the replica. The release force increased with each successive replication due to pinholes and defects. Incorporating a secondary, lower molecular weight SAM reagent significantly reduced both surface agglomeration and transfer of SAM material to the replicated resin surface. A 60% reduction in the replica release force and a 50% improvement in the replica surface figure were achieved due to reductions in the defect density of the SAM coating.

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