Vapor-phase infiltration (VPI) infuses polymers with metalorganics to create organic−inorganic hybrid materials with properties distinct from the parent polymer. While many studies exist demonstrating the utility of VPI, few studies investigate the stability of the chemical structure and properties of the hybrid material under longterm use conditions. Herein, the durability to simulated washing of AlO x -poly(ethylene terephthalate) hybrid fabrics prepared via VPI with trimethylaluminum (TMA) and water vapor at temperatures 60, 80, 100, 120, and 140 °C under excess TMA infiltration conditions is investigated. The inorganic loading of the fabrics varies with VPI process temperature, with fabrics prepared below 100 °C containing ∼25 wt % inorganic and fabrics prepared above 100 °C having ∼17 wt % inorganic as measured by thermogravimetric analysis. Consistent with literature reports, AlO x -PET fabrics exhibit changes in color and photoluminescence that vary with the infiltration temperature. Fabrics infiltrated at lower temperatures (100 °C and below) with high inorganic loading lose a significant quantity of inorganic following washing. This loss is attributed to the formation of highly brittle, oxide-rich hybrid layers near the fibers' surfaces that delaminate and are removed during the washing process. Decreasing the inorganic loading of fabrics at these low infiltration temperatures (by controlling the relative precursor/fabric quantity) improves the wash durability of these hybrid fabrics. At higher infiltration temperatures, a negligible amount of inorganic is lost. In addition to these physical changes, differences in the photoluminescence and chemical structure, indicated by infrared spectroscopy, are observed for all fabrics and provide insights into their chemical structure and degradation pathways.

In this work, the vapor-phase infiltration (VPI) of polyethylene terephthalate (PET) fabrics with trimethylaluminum (TMA) and coreaction with water vapor is explored as a function of limiting TMA reagent conditions versus excess TMA reagent conditions at two infiltration temperatures. TMA is found to sorb rapidly into PET fibers, with a significant pressure drop occurring within seconds of TMA exposure. When large quantities of polymer are placed within the chamber, minimal residual precursor remains at the end of the pressure drop. This rapid and complete sorption facilitates the control of inorganic loading by purposely delivering a limited quantity of the TMA reagent. The inorganic loading for this system scales linearly with a Precursor:C=O molar ratio of up to 0.35 at 140 °C and 0.5 at 80 °C. After this point, inorganic loading is constant irrespective of the amount of additional TMA reagent supplied. The SEM analysis of pyrolyzed hybrids indicates that this is likely due to the formation of an impermeable layer to subsequent infiltration as the core of the fibers remains uninfiltrated. The Precursor:C=O molar ratio in the subsaturation regime is found to tune the hybrid fabric morphology and material properties such as the optical properties of the fabric. Overall, this work demonstrates how a reagent-limited processing route can control the inorganic loading in VPI synthesized hybrid materials in a simpler manner than trying to control kinetics-driven methods.