Temperature and exposure dependence of hybrid organic-inorganic layer formation by sequential vapor infiltration into polymer fibers.

The characteristic processing behavior for growth of a conformal nanoscale hybrid organic-inorganic modification to polyamide 6 (PA6) by sequential vapor infiltration (SVI) is demonstrated. The SVI process is a materials growth technique by which exposure of organometallic vapors to a polymeric material promotes the formation of a hybrid organic-inorganic modification at the near surface region of the polymer. This work investigates the SVI exposure temperature and cycling times of sequential exposures of trimethylaluminum (TMA) on PA6 fiber mats. The result of TMA exposure is the preferential subsurface organic-inorganic growth by diffusion into the polymer and reaction with the carbonyl in PA6. Mass gain, infrared spectroscopy, and transmission electron microscopy analysis indicate enhanced materials growth and uniformity at lower processing temperatures. The inverse relationship between mass gain and exposure temperature is explained by the formation of a hybrid layer that prevents the diffusion of TMA into the polymer to react with the PA6 upon subsequent exposure cycles. As few as 10 SVI exposure cycles are observed to saturate the growth, yielding a modified thickness of ∼75 nm and mass increase of ∼14 wt %. Removal of the inherent PA6 moisture content reduces the mass gain by ∼4 wt % at low temperature exposures. The ability to understand the characteristic growth process is critical for the development of the hybrid materials fabrication and modification techniques.