Nanohybrid polyurethane (PUR)/functionalized silsesquioxane (PHIPOSS) systems. Part II. X-Ray structural investigations using WAXD and SAXS methods

The structure of the nanohybrid PUR/FOSS systems containing 2, 4, 6, 8 and 10 wt. % PHIPOSS has been characterized by WAXD and SAXS methods. WAXD diffraction patterns of the hybrid elastomers were analyzed by deconvolution into diffuse scattering maxima of the hard phase or soft phase and the diffraction peak corresponding to the (101) crystallographic plane of the POSS hexagonal unit cell. The dimension D-101 of the POSS crystallites formed in PUR/PHIPOSS elastomers, was determined using the Scherrer equation. Clear differences in the values of D-101 (34-22 nm), with changes not occurring on a regular basis, were found for various PHIPOSS contents. Moreover, for all the systems investigated, it was observed that the so-called 'prepeak' of the main amorphous halo in WAXD patterns was shifted to lower diffraction angles with an increase in PHIPOSS content. This was corresponding to an increase of correlation length associated with this peak, from 0.75 nm in case of the unmodified PUR to about 1.18 nm for the elastomer containing 10 wt.% PHIPOSS. One-dimensional correlation functions K(gamma) and CF(gamma) for the lamellar supramolecular structure of the investigated systems were determined from SAXS diffraction patterns. Based on the analysis of these functions, the following parameters have been determined: the long period of the lamellar supramolecular structure, the volume fraction and average thickness of the hard and soft phases, and the changes in the scattering power for hybrid polyurethane containing 4 and 10 wt. % of PHIPOSS compared to unmodified polyurethane.It was found that after the modification of polyurethane chains with PHIPOSS molecules the long period of the lamellar supramolecular structure of the investigated elastomers was not changed, whereas the thickness of the hard layers was reduced (from 4,1 nm to 3,8-3,4 nm) and the thickness of the soft layers was simultaneously increased (from 7,0 nm to 7,4-7,8 nm). It was also observed that the scattering power for the elastomers with FOSS mass fractions of 4 and 10 % is reduced by 11 % and 22 %, respectively. This effect has been attributed to the location of PHIPOSS crystallites in the regions between the lamellar stacks in the polyurethane matrix of nanohybrid elastomers.