Structure-property relationships in poly(urethane urea)s synthesized with ultra-low monol content poly(propylene glycol) soft segments were investigated as soft segment molecular weight (2000, 4000, and 8000 g/mol) and hard segment content (6.3 and 9.0 wt %) were varied. Morphological features such as interdomain spacing and interphase thickness were quantified and revealed with small-angle X-ray scattering (SAXS) and atomic force microscopy (AFM). The thermal and mechanical behavior was assessed with a dynamic mechanical analyzer (DMA) and by differential scanning calorimetry (DSC) and stress-strain tests. Hard segment content, over the limited range studied, had little effect on the morphology and soft segment thermal and mechanical properties. The molecular weight of the soft segments had considerably more influence on the morphology and mechanical properties. Increasing soft segment molecular weight resulted in greater interdomain spacings, as shown by SAXS, and a noticeable change in the structure, as shown by AFM. Additionally, as soft segment molecular weight decreased the soft segment glass transition broadened and rose to higher temperatures.
Recent advances in the catalyst technology associated with the production of poly(propylene glycol) (PPG) have allowed for the fabrication of ultralow monol content PPG macrodiols (Acclaim™ polyols), which are highly bifunctional and can be produced in substantially higher molecular weights and with narrower molecular weight distributions than previously possible. These factors have enabled the preparation of higher value elastomers and may allow for the first manufacture of economically attractive PPG-based poly(urethane-urea) (PUU) fibers. In the past, many performance polyurethane and PUU elastomers used poly(tetramethylene ether glycol) (PTMEG) for the soft segments either alone or in combination with other macrodiols. The work presented here details the investigation of the morphological features of PUU systems with mixed soft segments of PPG, PTMEG, and a low molecular analog of PPG, tri(propylene glycol) (TPG) in an effort to ascertain the influence of structural features on the mechanical and thermal properties of the elastomers. Also of interest was whether the incorporation of PPG and TPG would either prohibit or greatly hinder the formation of strain-induced PTMEG crystallites. It was found that, even when only 60 wt % of the soft segments consisted of PTMEG, those soft segments were still able to undergo recognizable straininduced crystallization as detected by wide-angle X-ray scattering. It was also seen that, as the ratio of PPG to PTMEG was varied, there were systematic changes in the soft segment glass transition and cold crystallization characteristics. Inclusion of PPG and TPG resulted in PTMEG's diminished ability to undergo cold and strain-induced crystallization, as seen with differential scanning calorimetry and wide-angle X-ray scattering.
Much effort has been put into improving the temporal stability of electric field-induced chromophore alignment in molecularly doped or functionalized polymers for second order nonlinear optical device applications. Characterization of the alignment decay in electric field-poled films is complicated by charge injection during poling. In order to optimize poling schemes and to accurately determine the orientational mobility of the chromophores it is necessary to develop methods to measure the spatial extent and time-dependence of any residual fields in the polymer films. Such Measurements will also be important for the development of polymer-based electro-optic devices, and in fact for any guided wave application in these materials since the residual field may induce a spatial dependence in the refractive index.
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