Jd. Vanheumen et Jr. Stevens, THE ROLE OF LITHIUM-SALTS IN THE CONDUCTIVITY AND PHASE MORPHOLOGY OFA THERMOPLASTIC POLYURETHANE, Macromolecules, 28(12), 1995, pp. 4268-4277
Fourier transform infrared spectroscopy (FT-IR), differential scanning
calorimetry (DSC), and impedance spectroscopy (IS) were utilized to m
onitor changes in the morphology of a thermoplastic polyurethane (TPU)
as a function of alkali-metal salt concentration. In this study, the
alkali-metal salts of LiCF3SO3 and Li(CF3SO2)(2)N were observed to inc
rease the overall bulk conductivity of a phase-segregated polyurethane
comprising soft segments of poly(tetramethylene oxide) (PTMO) and har
d segments of methylenebis(phenyl isocyanate) (MDI) and 1,4-butanediol
(BDO). Significant changes occur in the FTIR spectrum of the TPU abov
e the critical salt concentration (c(c)) of 0.5 mmol/g of TPU, suggest
ing an interaction of the lithium cation within the hard segment and b
etween the hard and soft phases. A loss in long-range ordering of the
hard domain above c(c) has also been observed by DSC. For temperatures
around the hard segment T-g (= 110 degrees C) and above, IS revealed
an increasing bulk conductivity as the salt concentration was increase
d. At lower temperatures a maximum in conductivity as a function of sa
lt concentration occurs again at c(c). The results of this study would
indicate that the characteristic phase-segregated morphology of the T
PU has been altered as a result of the interaction of lithium cations
within the polar hard domains and by the promotion of phase intermixin
g by the coupling of the hard and soft phases.