Glass transition temperature dielectric spectroscopy

At low temperature the material is in the glassy state and only small ampU-tude motions hke vibrations, short range rotations or secondary relaxations are possible. Below the glass transition temperature Tg the secondary /J-re-laxation as observed by dielectric spectroscopy and the methyl group rotations maybe observed. In addition, at high frequencies the vibrational dynamics, in particular the so called Boson peak, characterizes the dynamic behaviour of amorphous polyisoprene. The secondary relaxations cause the first small step in the dynamic modulus of such a polymer system. 

Abbreviations DEA, dielectric analysis >OC. degree of crystallinity DSC, di erential scanning calorimetry LM, local mobility (secondary relaxations) SR, structural relaxation 7g, determination of glass transition temperature TSDC. thermally stimulated depolarization current spectroscopy XRD, X-ray difTractometry. Source Adapted from Ref. 15. 

Does a shift of the glass transition temperature reflect a change in the relaxation time distribution or in its mean value only This makes a fundamental difference underlining the power of microscopic techniques like Broadband Dielectric Spectroscopy. 

Photophysical and photochemical processes in polymer solids are extremely important in that they relate directly to the functions of photoresists and other molecular functional devices. These processes are influenced significantly by the molecular structure of the polymer matrix and its motion. As already discussed in Section 2.1.3, the reactivity of functional groups in polymer solids changes markedly at the glass transition temperature (Tg) of the matrix. Their reactivity is also affected by the / transition temperature, Tp, which corresponds to the relaxation of local motion modes of the main chain and by Ty, the temperature corresponding to the onset of side chain rotation. These transition temperatures can be detected also by other experimental techniques, such as dynamic viscoelasticity measurements, dielectric dispersion, and NMR spectroscopy. The values obtained depend on the frequency of the measurement. Since photochemical and photophysical parameters are measures of the motion of a polymer chain, they provide means to estimate experimentally the values of Tp and Tr. In homogeneous solids, reactions are related to the free volume distribution. This important theoretical parameter can be discussed on the basis of photophysical processes. 

In the majority of cases the compatibility of the polymers is characterized by the glass-transition temperature Tg, determined by methods such as dilatometry, differential scanning calorimetry (DSC), reversed-phase gas chromatography (RGC), radiation thermal luminescence (RTL), dynamic mechanical spectroscopy (DMS), nuclear magnetic resonance (NMR), or dielectric loss. The existence of two... 

Similar to polyethylenes the morphology of these polymers is also described as a lamellar stack of crystalline and non-crystalline layers. This so-called two phase model is applied for the interpretation of X-ray diffraction data as well as for heat of fusion or density measurements. However, it is well known that several mechanical properties, as well as the relaxation strength at the glass transition temperature, cannot be described by such a simplistic two-phase approach, as discussed by Gupta [59]. Prom standard DSC measurements [60], dielectric spectroscopy, shear spectroscopy [61], NMR [62], and other techniques probing molecular dynamics at the glass transition (a-relaxation) temperature, the measured relaxation strength is always smaller than expected... 

Figure 9 Correlation of the segmental relaxation time ts measured in dilute solution and the glass transition temperature of the dense system. The data were taken from Adachi, K. Dielectric Spectroscopy of Polymeric Materials, American Chemical Society Washington, DC, p 261 and represent different chain structures. The line is a linear regression to the data.

Effect of nano particles of Al Oj on conventional SPE films have been examined by FTIR, DSC and B-G spectroscopy. The dispersal of Al O nano particles to the SPEs shows dechnation in the glass transition and melting temperature as established from DSC analysis. The FUR spectra show possible interactions between Al O nano particles and host SPE films. The optimum room temperature ionic conductivity of the order of 7 x 10 S/cm having minimum activation energy (E 0.22eV) is observed for NCPE films. This shows one order increment in the conductivity over the conventional SPE films. The temperature dependent conductivity shows Arrhenius type thermally activated behavior before as well as after glass transition temperature. Maximum value of ion transference number is found to be 0.96 which is indicative of predominant ionic (protonic) transport in the SPE and NCPE thin films. It has been observed that dielectric constant for SPE and NCPEs increases with temperature while it decreases with frequency. 

---