Dielectric thermal analysis transition temperatures

The relaxation methods employed are Dynamic Mechanical Thermal Analysis (DMTA) and Dielectric Thermal Analysis (DETA). Generally in both cases a single excitation frequency is used and the temperature is varied, typically over a range between — 100 °C and +200 °C. Changes in molecular motion, and hence 7, are detected by both techniques, but in the case of DETA the process has to involve movement of dipoles or fully developed electrical charges on the polymer in order to be detected. Thus the two techniques can be used to complement each other, since transitions can be detected on DMTA and assigned as due to dipoles according to whether or not they also occur with DETA. 

The dielectric thermal analysis technique normally obtains data from thermal scans at constant impressed frequency. The glass transition temperature at which molecular motions become faster than the impressed timescale are recorded as peaks in e" and tan 8. 

Differential scanning calorimetry, thermomechanical analysis, dynamic mechanical analysis, differential thermal analysis, dielectric thermal analysis, infrared and NMR spectroscopy, are some of the instrumental techniques that have been applied to the determination of glass transition and other transition temperatures in polymers (Chapter 13). 

The glass transition temperatures ofthe polyimides are 195-250 °C their 10% weight loss temperamres (dynamic thermogravimetric analysis, air, AT = 4.5 °C/min) are 390-422 °C. Of particular interest are the dielectric constants of these polyimides. At a relative humidity of 50% these constants are 2.70-2.90 and are comparable with constants of the best fluorinated polyimides [21, 50-55]. The lowest dielectric constant (2.70) was observed for polyimide based on 6F dianhydride, containing the highest amount of fluorine. Thermal treatment of this polymer film at 280-290 °C for 1 hour led to a decrease (2.45) of dielectric constant due to the possible formation of nanofoams [56]. 

Most of the physical properties of the polymer (heat capacity, expansion coefficient, storage modulus, gas permeability, refractive index, etc.) undergo a discontinuous variation at the glass transition. The most frequently used methods to determine Tg are differential scanning calorimetry (DSC), thermomechanical analysis (TMA), and dynamic mechanical thermal analysis (DMTA). But several other techniques may be also employed, such as the measurement of the complex dielectric permittivity as a function of temperature. The shape of variation of corresponding properties is shown in Fig. 4.1. 

Changes in physical state may be observed from changes in thermodynamic quantities, which can be measured by calorimetric techniques, dilatometry, and thermal analysis. Spectroscopic methods are also available for the determination of changes in molecular mobility around transition temperatures. In addition to the changes in thermodynamic quantities and molecular mobility, a glass transition has significant effects on mechanical and dielectric properties. 

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. 

Pentyl-4 -cyanobiphenyl and 4-octyl-4 -cyanobiphenyl liquid crystals (LCs) confined in molecular sieves of MCM-41 and cloverite types are studied in a wide temperature range by dielectric spectroscopy, thermal analysis and in-situ FTIR spectroscopy. The phase transitions of the bulk LCs cannot be detected when confined in MCM-41 sieve. A relaxational process occurs due to the molecular motions in the layer at the pore walls the temperature dependence of the characteristic frequency obeys a Vogel-Fulcher-Tamman law associated to a glassy state. In the cloverite cages, the LCs keep the phase transitions of the bulk but shifted. Interactions between Lewis and Brdnsted sites and the LC molecules are monitored by IR spectroscopy. DTA measurements put also in evidence strong guest-host interactions. 

Glass transition Oynamic-mechanical analysis, temperature dependence of the dielectric constant, viscosity, index of refraction and other properties, differential thermal analysis, dilatometry... 

The numerical value of the glass-transition temperature depends on the rate of measurement (see Section 10.1.2). The techniques are therefore subdivided into static and dynamic measurements. The static methods include determinations of heat capacities (including differential thermal analysis), volume change, and, as a consequence of the Lorentz-Lorenz volume-refractive index relationship, the change in refractive index as a function of temperature. Dynamic methods are represented by techniques such as broad-line nuclear magnetic resonance, mechanical loss, and dielectric-loss measurements. Static and dynamic glass transition temperatures can be interconverted. The probability p of segmental mobility increases as the free volume fraction / Lp increases (see also Section 5.5.1). For /wlf = of necessity, p = 0. For / Lp oo, it follows that p = 1. The functionality is consequently... 

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