Isobaric heating of polystyrene and evaluation of the Narayanaswamy parameter x from volume recovery data

Structure parameter x, defining the relative contributions of temperature and structure to the relaxation times, which is applied in Tool-Narayanaswamy-Moynihan (TNM) equation, was evaluated from volume heating isobars for polystyrene (PS) applying the peak shift method. The peak shifted with changing structural state of PS prior heating, which was reached by different period of aging time at 89 °C < T_g up to 2544 h. In this novelized procedure for volume data, originally tested only for enthalpic measurements, high sensitivity of peak temperature (position of inflection point of the heating isobar) was shown, together with high linearity of data. This allows to directly and sensitively calculate the shift and consequently structure parameter x. The value found in the research, x = 0.40 ± 0.02, is in good agreement with published results obtained by the peak-shift method from enthalpy data of PS.     

The relation between relaxed enthalpy and volume during physical aging of amorphous polymers and selenium

This paper reports physical aging results for PMMA, PMMA/PEO blends, PS, PC, PVC and PET (semicrystalline). Also included in this study is amorphous selenium. Temperature down-jumps from equilibrium above T_g to a temperature below T_g were carried out. Relaxed enthalpy, Δh and volume contraction, Δv, were measured. From the aging records, the constant ratio Δh/Δv = K_a was evaluated. For the polymeric samples K_a values of about 2 GPa were observed, thus similar to the inverse value of the isothermal compressibility close to T_g. Similarly for Se the K_a value obtained from Δh and Δv was in fair agreement with its isothermal compressibility.     

Volume and enthalpy relaxation in a-PMMA after temperature up-jumps

the volume and enthalpy relaxation in a-PMMA subjected to temperature jumps in t_g region has been analysed. The measured H and V data were compared with respect to aging time and proportionality between them as a slope of (∂H/∂V)_T dependencies has been found. According to previous works the slope was identified as an apparent bulk modulus, K _a. This method is applied to aging following temperature up-jumps after consolidation periods of varying lengths. the main finding is a marked increase of K _a with consolidation time, approaching a limiting value in an asymptotic fashion. This revised version was published online in July 2006 with corrections to the Cover Date.     

Volume and enthalpy relaxation response after combined temperature history in polycarbonate

Summary Volume and enthalpy relaxation in polycarbonate subjected to double temperature jumps in the T_g region has been analysed. It concerns both initial T_down-jump from equilibrium above T_g to consolidation temperature below T_g and fina1 T_up-jump to relaxation temperature, also below T_g. The measured H and V data after T_up-jump were compared with respect to aging time calculating (dH/dV) ratio denoted as aging bulk modulus, K_a. According this new methodology H and V relaxation response after T_up-jump demonstrates differences in relaxation responses.     

Multifunctional flexible and stretchable polyurethane/carbon nanotube strain sensor for human breath monitoring

Flexible and stretchable polyurethane/carbon nanotube composite with strain detection ability was used for human breath monitoring. The composite material consisted of a network of multiwalled carbon nanotubes and thermoplastic high elastic polyurethane. It was found that elongation of the composite led to a macroscopic increase in electrical resistance, which can be used as a principle for applied strain detection. This detection was reversible, durable, and sensitive with gauge factor reaching very promising value, as, for example, ~46 at applied deformation of 8.7%. Further, the composite could be elongated to very large extend of deformation without discontinuity in measured resistance change reaching gauge factor ~ 450 at composite mechanical break at ~300% of strain. Sensor durability was also confirmed by sine wave deformation cycling when any decrease in the sensor properties for more than 10³ cycles was observed. Simultaneously, the prepared composite possessed other utility properties also and was considered as multifunctional when it was tested as an organic solvent vapor sensor, an element for Joule heating and finally as a microstrip antenna.     

Rigid amorphous fraction in poly(ethylene terephthalate) determined by dilatometry

Volumetric thermal analysis of semicrystalline poly(ethylene terephthalate), PET, with different content of crystalline phase was carried out using mercury-in-glass dilatometry. The effect of crystals on the thermal properties of amorphous phase (glass transition temperature, T _g, thermal expansion coefficients, α) were determined. At cold-crystallization (106°C, up to 4 h), crystalline content of 2.4–25.3 vol.% was achieved. Increasing content of crystalline phase broadens the glass transition region and increases T _g. The change of thermal expansion coefficient during glass transition is lower than that predicted by the two-phase model, which indicates the presence of a third fraction — rigid amorphous fraction (RAF), whose content steadily increases during crystallization. However, its relative portion (specific RAF) is significantly reduced. Further significant decrease in specific RAF appears after annealing at a higher temperature.     

Crystallization kinetics of polypropylene/ethylene–octene copolymer blends

Blends of polypropylene and ethylene–octene copolymers (EOC) were investigated by transmission electron microscopy, optical microscopy and differential scanning calorimetry (DSC). The main focus was on phase morphology and crystallization for blends containing EOC with different octene content (28, 37 and 52 wt.%). Also, for a given octene content (37 wt.%), the effect of molecular weight (115, 180, 229k) of EOC on morphology was observed. The largest particles were found in the blend with EOC-28 and the smallest with EOC-52. This blend with the smallest particles exhibits the fastest crystallization kinetics by two independent methods, optical microscopy and DSC. This behavior was explained by a model. Crystallizing polypropylene lamellae have to travel a longer distance going around large particles, which slows down overall crystallization growth rate. In the case of smaller particles, the obstacles are smaller and the crystallization is faster.     

Evaluation of the structure (or nonlinearity) parameter x by peak-shift method from volumetric heating data of PET

The structure parameter x, defining the temperature and structure relative contribution to the relaxation times, was evaluated applying the peak-shift method (PSM) onto volumetric heating data of poly(ethylene terephthalate) (PET) with content of crystallinity 2.6 wt%. The method of mercury-in-glass (MIG) dilatometry and three-step thermal cycle procedure were used. Two sets of heating scans were measured as a function of the amount of volume isothermal relaxation for two different relaxation temperatures below T_g (60 and 52 °C), whereas other experimental variables were kept constant. The experimentally determined heating isobar inflection temperature is a linear function of the amount of volume relaxation, which satisfies the application of PSM method for structure parameter x determination from volumetric heating data. The value of structure parameter of the used PET is independent of relaxation temperature and equal to 0.50±0.02. Finally, the shift of heating isobar inflection temperature with relaxation temperature (60, 56, 52 and 48 °C) measured for constant amount of volume isothermal relaxation was found to be linear, with the slope of 0.13.