To treat data from temperature modulated differential scanning calorimetry (TMDSC) in terms of complex or reversing heat capacity
firstly one should pay attention that the response is linear and stationary because this is a prerequisite for data evaluation.
The reason for non-linear and non-stationary thermal response is discussed and its influence on complex (reversing) heat capacity
determination is shown. The criterion for linear and stationary response is proposed. This allows to choose correct experimental
conditions for any complex heat capacity measurement. In the case when these conditions can not be fulfilled because of experimental
restrictions one can estimate the influence of non-linearity and non-stationarity on measured value of complex or reversing
Temperature modulated dynamic mechanical analysis (TMDMA) was performed in the same way as temperature modulated DSC (TMDSC)
measurements. As in TMDSC TMDMA allows the investigation of reversible and non-reversible phenomena during crystallisation
of polymers. The advantage of TMDMA compared to TMDSC is the high sensitivity for small and slow changes in crystallinity,
e.g. during re-crystallisation. The combination of TMDMA and TMDSC yields new information about local processes at the surface
of polymer crystallites. It is shown that during and after isothermal crystallisation the surface of the individual crystallites
is in equilibrium with the surrounding melt.
Confinement of the glass-forming regions in the nanometer range influences the α-relaxation which is associated with the glass transition. These effects were investigated for semicrystalline poly(ethylene terephthalate) by dielectric spectroscopy and differential scanning calorimetry. The results are discussed within the concept of cooperative length, i.e. the characteristic length of the cooperative process of glass transition. Both experiments showed a dependence of the glass transition on the mean thickness of the amorphous layers. For the dielectric relaxation, the loss maximum was found to shift to higher temperatures with decreasing thickness of the amorphous layers, but no differences were observed in the curve shape for the differently crystallized samples. For the calorimetric measurements, in contrast, there was no correlation for the glass transition temperature, whereas the curve shape did correlate with the layer thickness of the mobile amorphous fraction. From the structure parameters, a characteristic length of approximately (2.5±1) nm was estimated for the unconfined glass relaxation (transition).
Quasi-isothermal temperature modulated DSC (TMDSC) were performed during crystallization to determine heat capacity as function of time and frequency. Non-reversible and reversible phenomena in the crystallization region of polymers were distinguished. TMDSC yields new information about the dynamics of local processes at the surface of polymer crystals, like reversible melting. The fraction of material involved in reversible melting, which is established during main crystallization, keeps constant during secondary crystallization for polycaprolactone (PCL). This shows that also after long crystallization times the surfaces of the individual crystallites are in equilibrium with the surrounding melt. Simply speaking, polymer crystals are living crystals. A strong frequency dependence of complex heat capacity can be observed during and after crystallization of polymers.
Electron paramagnetic resonance (EPR, ST-EPR) and differential scanning calorimetry(DSC) were used in conventional and temperature
modulated mode to study internal motions and energetics of myosin in skeletal muscle fibres in different states of the actomyosin
ATPase cycle. Psoas muscle fibres from rabbit were spin-labelled with an isothiocyanate-based probe molecule at the reactive
sulfhydryl site (Cys-707) of the catalytic domain of myosin. In the presence of nucleotides (ATP, ADP, AMP⋅PNP) and ATP or
ADP plus orthovanadate, the conventional EPR spectra showed changes in the ordering of the probe molecules in fibres. In MgADP
state a new distribution appeared; ATP plus orthovanadate increased the orientational disorder of myosin heads, a random population
of spin labels was superimposed on the ADP-like spectrum.
In the complex DSC pattern, higher transition referred to the head region of myosin. The enthalpy of the thermal unfolding
depended on the nucleotides, the conversion from a strongly attached state of myosin to actin to a weakly binding state was
accompanied with an increase of the transition temperature which was due to the change of the affinity of nucleotide binding
to myosin. This was more pronounced in TMDSC mode, indicating that the strong-binding state and rigor state differ energetically
from each other. The different transition temperatures indicated alterations in the internal microstructure of myosin head
region The monoton decreasing TMDSC heat capacities show that Cp of biological samples should not be temperature independent.
The relaxation strength at the glass transition for semi-crystalline polymers observed by different experimental methods shows
significant deviations from a simple two-phase model. Introduction of a rigid amorphous fraction, which is non-crystalline
but does not participate in the glass transition, allows a description of the relaxation behavior of such systems. The question
arises when does this amorphous material vitrify. Our measurements on PET identify no separate glass transition and no devitrification
over a broad temperature range. Measurements on a low molecular weight compound which partly crystallizes supports the idea
that vitrification of the rigid amorphous material occurs during formation of crystallites. The reason for vitrification is
the immobilization of co-operative motions due to the fixation of parts of the molecules in the crystallites. Local movements
(Β-relaxation) are only slightly influenced by the crystallites and occur in the whole non-crystalline fraction.
The results from temperature modulated DSC in the glass transition region of amorphous and semicrystalline polymers are described with the linear response approach. The real and the imaginary part of the complex heat capacity are discussed. The findings are compared with those of dielectric spectroscopy. The frequency dependent glass transition temperature can be fitted with a VFT-equation. The transition frequencies are decreased by 0.5 to 1 orders of magnitude compared to dielectric measurements. Cooling rates from standard DSC are transformed into frequencies. The glass transition temperatures are also approximated by the VFT-fit from the temperature modulated measurements. The differences in the shape of the curves from amorphous and semicrystalline samples are discussed.