Vitrification phenomena and further structural relaxation processes or physical ageing occurring in the isothermal curing reaction of an epoxy resin are studied by Differential Scanning Calorimetry (DSC). The vitrification time,tv, the limiting conversion degree and the limiting glass transition temperature (Tg) are evaluated at curing temperatures (Tc) between 30 and 100‡C. The dependence of limitingTg withTc permits the determination of the maximumTg of the resin (109‡C). The physical ageing, which appears as the the last step of curing reaction for curing times above to vitrification, is analyzed through the endothermic peak superposed to the glass transition temperature. The results obtained in partially reticulated resin show the kinetics of the physical ageing to slow down asTc increases, as a consequence that the segmental mobility is reduced.
The glass transition temperature of thermosets is determined by alternating differential scanning calorimetry (ADSC), which is a temperature modulated DSC technique. The different values of the glass transition obtained from heat flow measurements (total and reversible) and heat capacity (modulus of the complex heat capacity) are analysed and compared with the values obtained by conventional DSC. The effect of the sample mass on the values of Tg, heat capacity and phase angle has been analysed. The effect of the thermal contact between sample and pan has been studied using samples cured directly inside the pan and disc-shaped samples of different thickness. The results obtained for the thermal properties and the phase angle are compared and analysed. The modulus of the complex heat capacity enables the determination of the dynamic glass transition, Tg, which is frequency dependent. The apparent activation energy ofthe relaxation process associated with the glass transition has been evaluated from the dependence of Tg on the period of the modulation.
The measurement of the maximum glass transitionTg∞ of a thermosetting resin is usually performed by differential scanning calorimetry in the second scan (Tg2scan), after a previous scan by heating up the sample to a temperature where the exothermic curing reaction has been completed.
However, this method can eventually produce thermal degradation, decreasing the crosslinking density and theTg of the sample. Values ofTg2scan between 95† and 102†C were found in an epoxy resin based on DGEBA cured with phthalic anhydride. Thermal degradation effects
can be avoided if the measurement is performed by isothermal curing and further determination ofTg. ATg∞ value of 109†C is achieved, which is the maximum value ofTg according to the topological limit of conversion.
The modulated differential scanning calorimetry (MDSC) technique superimposes upon the conventional DSC heating rate a sinusoidally varying modulation. The result of this modulation of the heating rate is a periodically varying heat flow, which can be analysed in various ways. In particular, MDSC yields two components (‘reversing’ and ‘non reversing’) of the heat flow, and a phase angle. These each show a characteristic behaviour in the glass transition region, but their interpretation has hitherto been unclear. The present work clarifies this situation by a theoretical analysis of the technique of MDSC, which introduces a kinetic response of the glass in the transition region. This analysis is able to describe all the usual features observed by MDSC in the glass transition region. In addition, the model is also able to predict the effects of the modulation variables, and some of these are discussed briefly.
Authors:F. Román, S. Montserrat, and J. Hutchinson
The procedure for
the fabrication of epoxy-based polymer layered silicate nanocomposites is
important in respect of the nanostructure that is developed. To further our
understanding of this, the influence of an organically modified clay (montmorillonite,
MMT) on the curing kinetics of an epoxy resin has been studied by differential
scanning calorimetry. Clay loadings of 10 and 20 mass% are used, and isothermal
as well as dynamic cures have been investigated. For both cure schedules the
effect of the MMT is to advance the reaction. Kinetic analysis yields values
for the activation energy, but shows that the reaction cannot be described
simply by the usual autocatalytic equation. The glass transition of the cured
nanocomposites is lower than that for the cured neat resin, a result that
is attributed to homopolymerisation taking place in addition to the epoxy–amine
Authors:I. Fraga, J. Hutchinson, and S. Montserrat
The processes of vitrification and devitrification that occur in an epoxy resin when it cures non-isothermally with a hardener
are studied in terms of their frequency dependence and as a function of the heating rate. A novel modulated DSC technique,
TOPEM, has been used which permits the evaluation of the frequency dependence for a single sample in a scan at constant underlying
heating rate, thus avoiding errors arising from the composition of the sample. The effects of both frequency and heating rate
on vitrification and devitrification are investigated. Some advantages of this technique are observed and discussed.
Authors:Iria Fraga, S. Montserrat, and J. Hutchinson
TOPEM is a new temperature modulated DSC technique, introduced by Mettler-Toledo
in late 2005, in which stochastic temperature modulations are superimposed
on the underlying rate of a conventional DSC scan. These modulations consist
of temperature pulses, of fixed magnitude and alternating sign, with random
durations within limits specified by the user. The resulting heat flow signal
is analysed by a parameter estimation method which yields a so-called ‘quasi-static’
specific heat capacity and a ‘dynamic’ specific heat capacity
over a range of frequencies. In a single scan it is thus possible to distinguish
frequency-dependent phenomena from frequency-independent phenomena. Its application
to the glass transition is examined here.
Authors:I. Fraga, S. Montserrat, and J. Hutchinson
The process of vitrification that occurs during the isothermal cure of a cross-linking system at temperatures below Tg∞, the glass transition temperature of the fully cured resin, has been studied by TOPEM, a new temperature modulated DSC (TMDSC)
technique based upon the use of stochastic temperature pulses. A comparison is made between TOPEM and another TMDSC technique,
and some advantages of TOPEM are considered. The TOPEM technique is used to show that the mobility factor is not always a
reliable approach to predicting the cure rate during vitrification, in view of its frequency dependence. Also, the dependence
of the apparent vitrification time on frequency is examined. There appears to be a non-linear relationship between the apparent
vitrification time and log(frequency), which is further discussed in the second part of this series.
Authors:S. Montserrat, P. Cortés, Y. Calventus, and J. Hutchinson
Structural relaxation in different epoxy-anhydride and epoxy-diamine resins has been investigated by differential scanning
calorimetry using annealing and cooling rate experiments. The annealing experiments lead to the determination of enthalpy
loss,δH, at an equivalent annealing temperatureTa=Tg-20, and for periods of annealing time, ta, between 1 h and 4 months. The variation ofδH with logta, defines a relaxation rate per decade,rrpd, which is very sensitive to changes of the epoxy network. The cooling rate experiments allow the determination of the apparent
activation energy,δh*. The effect of the degree of crosslinking, the addition of a reactive diluent, which acts as flexibilizer, and the length
of cross-link onrrpd and δh* was studied.