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- Author or Editor: N. Sbirrazzuoli x
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Abstract
Feedforward neural networks have been used for kinetic parameters determination and signal filtering in differential scanning calorimetry. The proper learning function was chosen and the network topology was optimized, using an empiric procedure. The learning process was achieved using simulated thermoanalytical curves. The resilient-propagation algorithm have led to the best minimization of the error computed over all the patterns. Relative errors on the thermodynamic and kinetic parameters were evaluated and compared to those obtained with the usual thermal analysis methods (single scan methods). The errors are much lower, especially in presence of noisy signals. Then, our program was adapted to simulate thermal effects with known thermodynamic and kinetic parameters, generated electrically, using a PC computer and an electronic interface on the serial port. These thermal effects have been generated by using an inconel thread.
Summary By applying an advanced isoconversional method to DSC data one can evaluate a dependence of the effective activation energy (the temperature coefficient of the growth rate) on the relative extent of melt crystallization. The conversion dependence can further be converted into a temperature dependence and parameterized in terms of the Hoffman-Lauritzen equation. For poly(ethylene terephthalate) (PET) we observe a transition from regime I to II. Poly(ethylene oxide) (PEO) crystallization appears to begin in regime II and then undergoes 2 consecutive changes that however cannot be clearly interpreted as regime III. The K g and sse parameters obtained for regime I and II (PET) and regime II (PEO) are consistent with the respective parameters reported for isothermal crystallization.
Abstract
In the case of a complex mechanism of two parallel independent reactions, peak maximum evolution methods and model-fitting methods give only a mean value of the kinetic parameters, while isoconversional methods are useful to describe the complexity of the mechanism. Isothermal and non-isothermal isoconversional methods can be used to elucidate the kinetics of the process. Nevertheless, isothermal isoconversional methods can be limited by restrictions on the temperature regions experimentally available because of duration times or detection limits.
Solid-plastic transitions kinetics by DSC
Application to alcohols derived from neopentane
The kinetic parameters of solid-plastic transitions on alcohols derived from neopentane were determined using differential scanning calorimetry (DSC) by a single or multiple scan analysis. The methods studied (Borchard-Daniels, Ellerstein, Multilinear law, Freeman-Carroll, Ozawa, Kissinger), never used before for that kind of transition, imply a single Arrhenius behaviour. These methods werre applied to 2,2-dimethyl 1-propanol (DP), 2,2-dimethyl 1,3-propanediol or neopentylglycol (NPG), 2-hydroxymethyl 2-methyl 1,3-propanediol or pentaglycerine (PG), and 2,2-dihydroxymethyl 1,3-propanediol or pentaerythritol (PE). A simple isothermal test is recommended to check the validity of activation energies experimentally obtained and Arrhenius frequency factors. Taking some restrictions on the heating rate for the heat evolution methods, the results are in agreement with the data obtained by isothermal tests. We have noted a linear dependence of the activation energy values on the number of hydroxyl groups with the exception of pentaerythritol. Isothermal simulations of the solid-plastic transition are an example of industrial applications.
Abstract
The thermal behaviour of authentic honeys and sugar syrups (industrial and homemade) was investigated by DSC. To confirm the first previous results concerning the effect of adulteration on the thermal behaviour of authentic honeys, 30 honey samples (Robinia, Lavender, Chestnut and Fir) were analyzed by DSC and their T g were measured following a suited experimental protocol. The results indicated that this parameter was useful to characterize and to distinguish significantly these varieties between them. Applied to honey samples artificially adulterated with different industrial syrups, DSC showed a detection level of 5–10% depending on the type of syrup. An endothermic phenomenon occurring between 40–90°C during the heating was studied by TMDSC and a new thermal transition similar to a glass-transition was highlighted.
