Authors:M. Reading, D. Dollimore, and R. Whitehead
Following previous work on the measurement of meaningful activation energies and the application of Constant Rate Thermal Analysis (CRTA) to the determination of kinetic parameters [1, 2], here we further examine sources of error in determining activation energies and go on to consider the form of the alpha function and the value ofA. Using theoretical arguments based on transition state theory, we conclude that allowing significant pressures of product gas to appear in the reaction environment will lead to very high values for apparent activation energies. We note that, although this is observed in practice for calcium carbonate, it in no way invalidates the application of the Arrhenius equation to solid state decomposition reactions, provided care is taken to avoid this type of distortion of experimental results. We attempt to determine the alpha function for the decomposition of calcium carbonate using data gathered from a variety of different types of temperature programme and reaction conditions. We find that the apparent alpha function depends on the method adopted and the experimental conditions used. We propose an explanation of why this occurs and tentatively introduce a new way of looking at the development of a reaction interface for this type of reaction. We review the literature and conclude that, while significant variations for the activation energy for the decomposition of calcium carbonate exist, a critical appraisal leads to good agreement amongst values that follow good experimental practice and reliable methods of data reduction. The apparent divergence of results can be explained in the light of the theoretical arguments advanced and the easily understood sources of experimental error.
Reading and co-workers introduced a new technique a few years ago called Modulated Differential Scanning Calorimetry or MDSC.
Here the first part of a theoretical analysis for this technique is given. A simple mathematical model for modulated differential
scanning calorimetry in the form of an ordinary differential equation is derived. The model is analysed to find the effect
of a kinetic event in the form of a chemical reaction. Some possible sources of error are discussed. A more sophisticated
version of the model allowing for spatial variation in a calorimeter is developed and it is seen how it can be reduced to
the earlier model. Some preliminary work on a phase change is also presented.
Micro-thermal analysis combines the imaging facility of scanning probe microscopy with the ability to characterize, with high
spatial resolution, the thermal behavior of materials. A sample may be visualized according to its surface topography and
also its relative thermal conductivity. Areas of interest may then be selected and localized thermal analysis (TMA and modulated
temperature DTA) performed. Applications of this new technique to study semiconductors, polymer blends and biological specimens
Modulated DSCTM (MDSC) is a new, patent-pending extension to conventional DSC which provides information about the reversing and nonreversing
characteristics of thermal events, as well as the ability to directly measure heat capacity. This additional information aids
interpretation and allows unique insights into the structure and behaviour of materials., A number of examples of its use
Authors:M. Bahra, D. Elliott, M. Reading, and R. Ryan
A novel instrument is described called the Thin film Analyser (TFA) which quantitatively measures changes in mechanical and rheological properties of drying films in-situ on a test panel. It is based around a simple force-sensing device, capable of carrying various probes, which can be positioned in anX-Y plane over the panel. Temperature control is achieved by means of a heating block under the sample. By imposing a thermal gradient along the block, measurements can be obtained at a series of temperatures in a single experiment. Several applications of the TFA to the drying of curable and latex-based coatings are discussed, as well as some more specialized uses. The TFA concept represents a novel approach to the thermal analysis of thin films.
Authors:M. Song, D. Hourston, M. Reading, H. Pollock, and A. Hammiche
A modulated-temperature differential scanning calorimetry (M-TDSC) method for the analysis of interphases in multi-component
polymer materials has been developed further. As examples, interphases in a polybutadiene-natural rubber (50:50 by mass) blend,
a poly(methyl methacrylate)-poly(vinyl acetate) (50:50 by mass) structured latex film, a polyepichlorohydrinpoly(vinyl acetate)
bilayer film, and polystyrene-polyurethane (40:60 by mass) and poly(ethyl methacrylate)-polyurethane (60:40 by mass) interpenetrating
polymer networks were investigated. The mass fraction of interphase and its composition can be calculated quantitatively.
These interphases do not exhibit clear separate glass transition temperatures, but occur continually between the glass transition
temperatures of the constituent polymers.