The relevance of the amorphous state to pharmaceutical dosage forms: glassy drugs and freeze dried systems

Mathematical description of differential scanning calorimetry based on periodic temperature modulation

This paper reviews the best-known differential scanning calorimetries (DSCs), such as conventional DSC, microelectromechanical systems-DSC, infrared-heated DSC, modulated-temperature DSC, gas flow-modulated DSC, parallel-nano DSC, pressure perturbation calorimetry, self-reference DSC, and high-performance DSC. Also, we describe here the most extensive applications of DSC in biology and nanoscience.

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Differential Scanning Calorimetry Techniques: Applications in Biology and Nanoscience

Modulated differential scanning calorimetry

Characterization of solid dispersions of itraconazole and hydroxypropylmethylcellulose prepared by melt extrusion—part I

The theoretical basis for Modulated DSC is described and the additional information in can give over conventional DSC illustrated for some polymers.

A new approach to the calorimetric investigation of physical and chemical transitions

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.

The measurement of meaningful kinetic parameters for solid state decomposition reactions

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.

A mathematical model for Modulated Differential Scanning Calorimetry

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.

M. Reading

Papers

A new approach to the calorimetric investigation of physical and chemical transitions

The measurement of meaningful kinetic parameters for solid state decomposition reactions

A mathematical model for Modulated Differential Scanning Calorimetry

A novel approach to thermal Analysis of Thin films