Thermal properties analysis, methods

Analysis. Excellent reviews of phosphate analysis are available (28). SoHds characterization methods such as x-ray powder diffraction (xrd) and thermal gravimetric analysis (tga) are used for the identification of individual crystalline phosphates, either alone or in mixtures. These techniques, along with elemental analysis and phosphate species deterrnination, are used to identify unknown phosphates and their mixtures. Particle size analysis, surface area, microscopy, and other standard soHds characterizations are useful in relating soHds properties to performance. SoHd-state nmr is used with increasing frequency. 

Thermal Properties. The thermal stabiUty of cellulose esters is deterrnined by heating a known amount of ester in a test tube at a specific temperature a specified length of time, after which the sample is dissolved in a given amount of solvent and its intrinsic viscosity and solution color are deterrnined. Solution color is deterrnined spectroscopically and is compared to platinum—cobalt standards. Differential thermal analysis (dta) has also been reported as a method for determining the relative heat stabiUty of cellulose esters (127). 

Two standard estimation methods for heat of reaction and CART are Chetah 7.2 and NASA CET 89. Chetah Version 7.2 is a computer program capable of predicting both thermochemical properties and certain reactive chemical hazards of pure chemicals, mixtures or reactions. Available from ASTM, Chetah 7.2 uses Benson s method of group additivity to estimate ideal gas heat of formation and heat of decomposition. NASA CET 89 is a computer program that calculates the adiabatic decomposition temperature (maximum attainable temperature in a chemical system) and the equilibrium decomposition products formed at that temperature. It is capable of calculating CART values for any combination of materials, including reactants, products, solvents, etc. Melhem and Shanley (1997) describe the use of CART values in thermal hazard analysis. 

US patent 6,723,728, Polymorphic and other crystalline forms cis-FTC [106], The present invention relates to polymorphic and other crystalline forms of (—)-and ( )-cA-(4-amino-5-fluoro-l-(2-(hydroxymethyl)-l,3-oxathiolan-5-yl)-2(lH)-pyrimidinone, or FTC) [106]. Solid phases of (—)-cz>FTC that were designated as amorphous (—)-FTC, and Forms II and III were found to be distinguishable from Form I by X-ray powder diffraction, thermal analysis properties, and their methods of manufacture. A hydrated crystalline form of ( )-cA-FTC and a dehydrated form of the hydrate, were also disclosed, and can similarly be distinguished from other forms of FTC by X-ray powder diffraction, thermal properties, and their methods of manufacture. These FTC forms can be used in the manufacture of other forms of FTC, or as active ingredients in pharmaceutical compositions. Particularly preferred uses of these forms are in the treatment of HIV or hepatitis B. 

Thermal analysis methods are defined as those techniques in which a property of the analyte is determined as a function of an externally applied temperature... 

The sample temperature is increased in a linear fashion, while the property in question is evaluated on a continuous basis. These methods are used to characterize compound purity, polymorphism, solvation, degradation, and excipient compatibility [41], Thermal analysis methods are normally used to monitor endothermic processes (melting, boiling, sublimation, vaporization, desolvation, solid-solid phase transitions, and chemical degradation) as well as exothermic processes (crystallization and oxidative decomposition). Thermal methods can be extremely useful in preformulation studies, since the carefully planned studies can be used to indicate the existence of possible drug-excipient interactions in a prototype formulation [7]. 

An associated technique which links thermal properties with mechanical ones is dynamic mechanical analysis (DMA). In this, a bar of the sample is typically fixed into a frame by clamping at both ends. It is then oscillated by means of a ceramic shaft applied at the centre. The resonant frequency and the mechanical damping exhibited by the sample are sensitive measurements of the mechanical properties of a polymer which can be made over a wide range of temperatures. The effects of compositional changes and methods of preparation can be directly assessed. DMA is assuming a position of major importance in the study of the physico-chemical properties of polymers and composites. 

Thermal analysis techniques (DSC,TGA, DMTA...) operating on mini or micro samples can detect pinpoint heterogeneities in final parts that bulk analysis methods such as rheom-etry are unable to do. Transient variations of moulding parameters, local design mistakes, internal stresses that influence the properties of the final product, notably impact behaviour, dimensional stability, warpage. .. can be displayed. 

Thermal analysis methods investigate the properties of solids as a function of a change in temperature. They are useful for investigating phase changes, decomposition, loss of water or oxygen, and for constructing phase diagrams. 

Major methods involved with the generation of information about thermal property behavior of materials include thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), differential thermal analysis (DTA), torsional braid analysis (TBA), thermal mechanical analysis (TMA), and pyrolysis gas chromatography (PGC). 

For materials generally, change in expansion (or density) by dilatometry was traditionally the most often used method for measuring Tg. Thermal properties, for example specific heat, are also widely used, particularly the methods of differential thermal analysis". A method for rubbers using DSC is being developed in ISO TC 45 as ISO 22768, but is not yet published. The inflection point on the heat input - temperature curve is usually obtained automatically by the analyser s software but, if obtained manually, is best found from the derivative of the curve. 

Thermal properties are measured and evaluated by some of the methods also mentioned in Chapter 2. For identification of transition temperatures, measurements of heats of fusion, and so on, differential thermal analysis (DTA) and differential scanning calorimetry (DSC) are much used. Thermal stability is measured by thermogravimetric analysis (TGA), although this technique can give overly optimistic results unless used with great care. 

The development of thermal analysis methods in materials research has led to a plethora of new methodologies since the elaboration of the first thermal method by by Le Chatelier and Robert-Austen [16,86], Thermal analysis consists of a group of techniques in which a physical property of a material is measured as a function of temperature at the same time when the substance is subjected to a controlled increase, or in some cases, decrease of temperature. Temperature-programmed techniques, such as DTA [87-89], TGA [87], DSC [53,90], TPR [91,92], and TPD [93-96], contribute to perform a more complete characterization of materials. 

The above derivation for LMTD involves two important assumptions (1) the fluid specific heats do not vary with temperature, and (2) the convection heat-transfer coefficients are constant throughout the heat exchanger. The second assumption is usually the more serious one because of entrance effects, fluid viscosity, and thermal-conductivity changes, etc. Numerical methods must normally be employed to correct for these effects. Section 10-8 describes one way of performing a variable-properties analysis. 

A primary method that is used to characterize the thermal properties of a bulk material is thermogravimetric analysis (TGA). This method provides detailed information regarding the thermal stability and decomposition pathway of a material e.g., stepwise loss of ligands for an organometallic compound), as well as structural information for complex composites (Figure 7.52). The operating principle of TGA is... 

Glass transition temperature, Tg, and storage modulus, E , were measured to explore how the pigment dispersion affects the material (i.e. cross-link density) and mechanical properties. Both Tg and E were determined from dynamic mechanical analysis method using a dynamic mechanical thermal analyzer (DMTA, TA Instruments RSA III) equipped with transient testing capability. A minimum of 3 to 4 specimens were analyzed from each sample. The estimated uncertainties of data are one-standard deviation. 

Based on the measured thermomechanical properties and the microstructure of the graded layer of TiC-NiaAl functionally graded material, using the analysis method, the interface residual thermal stress of TiC-NiyAl sphere in the sintering process was calculated. The relationship between the stress and the content of NiyAl was presented. The results show that the failure mechanics of TiC-NijAl composite may be different in different content of NiyAl. 

In the present work, the graded layer properties of the thermal stress relaxation type functionally gradient material TiC-NiyAl were investigated. First, the thermomechanical properties of the each layer of the composite was tested. Second, the microstructure of the composite was examined. Next, the interface residual thermal stress of TiC-NiaAl sphere in the sintering process was calculated by the analysis method. Then, the relationship between the stress and the thickness of NisAl was also presented. Finally, the effect of the residual thermal stress on the properties of TiC-NiaAl composite was discussed. 

A computational design procedure of a thermoelectric power device using Functionally Graded Materials (FGM) is presented. A model of thermoelectric materials is presented for transport properties of heavily doped semiconductors, electron and phonon transport coefficients are calculated using band theory. And, a procedure of an elastic thermal stress analysis is presented on a functionally graded thermoelectric device by two-dimensional finite element technique. First, temperature distributions are calculated by two-dimensional non-linear finite element method based on expressions of thermoelectric phenomenon. Next, using temperature distributions, thermal stress distributions are computed by two-dimensional elastic finite element analysis. 

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