Experimental thermal analysis

The equilibrium constitution of an alloy can be determined experimentally by metallography and thermal analysis (described later). If the pressure is held constant at 1 atm., then the independent variables which control the constitution of a binary alloy are T and Xr or Wg. 

Shrinkage during sintering at high T can be determined experimentally by dilatometry, electrical conductivity, acoustic waves or thermal analysis . 

Phase diagrams give valuable information about the compounds that can form in a system of components. These compounds can then be prepared and studied. For the experimental determination of phase diagrams the following methods are used. In differential thermal analysis (DTA) a sample of a given composition is heated or cooled slowly... 

Fig. 3 Schematic diagram illustrating the essential aspects of the differential thermal analysis technique. The experimental observable is the differential temperature between sample and reference, which will be plotted as a function of the system temperature.

Experimental Methods In Differential thermal analysis (DTA) the sample and an inert reference substance, undergoing no thermal transition in the temperature range under study are heated at the same rate. The temperature difference between sample and reference is measured and plotted as a function of sample temperature. The temperature difference is finite only when heat is being evolved or absorbed because of exothermic or endothermic activity in the sample, or when the heat capacity of the sample changes abruptly. As the temperature difference is directly proportional to the heat capacity so the curves are similar to specific heat curves, but are inverted because, by convention, heat evolution is registered as an upward peak and heat absorption as a downward peak. 

Autocatalysis happens when a reaction product, formed during reaction, acts as a catalyst which accelerates the progress of the reaction even at constant temperature. An example is the acid-catalysed saponification of various esters and related compounds. Autocatalytic reactions can be easily experimentally identified by means of differential thermal analysis methods. 

It must however be pointed out that a sound experimental definition of a phase diagram can be obtained from the results of a number of concerted investigations such as thermal analysis, thermodynamic analysis, micrographic examination and phase analysis and identification by means of techniques such as X-ray diffraction measurements, microprobe analysis, etc. 

Emphasis has already been placed on the different experimental methodologies, for instance by Hume-Rothery et al. (1953) who stressed the need to use different complementary techniques in the definition of ternary or more complex systems. The necessity of combining thermal analysis with microscopic techniques was especially highlighted, for example, in the determination of solid liquid equilibria. 

Experimental studies on the thermal decomposition and combushon processes of AP have been carried out and their detailed mechanisms have been reported.P-iil Fig. 5.1 shows the thermal decomposition of AP as measured by differential thermal analysis (DTA) and thermal gravimetry (TG) at a heating rate of 0.33 K s"f An endothermic peak is seen at 520 K, corresponding to an orthorhombic to cubic lattice crystal structure phase transition, the heat of reaction for which amounts to... 

Ignition temperatures can also be determined by differential thermal analysis (DTA), and these values usually correspond well to those obtained by a Henkin-McGill study. Differences in heating rate can cause some variation in values obtained with this technique. For any direct comparison of ignition temperatures, it is best to run all of the mixtures of interest under identical experimental conditions, thereby minimizing the number of variables. 

Fig. 12. Calculated liquidus and solidus in the InSb-GaSb pseudobinary section and experimental points. Squares from differential thermal analysis, circles from thermal analysis, and triangles from x-ray diffraction, all from Wooley and Lees (1959). Diamonds are from Blom and Plaskett (1971).

Any compd or mixt whose heat of formation is smaller by 500 J/g (or more) than the sum of the heats of formation of its reaction products must be regarded with suspicion and handled with more than usual care. The hazards involved in working with a potentially expl system are directly proportional to the amount and to the rate of energy release. Because the reaction kinetics cannot be predicted, the propensity of a new system for expl reaction must be determined. The sensitivity of the system can be evaluated by means of impact, friction, shock and electrostatic discharge. Appropriate methods are reviewed in the Experimental and Hazard Assessment section of this article. Sensitivity to heat or elevated temp may be evaluated by use of differential thermal analysis (DTA)... 

Accurate temperature calibration using the ASTM temperature standards [131, 132] is common practice for DSC and DTA. Calibration of thermobalances is more cumbersome. The key to proper use of TGA is to recognise that the decomposition temperatures measured are procedural and dependent on both sample and instrument related parameters [30]. Considerable experimental control must be exercised at all stages of the technique to ensure adequate reproducibility on a comparative basis. For (intralaboratory) standardisation purposes it is absolutely required to respect and report a number of measurement variables. ICTA recommendations should be followed [133-135] and should accompany the TG record. During the course of experiments the optimum conditions should be standardised and maintained within a given series of samples. Affolter and coworkers [136] have described interlaboratory tests on thermal analysis of polymers. 

---