Phase change melting

Differential Thermal Analysis. Differential thermal analysis (DTA) is a technique in which differences in temperature between a sample under investigation and an inert reference material are measured as both materials are simultaneously heated at a uniform rate. Endotherros and exotherms due to melting, phase changes, or chemical changes are thus seen. Changes in heat capacity at Tg are often noted. 

Melt (phase change) To convert from a solid to a liquid. 

Unlike melting and the solid-solid phase transitions discussed in the next section, these phase changes are not reversible processes they occur because the crystal stmcture of the nanocrystal is metastable. For example, titania made in the nanophase always adopts the anatase stmcture. At higher temperatures the material spontaneously transfonns to the mtile bulk stable phase [211, 212 and 213]. The role of grain size in these metastable-stable transitions is not well established the issue is complicated by the fact that the transition is accompanied by grain growth which clouds the inteiyDretation of size-dependent data [214, 215 and 216]. In situ TEM studies, however, indicate that the surface chemistry of the nanocrystals play a cmcial role in the transition temperatures [217, 218]. 

Eig. 15. Time—temperature transformation ia a thin-phase change layer during recording/reading/erasiug (3,105). C = Crystalline phase A = amorphous phase = melting temperature = glass-transition temperature RT = room temperature. 

Polyamides, like other macromolecules, degrade as a result of mechanical stress either in the melt phase, in solution, or in the soHd state (124). Degradation in the fluid state is usually detected via a change in viscosity or molecular weight distribution (125). However, in the soHd state it is possible to observe the free radicals formed as a result of polymer chains breaking under the appHed stress. If the polymer is protected from oxygen, then alkyl radicals can be observed (126). However, if the sample is exposed to air then the radicals react with oxygen in a manner similar to thermo- and photooxidation. These reactions lead to the formation of microcracks, embrittlement, and fracture, which can eventually result in failure of the fiber, film, or plastic article. 

The sharpness of the transition in pure lipid preparations shows that the phase change is a cooperative behavior. This is to say that the behavior of one or a few molecules affects the behavior of many other molecules in the vicinity. The sharpness of the transition then reflects the number of molecules that are acting in concert. Sharp transitions involve large numbers of molecules all melting together. 

Many metals and metallic alloys show martensitic transformations at temperatures below the melting point. Martensitic transformations are structural phase changes of first order which belong to the broader class of diffusion js solid-state phase transformations. These are structural transformations of the crystal lattice, which do not involve long-range atomic movements. A recent review of the properties and the classification of diffusionless transformations has been given by Delayed... 

The candle flame gives off heat, melting the candle wax. Wax melting is a phase change from solid to liquid and an endothermic reaction. 

On the other hand, this simple rule fails for many familiar phase changes. An example of a spontaneous reaction that is not exothermic is the melting of ice. This takes place spontaneously at 1 atm above 0°C, even though it is endothermic... 

Notice from the figure that the effect of temperature on entropy is due almost entirely to phase changes. The slope of the curve is small in regions where only one phase is present. In contrast, there is a large jump in entropy when the solid melts and an even larger one when the liquid vaporizes. This behavior is typical of all substances melting and vaporization are accompanied by relatively large increases in entropy. 

We have discovered that a solid can be converted to a liquid by warming it at or above its melting point. Then the solid can be restored merely by recooling. The solid and the liquid are similar in many respects and one is easily obtained from the other. Hence they are called different phases of the same substance. Ice is the solid phase of water and, at room temperature, water is in the liquid phase. The change that occurs when a solid melts or a liquid freezes is called a phase change. 

The heat accompanying the phase change (2) is 1.44 kcal/mole. This is much less than the molar heat of vaporization of water, 10 kcal/mole. Table 5-II contrasts the melting points and the heats of melting per mole (the molar heat of melting, or the molar heat of fusion) of the same pure substances listed in Table 5-1. 

Let us compare the behavior of these two systems during a phase change. Consider, first, how water acts when it is frozen or vaporized. Pure water freezes at a fixed temperature, 0°C. If we freeze half of a water sample to ice, remove the ice, melt it in another container, and compare the separate samples, we find that the two fractions of the original sample are indistinguishable. 

Phase changes are examples of (c). In order to melt a mole of ice in contact with air at 298.15 K, heat must flow into the system from the air. The increase in entropy of the system is 22.00 J K-1 - mol-1. The heat leaving the air decreases its entropy by 20.15 J K-1 mol-1. The net change in the universe is once again positive ... 

Changing the pressure will have a similar effect. If we increase p by dp, the solid melts. This process can be reversed at any time by decreasing the pressure by dp. Note that at p = 1 atm (101.325 kPa), only at T = 273.15 K can the phase change be made to occur reversibly because this is the temperature where solid and liquid are in equilibrium at this pressure. If we tried to freeze liquid water aip— atm and a lower temperature such as 263.15 K, the process, once started, would proceed spontaneously and could not be reversed by an infinitesimal change in p or T. 

The thermal decomposition of a solid, which necessarily (on the above definition) incorporates a chemical step, is sometimes associated with the physical transformations to which passing reference was made above melting, sublimation, and recrystallization. Aspects of the relationships between physical transitions and decomposition reactions of solids are discussed in a book by Budnikov and Ginstling [1]. Since, in general, phase changes exert significant influence upon concurrent or subsequent chemical processes, it is appropriate to preface the main survey of the latter phenomena with a brief account of those features of melting, sublimation, and recrystallization which are relevant to the consideration of thermal decomposition reactions. 

As with other properties of solids, the increased relative significance of surface energy in very small (i.e. micrometre-sized) crystals influenced the melting points [2,16,17] and diffusion at this temperature. Quantitative studies of rates of melting of solids are impracticable since superheating is effectively forbidden and the rate of the endothermic phase change is determined by the rate of heat supply and the thermal conductivity of the solid. 

Although there are experimental and interpretative limitations [189, 526] in the kinetic analysis of non-isothermal data, DTA or DSC observations are particularly useful in determining the temperature range of occurrence of one or perhaps a sequence of reactions and also of phase changes including melting. This experimental approach provides, in addition, a useful route to measurements of a in the study of reactions where there is no gas evolution or mass loss. The reliability of conclusions based on non-isothermal data can be increased by quantitatively determining the... 

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