Phase change, kinetics

The kinetics of melt-crystallization of PLA has been analyzed by a number of research groups [14, 35, 39, 71-75]. Isothermal bulk crystallization rates were determined in a wide temperature range from 70 to 165 C [71,72]. The maximum crystaUization rate is observed around 100 C, and the most peculiar behavior is a discontinuity in the phase change kinetics around 110-120°C, an example of which is shown in Figure 5.10. Figure 5.10a reports the half-time of crystallization of PLA as function of the isothermal crystallization temperature. The data set shows a broad minimum around 108 C and a step/discontinuity around 116-118°C, indicated by the arrow. The sudden variation in crystallization rate... 

The foregoing indicates that the ideal process characteristic for the application of intensification is that the reaction or phase change kinetics should be as fast as possible. If we regard the H2/O2 rocket motor as a chanical reactor, its performance is very definitely limited by heat and mass transfer considerations. Nevertheless the very fast combustion kinetics allows residence times of several milliseconds and... 

Advantages to Membrane Separation This subsertion covers the commercially important membrane applications. AU except electrodialysis are pressure driven. All except pervaporation involve no phase change. All tend to be inherently low-energy consumers in the-oiy if not in practice. They operate by a different mechanism than do other separation methods, so they have a unique profile of strengths and weaknesses. In some cases they provide unusual sharpness of separation, but in most cases they perform a separation at lower cost, provide more valuable products, and do so with fewer undesirable side effects than older separations methods. The membrane interposes a new phase between feed and product. It controls the transfer of mass between feed and product. It is a kinetic, not an equihbrium process. In a separation, a membrane will be selective because it passes some components much more rapidly than others. Many membranes are veiy selective. Membrane separations are often simpler than the alternatives. 

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... 

Chemical dynamics and modeling were identified as important research frontiers in Chapter 4. They are critically important to the materials discussed in this chapter as well. At the molecular scale, important areas of investigation include studies of statistical mechaiucs, molecular and particle dynamics, dependence of molecular motion on intermolecular and interfacial forces, and kinetics of chemical processes and phase changes. 

Experience profound compositional shifts in use May experience phases changes in use Site in the disease s location Operate at variable drug activity Highly nonstationary state kinetics Application technique and amount are highly individualized Applications short-acting Local tissue levels tied to efficacy Used on diseased, damaged skin No easy bioequivalency endpoint Systemic absorption absolutely undesirable, but some unavoidable... 

From the discussion presented of reactions in solids, it should be apparent that it is not practical in most cases to determine the concentration of some species during a kinetic study. In fact, it may be necessary to perform the analysis in a continuous way as the sample reacts with no separation necessary or even possible. Experimental methods that allow measurement of the progress of the reaction, especially as the temperature is increased, are particularly valuable. Two such techniques are thermo-gravimetric analysis (TGA) and differential scanning calorimetry (DSC). These techniques have become widely used to characterize solids, determine thermal stability, study phase changes, and so forth. Because they are so versatile in studies on solids, these techniques will be described briefly. 

Intermolecular forces can affect phase changes. Strong intermolecular forces require more kinetic energy to convert a liquid into a gas. Stronger intermolecular forces, make it easier to condense a gas into a liquid. 

M. Avrami, Kinetics of phase change. II Transformation-time relations for random distribution of nuclei, J. Chem. Phys. 8 (1940) 212. 

Kinetics of phase change, II transformation-time relations for random... 

Kinetics of phase change. III granulation, phase change, and microstruc-... 

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