Solid-phase transitions, kinetics

T.B. Brill, R.J. Karpowicz, "Solid Phase Transition Kinetics. The Role of... 

More recently, studies of the hysteresis of these phase transitions have illuminated the importance of kinetic factors in solid-solid phase transitions [224]. The change between crystal stmctures does not occur at the same point when pressure is increasing, as when it is decreasing the difference between this up-stroke and down-stroke pressure... 

The following section deals with the crystallization and interconversion of polymorphic forms of polymers, presenting some thermodynamic and kinetic considerations together with a description of some experimental conditions for the occurrence of solid-solid phase transitions. 

Rosakis, P., and Knowles, J.K., 1997, Unstable kinetic relations and the dynamics of solid-solid phase transitions. In preparation. 

SAXSAVAXS/RAMAN is especially useful when dealing with chemically induced phase transitions. The example shown in Figure 2(e) is the polymerisation of solvent styrene into polystyrene in which polyethylene is in solution. Polyethylene is soluble in styrene but insoluble in polystyrene. RAMAN allows the determination of the reaction kinetics of polystyrene formation and monitors the crystallisation of the polyethylene. The SAXS monitors the liquid-liquid phase separation followed by the liquid-solid phase transition, whilst the WAXS also observes the liquid solid phase by monitoring the appearance of peaks due to the crystallisation of polyethylene. These are very valuable parameters when trying to define any new manufacturing process. ... 

The principle of studies of coexistence and kinetics in solid-solid phase transitions by NMR is rather simple, since it relies on peak attribution and... 

Differential scanning calorimetry was used by Murrill and co-workers (43-45) to elucidate solid - solid phase transitions in a large number of organic compounds. First-order transitions were reported for tetrahedral compounds of the type CR1R2R2R4, where R is methyl, methylol, amino, nitro, and carboxy, as well as for octahedral-type compounds. This technique was also used to detect phase transitions in alkali metal stearates (46), some dibenzazepines, carbazoles, and phenothiazines (16), and the half esters of O-phthalic acid (31). The solid-state decomposition kinetics and activation parameters of N-aryl-N -tosyl-oxydt-imide N-oxides were determined using DSC by Dorko et al. (49). 

Figure 7. Experimental pressure-temperature phase diagram of AS2S3. Crosses show points and their uncertainties for the experimentally observed phase transitions. Solid line is an approximation of the melting curve, and dashed lines are approximations for the experimental kinetic curves of the solid-solid phase transitions. The points of viscosity measurements are shown hy solid circles and marked by measured values of viscosity (in Pa s units). Shaded region selects a boundary between the melting states with low and high conductivities.

Reliable revealing micro- and submlcro-plasticity, relaxation and solid-solid phase transitions in brittle and ultra-brittle materials. Some correlations between conductivity (electronic processes) and micro-plasticity, and between the creep rate peaks and brittle-ductile transition could be detected. On this basis, the method for predicting the comparable inclination of materials towards the brittle fracture has been developed. In addition, the kinetic analysis of microplasticity in brittle solids could be performed. 

A collection of hard, identical spheres is the simplest possible model system that undergoes a first order phase transition. For low packing fractions the particles are in a liquid state, but when the packing fractions exceeds a value of 49.4% a ordered solid state becomes more stable. This was first shown in computer simulations by Hoover and Ree [27] in 1968. The experimental realization of a colloidal suspension that closely mimics the phase behavior of hard spheres followed about 20 years later and was a milestone in soft matter physics [28, 29]. More recently the phase transition kinetics of hard sphere colloids has been studied extensively in experiments [5, 30, 31]. However as mentioned in the introduction the interpretation of the data with CNT was rather indirect. 

Surface SHG [4.307] produces frequency-doubled radiation from a single pulsed laser beam. Intensity, polarization dependence, and rotational anisotropy of the SHG provide information about the surface concentration and orientation of adsorbed molecules and on the symmetry of surface structures. SHG has been successfully used for analysis of adsorption kinetics and ordering effects at surfaces and interfaces, reconstruction of solid surfaces and other surface phase transitions, and potential-induced phenomena at electrode surfaces. For example, orientation measurements were used to probe the intermolecular structure at air-methanol, air-water, and alkane-water interfaces and within mono- and multilayer molecular films. Time-resolved investigations have revealed the orientational dynamics at liquid-liquid, liquid-solid, liquid-air, and air-solid interfaces [4.307]. 

V. P. Zhdanov, B. Kasemo. Kinetic phase transitions in simple reactions on solid surfaces. Surf Sci Rep 20 111-189, 1994. 

Raghavan, V., and Cohen, M. (1975). "Solid-State Phase Transformations," Chapter 2, in N. B. Hannay, Ed., Treatise on Solid State Chemistry Changes in State, Vol. 5. Plenum Press, New York. A mathematical treatment of the subject including a good treatment of the kinetics of phase transitions. 

An enormous number of phase transitions are known to occur in common solid compounds. For example, silver nitrate undergoes a displacive phase transition from an orthorhombic form to a hexagonal form at a temperature of approximately 162°C that has a enthalpy of 1.85 kj/mol. In many cases, the nature of these transitions are known, but in other cases there is some uncertainty. Moreover, there is frequently disagreement among the values reported for the transition temperatures and enthalpies. Even fewer phase transitions have been studied from the standpoint of kinetics, although it is known that a large number of these transformations follow an Avrami rate law. There is another complicating feature of phase transitions that we will now consider. 

A second reason for the turn-over in the osmotic modulus may arise from a decrease in A2 until it becomes zero or even negative. This would be the classical situation for a phase separation. The reason why in a good solvent such a phase separation should occur has not yet been elucidated and remains to be answered by a fundamental theory. In one case the reason seems to be clear. This is that of starches where the branched amylopectin coexists with a certain fraction of the linear amylose. Amylose is well known to form no stable solution in water. In its amorphous stage it can be brought into solution, but it then quickly undergoes a liquid-solid transition. Thus in starches the amylose content makes the amylopectin solution unstable and finally causes gelation that actually is a kinetically inhibited phase transition [166]. Because of the not yet fully clarified situation this turn-over will be not discussed any further. 

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