Spinodal demixing behavior

Fig. 39. Micro-EDX analysis of Ndl23 crystals grown by the modified TSSG method in low-Po, atmosphere from contamination-firee Nd Oj crucibles with different post-growth heat treatments. In all the cases final oxygenation at 340°C in oxygen was applied. The picture demonstrates (a) tweed structure formation and (b) nanoscale composition fluctuations in crystals with the anomalous peak effect on a magnetization curve. Note that the composition profile for heavy atoms (Ba/Nd ratio) is similar to wave-like fluctuations typical for demixing behavior or a spinodal homophase decomposition rather than for a heterophase decomposition with the formation of a boundary between the crystal matrix and the precipitated phase (M. Nakamura et al. 1996c).

In summary, the predictions of analytic PRISM theory [67] for the phase behavior of asymmetric thread polymer Uends display a ly rich dependence on the single chain structural asymn try variables, the interchain attractive potential asymmetries, the ratio of attractive and repulsi interaction potential length scales, a/d, and the thermodynamic state variaUes t) and < ). Moreover, these dependences are intimately coupled, which mathematically arises within the compressible PRISM theory from cross terms between the repulsive (athermal) and attractive potential contributions to the k = 0 direct correlations in the spinodal condition of Eq. (6.6). The nonuniversality and nonadditivity of the consequences of molecular structural and interaction potential asymmetries on phase stability can be viewed as a virtue in the sense that a great variety of phase behaviors are possible by rational chemical structure modification. Finally, the relationship between the analytic thread model predictions and numerical PRISM calculations for more realistic nonzero hard core diameter models remains to be fully established, but preliminary results suggest the thread model predictions are qualitatively reliable for thermal demixing [72,85]. 

When polymers undergo phase separation in thin films, the kinetic and thermodynamic effects are expected to be pronounced. The phase separation process can be controlled to effect desired morphologies. Under suitable conditions a film deposition process can lead to pattern replication. Demixing of polymer blends can lead to structure formation. The phase separation process can be characterized by the binodal and spinodal curves. UCST is the upper critical solution temperature, which is the temperature above which the blend constituents are completely miscible in each other in all proportions. LUST behavior is not found as often in systems other than among polymers. LUST is the lower critical solution temperature. This is the... 

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