Freezing-in and production of entropy in vitrification.

Following the classical concepts developed by Simon [Z. Anorg. Allg. Chem. 203, 219 (1931)], vitrification in the cooling of glass-forming melts is commonly interpreted as the transformation of a thermodynamically (meta)stable equilibrium system into a frozen-in, thermodynamically nonequilibrium system, the glass. Hereby it is assumed that the transformation takes place at some well-defined sharp temperature, the glass transition temperature Tg. However, a more detailed experimental and theoretical analysis shows that the transition to a glass proceeds in a broader temperature range, where the characteristic times of change of temperature, tauT=-(TT), and relaxation times, tau, of the system to the respective equilibrium states are of similar order of magnitude. In this transition interval, the interplay of relaxation and change of external control parameters determines the value of the structural order parameters. In addition, irreversible processes take place in the transition interval, resulting both in an entropy freezing-in as well as in an irreversible increase of entropy and, as a result, in significant changes of all other thermodynamic parameters of the vitrifying systems. The effect of entropy production on glass transition and on the properties of glasses is analyzed here for the first time. In this analysis, the structural order-parameter concept as developed by de Donder and van Rysselberghe [Thermodynamic Theory of Affinity (Stanford University Press, Stanford, 1936)] and Prigogine and Defay [Chemical Thermodynamics (Longmans, London, 1954)] is employed. In the framework of this approach we obtain general expressions for the thermodynamic properties of vitrifying systems such as heat capacity, enthalpy, entropy, and Gibbs' free energy, and for the entropy production. As one of the general conclusions we show that entropy production has a single maximum upon cooling and two maxima upon heating in the glass transition interval. The theoretical concepts developed allow us to explain in addition to the thermodynamic parameters also specific features of the kinetic parameters of glass-forming melts such as the viscosity. Experimental results are presented which confirm the theoretical conclusions. Further experiments are suggested, allowing one to test several additional predictions of the theory.

Nucleation versus spinodal decomposition in phase formation processes in multicomponent solutions.

In the present paper, some further results of application of the generalized Gibbs' approach to describing new-phase formation processes are outlined. The path of cluster evolution in size and composition space is determined taking into account both thermodynamic and kinetic factors. The basic features of these paths of evolution are discussed in detail for a simple model of a binary mixture. According to this analysis, size and composition of the clusters of the newly evolving phase change in an unexpected way which is qualitatively different as compared to the classical picture of nucleation-growth processes. As shown, nucleation (i.e., the first stage of cluster formation starting from metastable initial states) exhibits properties resembling spinodal decomposition (the size remains nearly constant while the composition changes) although the presence of an activation barrier distinguishes the nucleation process from true spinodal decomposition. In addition, it is shown that phase formation both in metastable and unstable initial states near the classical spinodal may proceed via a passage of a ridge of the thermodynamic potential with a finite work of the activation barrier even though (for unstable initial states) the value of the work of critical cluster formation (corresponding to the saddle point of the thermodynamic potential) is zero. This way, it turns out that nucleation concepts-in a modified form as compared with the classical picture-may govern also phase formation processes starting from unstable initial states. In contrast to the classical Gibbs' approach, the generalized Gibbs' method provides a description of phase changes both in binodal and spinodal regions of the phase diagram and confirms the point of view assuming a continuity of the basic features of the phase transformation kinetics in the vicinity of the classical spinodal curve.

Assessment of coronary artery stent patency by electron-beam CT.

Following coronary angioplasty and stent implantation, restenosis remains common and its outcome difficult to predict. We set out to determine the diagnostic accuracy of electron-beam computed tomography (EBCT) for the non-invasive detection of stent obstruction. In a prospective, blinded investigation, we included 152 coronary artery segments in 117 patients treated with a stent implant. All segments were evaluated by a dynamic EBCT study that depicted contrast bolus passage distal to the stent and a CT angiographic study of the entire coronary arteries. It was found that delayed contrast enhancement in the distal segment correlated with angiographic stent obstruction (Spearman's rank correlation, P=0.008), while all other indicators of stent occlusion did not correlate with angiographic diagnosis. However, direct comparison of patients with obstruction of less vs. more than 75% of luminal diameter did not yield any statistically significant differences of distal enhancement delay, and for the detection of >90% occlusion, the sensitivity was 72% at a specificity of 60%. Although delayed contrast enhancement distal to the stent upon EBCT did correlate with angiographical obstruction, the correlation did not suffice to appear clinically satisfactory.