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Induced crystallization of glass-forming melts : Part 1. Heterogeneous nucleation. Effect of noble metal microcrystals on the crystallization of calcium metaphosphate glasses
The possibilities of initiating crystallization in glass-forming melts are analyzed, using experimental evidence, obtained with several model glass-forming systems. In the present Part 1 of the investigation the process of heterogeneous nucleation, catalyzed by insoluble crystallization cores is studied, using a new theoretieal thermodynamie model. The nucleation activity coefficient, Φ, of the aubstrates is described by the adhesion energy, β, at the interface crystallization core/overgrowing crystal. Lattice disregistry is accounted for as an additional correlation factor, influencing the thermodynamie work of adhesion.
The crystallization of calcium metaphosphate glass-forming melts, initiated by noble metal microerystals (Ag, Au, Pd, Pt, Rh, Ru, Ir, Os), is studied by differential thermal analysis, optical and scanning electron microseopy. Ir microerystals show highest nucleation activity promoting intensive bulk crystallization in the Ca(PO3)2 systems investigated. The activity of other crystallization cores decreases in the following sequence: Ru > Rh > Os > Pt > Pd > Au > Ag. The above outlined thermodynamic theory of nucleation activity is used to correlate experimental data and to calculate activity coefficients, Φ, in dependence on the properties of the substrates employed.
Under tangential stress, applied by pressure in extrusion experiments, the metal microcrystals in the glass samples are stratified in concentric rings with particle density increasing towards the sample surface. Thus a new method of formation of pre-oriented glass-ceramic materials is indicated.
In Part 2 of the investigation the effect of soluble oxide additives on nucleation and crystallization in glass-forming melts is considered
Non-equilibrium thermodynamics. IV: Generalization of Maxwell, Claussius-Clapeyron and Response Functions Relations, and the Prigogine-Defay Ratio for Systems in Internal Equilibrium
We follow the consequences of internal equilibrium in non-equilibrium systems
that has been introduced recently [Phys. Rev. E 81, 051130 (2010)] to obtain
the generalization of Maxwell's relation and the Clausius-Clapeyron relation
that are normally given for equilibrium systems. The use of Jacobians allow for
a more compact way to address the generalized Maxwell relations; the latter are
available for any number of internal variables. The Clausius-Clapeyron relation
in the subspace of observables show not only the non-equilibrium modification
but also the modification due to internal variables that play a dominant role
in glasses. Real systems do not directly turn into glasses (GL) that are frozen
structures from the supercooled liquid state L; there is an intermediate state
(gL) where the internal variables are not frozen. Thus, there is no single
glass transition. A system possess several kinds of glass transitions, some
conventional (L \rightarrow gL; gL\rightarrow GL) in which the state change
continuously and the transition mimics a continuous or second order transition,
and some apparent (L\rightarrow gL; L\rightarrow GL) in which the free energies
are discontinuous so that the transition appears as a zeroth order transition,
as discussed in the text. We evaluate the Prigogine-Defay ratio {\Pi} in the
subspace of the observables at these transitions. We find that it is normally
different from 1, except at the conventional transition L\rightarrow gL, where
{\Pi}=1 regardless of the number of internal variables.Comment: 42 pages, 3 figures, citations correcte
Avrami exponent under transient and heterogeneous nucleation transformation conditions
The Kolmogorov-Johnson-Mehl-Avrami model for isothermal transformation
kinetics is universal under specific assumptions. However, the experimental
Avrami exponent deviates from the universal value. In this context, we study
the effect of transient heterogeneous nucleation on the Avrami exponent for
bulk materials and also for transformations leading to nanostructured
materials. All transformations are assumed to be polymorphic. A discrete
version of the KJMA model is modified for this purpose. Scaling relations for
transformations under different conditions are reported.Comment: 19 pages, 6 figures Accepted for publication in Journal of
Non-Crystalline Solid
Simulations of metastable decay in two- and three-dimensional models with microscopic dynamics
We present a brief analysis of the crossover phase diagram for the decay of a
metastable phase in a simple dynamic lattice-gas model of a two-phase system.
We illustrate the nucleation-theoretical analysis with dynamic Monte Carlo
simulations of a kinetic Ising lattice gas on square and cubic lattices. We
predict several regimes in which the metastable lifetime has different
functional forms, and provide estimates for the crossovers between the
different regimes. In the multidroplet regime, the
Kolmogorov-Johnson-Mehl-Avrami theory for the time dependence of the
order-parameter decay and the two-point density correlation function allows
extraction of both the order parameter in the metastable phase and the
interfacial velocity from the simulation data.Comment: 14 pages, 4 figures, submitted to J. Non-Crystalline Solids,
conference proceeding for IXth International Conference on the Physics of
Non-Crystalline Solids, October, 199
Non-equilibrium Thermodynamics: Structural Relaxation, Fictive temperature and Tool-Narayanaswamy phenomenology in Glasses
Starting from the second law of thermodynamics applied to an isolated system
consisting of the system surrounded by an extremely large medium, we formulate
a general non-equilibrium thermodynamic description of the system when it is
out of equilibrium. We then apply it to study the structural relaxation in
glasses and establish the phenomenology behind the concept of the fictive
temperature and of the empirical Tool-Narayanaswamy equation on firmer
theoretical foundation.Comment: 20 pages, 1 figur
Feasibility of single-order parameter description of equilibrium viscous liquid dynamics
Molecular dynamics results for the dynamic Prigogine-Defay ratio are
presented for two glass-forming liquids, thus evaluating the experimentally
relevant quantity for testing whether metastable-equilibrium liquid dynamics to
a good approximation are described by a single parameter. For the Kob-Andersen
binary Lennard-Jones mixture as well as for an asymmetric dumbbell model liquid
a single-parameter description works quite well. This is confirmed by
time-domain results where it is found that energy and pressure fluctuations are
strongly correlated on the alpha-time scale in the NVT ensemble; in the NpT
ensemble energy and volume fluctuations similarly correlate strongly.Comment: Phys. Rev. E, in pres
Properties of the energy landscape of network models for covalent glasses
We investigate the energy landscape of two dimensional network models for
covalent glasses by means of the lid algorithm. For three different particle
densities and for a range of network sizes, we exhaustively analyse many
configuration space regions enclosing deep-lying energy minima. We extract the
local densities of states and of minima, and the number of states and minima
accessible below a certain energy barrier, the 'lid'. These quantities show on
average a close to exponential growth as a function of their respective
arguments. We calculate the configurational entropy for these pockets of states
and find that the excess specific heat exhibits a peak at a critical
temperature associated with the exponential growth in the local density of
states, a feature of the specific heat also observed in real glasses at the
glass transition.Comment: RevTeX, 19 pages, 7 figure
A stroll among effective temperatures in aging systems: limits and perspectives
In this paper we present a short survey on the concept of effective
temperature, on its onset as a glass former vitrifies, on the various
definitions in literature and their limits of applicability. An exactly
solvable model glass is employed to compare effective temperatures among them
and to set a criterion for the occurrence of a universal extra temperature in
the framework of a "two temperature thermodynamics" for off-equilibrium aging
systems. It will be shown that aging in glass formers is not a sufficient
requirement. As an instance, memory effects typical of glasses are not
compatible with a unique effective temperature. Yet, a reduced range of
applicability can still be established and investigated.Comment: 9 pages, 5 figures, contribution to the "Glass and Entropy" special
volume of J. Non-Cryst. Solid
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