Structural Relaxation Kinetics for First and Second-Order Processes: Application to Pure Amorphous Silicon

The structural relaxation of amorphous materials is described as arising from the superposition of elementary processes with varying activation energies. We show that it is possible to obtain the kinetic parameters of these processes from differential scanning calorimetry experiments. The transformation rate is predicted for the transient decay when an isotherm is reached and for the relaxation threshold detected in partially relaxed samples. Good agreement is obtained with experiment if the individual components transform through first-order kinetics, but inconsistencies arise for second-order components. Our analysis, that improves the classical treatment by Gibbs et al.[1], allows the activation energies and the pre-exponential rate constants to be extracted independently. When applied to a-Si, we conclude that the pre-exponential rate constant is far from constant. The kinetic parameters obtained from DSC are used to analyze the relaxation of a-Si in pulsed laser experiments and to discuss the relationship between structural relaxation and crystallization.Comment: 21 pages and 10 figures; accepted for publication in Acta Materialia (2009

Numerical model of solid phase transformations governed by nucleation and growth. Microstructure development during isothermal crystallization

A simple numerical model which calculates the kinetics of crystallization involving randomly distributed nucleation and isotropic growth is presented. The model can be applied to different thermal histories and no restrictions are imposed on the time and the temperature dependencies of the nucleation and growth rates. We also develop an algorithm which evaluates the corresponding emerging grain size distribution. The algorithm is easy to implement and particularly flexible making it possible to simulate several experimental conditions. Its simplicity and minimal computer requirements allow high accuracy for two- and three-dimensional growth simulations. The algorithm is applied to explore the grain morphology development during isothermal treatments for several nucleation regimes. In particular, thermal nucleation, pre-existing nuclei and the combination of both nucleation mechanisms are analyzed. For the first two cases, the universal grain size distribution is obtained. The high accuracy of the model is stated from its comparison to analytical predictions. Finally, the validity of the Kolmogorov-Johnson-Mehl-Avrami model is verified for all the cases studied

Nonlinear oscillatory mixing in the generalized Landau scenario

We present a set of phase-space portraits illustrating the extraordinary oscillatory possibilities of the dynamical systems through the so-called generalized Landau scenario. In its simplest form the scenario develops in N dimensions around a saddle-node pair of fixed points experiencing successive Hopf bifurcations up to exhausting their stable manifolds and generating N-1 different limit cycles. The oscillation modes associated with these cycles extend over a wide phase-space region by mixing ones within the others and by affecting both the transient trajectories and the periodic orbits themselves. A mathematical theory covering the mode-mixing mechanisms is lacking, and our aim is to provide an overview of their main qualitative features in order to stimulate research on it.Peer ReviewedPostprint (author's final draft

Nonlinear complexification of periodic orbits in the generalized Landau scenario

We have found a way for penetrating the space of the dynamical systems towards systems of arbitrary dimension exhibiting the nonlinear mixing of a large number of oscillation modes through which extraordinarily complex time evolutions may arise. The system design is based on assuring the occurrence of a number of Hopf bifurcations in a set of fixed points of a relatively generic system of ordinary differential equations, in which the main peculiarity is that the nonlinearities appear through functions of a linear combination of the system variables. The paper outlines the design procedure and presents a selection of numerical simulations with a variety of designed systems whose dynamical behaviors are really rich and full of unknown features. For concreteness, the presentation is focused to illustrating the oscillatory mixing effects on the periodic orbits, through which the harmonic oscillation born in a Hopf bifurcation becomes successively enriched with the intermittent incorporation of other oscillation modes of higher frequencies while the orbit remains periodic and without necessity of bifurcating instabilities. Even in the absence of a proper mathematical theory covering the nonlinear mixing mechanisms we find enough evidence to expect that the oscillatory scenario be truly scalable concerning the phase space dimension, the multiplicity of involved fixed points and the range of time scales, so that extremely complex but ordered dynamical behaviors could be sustained through it.Peer ReviewedPostprint (author's final draft

Thermal decomposition of CuProp2: In-situ analysis of film and powder pyrolysis

The thermal decomposition of CuProp2 in the form of film and powder was studied in different atmospheres by means of thermal analysis techniques (TG-MS, TG-IR, EGA), chemical-structural methods (FTIR, XRD, EA) and computational thermochemistry (VASP/PBE). The decomposition mechanism in terms of volatiles evolved was disclosed with the aid of ab-initio modeling; it was found to be dependent on the gas diffusion in and out of the sample and accelerated by a humid atmosphere. In films, the copper redox behavior showed sensitivity to the residual atmosphere. Finally, the role of the metal center is discussed in the frame of a general decomposition mechanism for metal propionates

Melting temperature of YBa2Cu3O7−x and GdBa2Cu3O7−x at subatmospheric partial pressure

AbstractThe melting temperature, Tm, of YBa2Cu3O7−x and GdBa2Cu3O7−x superconductor ceramic compounds has been measured by differential thermal analysis (DTA) over a large oxygen partial pressure range of five orders of magnitude (2·10−5 < PO2 < 1 bar). It is shown that the DTA peak and endset temperatures are closer to Tm than the onset temperature. Correct measurement of Tm requires low heating rates and subatmospheric pressure conditions to avoid temperature shifts due to local oxygen overpressure and kinetic effects

Low temperature processing of solution-derived ceria deposits on flat surfaces of 3D-printed polyamide

Doped ceria deposits have been prepared on 3D-printed polyamide-12 components starting from inkjet-compatible solutions in an attempt to functionalize the surface of the plastic part, followed by a low temperature decomposition process at 160¿°C in air. The non-continuous deposits were characterized by simultaneous thermogravimetric analysis, differential scanning calorimetry and evolved gas analysis, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy with energy dispersive X-ray spectroscopy, transmission electron microscopy and electron diffraction. After thermal treatment, the deposits are still clearly visible at the surface of the polymer. However, no crystallinity of the ceria is observed, in contrast to identical low temperature processing on inert substrates such as glass where nanoparticle ceria aggregates were produced. This is tentatively explained by the chemically-reducing character of the polyamide, and in particular to CO and hydrocarbon gases released during the heating process, which would continuously induce the reduction of Ce4+ to Ce3+ at the low temperature of 160¿°C, influencing the non-detection of crystalline ceria.Peer ReviewedPostprint (published version

Cell size distribution in a random tessellation of space governed by the Kolmogorov-Johnson-Mehl-Avrami model: Grain size distribution in crystallization

The space subdivision in cells resulting from a process of random nucleation and growth is a subject of interest in many scientific fields. In this paper, we deduce the expected value and variance of these distributions while assuming that the space subdivision process is in accordance with the premises of the Kolmogorov-Johnson-Mehl-Avrami model. We have not imposed restrictions on the time dependency of nucleation and growth rates. We have also developed an approximate analytical cell size probability density function. Finally, we have applied our approach to the distributions resulting from solid phase crystallization under isochronal heating conditions

The configurational energy gap between amorphous and crystalline silicon

The crystallization enthalpy of pure amorphous silicon (a-Si) and hydrogenated a-Si was measured by differential scanning calorimetry (DSC) for a large set of materials deposited from the vapour phase by different techniques. Although the values cover a wide range (200-480 J/g), the minimum value is common to all the deposition techniques used and close to the predicted minimum strain energy of relaxed a-Si (240 ± 25 J/g). This result gives a reliable value for the configurational energy gap between a-Si and crystalline silicon. An excess of enthalpy above this minimum value can be ascribed to coordination defects