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Nanocrystallization by heat treatment of initially amorphous alloys occurs for high nucleation frequency I and low crystal growth rate u values. Calorimetrie data extracted, for instance, from differential scanning calorimetry are normally presented by the dependence of the crystallized fraction x, on: i) x=x(T,t) when obtained under isothermal annealing at temperature T as a function of time t; ii) x=x(τ,β) when obtained under continuous heating at a scan rate β as a function of temperature. Theoretical analysis of the crystallization kinetics is presented which accounts for nuclei either pre-quenched or created by homogeneous nucleation whose initial steps of growth are controlled by the interface formation between the nanocrystals and the matrix and subsequent growth is limited by diffusion.
The evolution of the B2-AlFe phase during mechanical grinding in Ar has been examined as a function of milling time by X-Ray diffraction, transmission Mössbauer spectroscopy and differential scanning calorimetry. Short and long range disorder was observed to increase with the mechanical treatment up to the attainment of a steady state. The evolution of the long range order parameter and of the local atomic configurations at Fe sites were analyzed in terms of possible mechanisms for milling induced disordering. The kinetics of the thermal reordering was studied under continuous heating and isothermal calorimetrie regimes. Modeling of the reordering processes by diffusion controlled growth of pre-existing ordered grains is presented as well as the estimated values of both the enthalpy and the activation energy of the reordering process. The results are consistent with a non uniform distribution of disorder throughout the sample and will be compared with preceding information on related systems.
The kinetics of intermediate phase formation in the Cu/Mg multilayer system is analyzed using Differential Scanning Calorimetry. Three main exothermic processes are found during the continuous DSC treatments. The first two, significantly overlapped, are related to the same process, nucleation and growth of the Mg2Cu along the interface. We interpret differences between the Mg/Cu and Cu/Mg interfaces are at the origin of this unexpected behavior. The third exothermic reaction is due to the growth of the Mg2Cu phase perpendicular to the original interface. A kinetic model is developed which yields calorimetric traces in good agreement with the experimental data.
Differential Scanning Calorimetry (DSC), X-ray Diffraction (XRD), Neutron Diffraction (ND) and Mössbauer Spectroscopy (MS) were used to study the nanocrystallization process of Fe73.5Cu1Nb3Si22.5–xBx (x=5, 7, 8, 9 and 12) amorphous alloys. Both the temperature range and the activation energy of Fe(Si) phase precipitation from the amorphous martrix increase with the initial B composition. The initial Si composition influences the mechanism of the nanocrystallization: for the Si rich samples, the beginning of nucleation and growth processes is interface controlled, for the B rich samples it is diffusion controlled. Secondary crystallization from the remaining amorphous is mainly Fe3B and Fe2B, the ratio of Fe3B/Fe2B being dependent on the initial composition too.
Mechanical alloying and rapid solidification are two important routes to obtain glassy alloys. New Fe-Ni based metal-metalloid (P-Si) alloys prepared by these two different processing routes were studied by differential scanning calorimetry and transmission Mössbauer spectroscopy. Mechanical alloyed samples were prepared with elemental precursors, and different nominal compositions. Rapidly solidified alloys were obtained by melt-spinning. The structural analyses show that, independent of the composition, the materials obtained by mechanical alloying are not completely disordered whereas fully amorphous alloys were obtained by rapid solidification. Consequently, the thermal stability of mechanically alloyed samples is lower than that of the analogous material prepared by rapid solidification. The P/Si ratio controls the magnetic interaction of the glassy ribbons obtained by rapid solidification. The experimental results are discussed in terms of the degree of amorphization and crystallization versus processing route and P/Si ratio content.
The aim of the present paper is to analyse the melting/solidification of pure metals resulting from non-equilibrium conditions. Attention is focused on the direct measurement of the calorimetric signal obtained under isothermal hold of the sample at a temperature close to the equilibrium melting temperature Tm, which results in both melting of an overheated solid and solidification of an undercooled melt. The non-equilibrium transformations are monitored by DSC under isothermal regime, with previous continuous heating/continuous cooling of the sample. The dependence of the calorimetric signal on thermodynamic factors, ΔH and ΔG, is explored. Here ΔH and ΔG are, respectively, the melting enthalpy and Gibbs free energy difference between the crystal and the liquid. In particular, the results of the investigation performed on the melting/solidification behaviour of pure In and Pb are presented.
The aim of the present paper is to analyse the glass formation and stability of bulk metallic glasses. Attention is focused to metallic alloys as systems which may develop a large glassforming ability. Glass formation when quenching from the liquid state is discussed in terms of the thermodynamics and kinetics of the stable/metastable competing phases. Thermodynamics is required to relate glass transition temperature, Tg, to the energetics of the supercooled liquid. Kinetic destabilisation of equilibrium solidification and, consequently, glass forming ability are favoured by the high viscosity values achieved under continuous cooling. The relative thermal stability of the supercooled liquid depends on the thermodynamic driving force and interfacial energy between each competing nucleating phase and the molten alloy. It is shown that the quantities representative of the process, once scaled, have a temperature dependence that is mostly fixed by the reduced glass transition temperature, Tgr= Tg/Tm, Tm being the melting temperature. Based on the classical models of nucleation and crystal growth, the reduced critical cooling rate is shown to follow master curves when plotted against Tgr. Experimental trends for specific systems are compared to predicted values from these master curves.
The microstructure developed in primary crystallizations is studied under realistic conditions. The primary crystallization of an amorphous alloy is modeled by considering the thermodynamics of a metastable phase transition and the kinetics of nucleation and crystal growth under isothermal annealing. A realistic growth rate, including an interface controlled growth at the beginning of the growth of each single grain and diffusion controlled growth process with soft impingement afterwards is considered. The reduction in the nucleation rate due to the compositional change in the remaining amorphous matrix is also taken into account. The microstructures developed during the transformation are obtained by using the Populational KJMA method, from the above thermodynamic and kinetic factors. Experimental data of transformed fraction, grain density, average grain size, grain size distribution and other related parameters obtained from annealed metallic glasses are modeled.
A theoretical analysis of the transformation kinetics which accounts for nuclei, either prequenched or created homogeneously, and whose growth are controlled by diffusion is presented. The change in growth habit intervening during the transformation is analysed in terms of the evolution of the free energy difference between the precipitate and the matrix at the interface, ΔG1. In the Avrami formalism, this quantity accounts for the competition between interface and diffusion controlled growth whereas the nucleation events are driven by the free energy difference between the precipitate and the bulk matrix. Competition and selection of precipitate phases in highly undercooled melts using the CALPHAD approach for the evaluation of the free energies and the changes in diffusivity with concentration are analysed. Experimental vs. calculated data are discussed in some rapidly solidified metallic systems.
The uncertainties inherent to experimental differential scanning calorimetric data are evaluated. A new procedure is developed to perform the kinetic analysis of continuous heating calorimetric data when the heat capacity of the sample changes during the crystallization. The accuracy of isothermal calorimetric data is analyzed in terms of the peak-to-peak noise of the calorimetric signal and base line drift typical of differential scanning calorimetry equipment. Their influence in the evaluation of the kinetic parameter is discussed. An empirical construction of the time-temperature and temperature-heating rate transformation diagrams, grounded on the kinetic parameters, is presented. The method is applied to the kinetic study of the primary crystallization of Te in an amorphous alloy of nominal composition Ga20Te80, obtained by rapid solidification.
The kinetics of crystallization of four amorphous (or partially amorphous) melt spun Nd–Fe–B alloys induced by thermal treatment is studied by means of differential scanning calorimetry and scanning electron microscopy, In the range of temperatures explored experimentally, the crystallization process is thermally activated and generally proceeds in various stages. The Curie temperature and the crystallization behavior have been measured. The apparent activation energy of crystallization of most of the crystallization stages has been determined for each melt spun alloy. The explicit form of the kinetic equation that best describes the first stage of crystallization has been found. It follows in general the Johnson-Mehl-Avrami-Erofe'ev model, but clear deviations to that model occur for one alloy. Scanning electron microscopy demonstrates that preferentially hetereogeneous nucleation occurs at the ribbon surface which was in contact with the wheel. From crystallization kinetics results the lower part of the experimental time-temperature-transformation curves for all studied alloys are deduced and extrapolated to the high temperature limit of their range of validity, also deduced.
A simple expression for the Gibbs free energy of formation of a pure component or a eutectic alloy glass, relative to the stable crystalline phase (or phases) at the same temperature is deduced by use of thermodynamic arguments. The expression obtained is supposed to apply to both monocomponent and multicomponent liquid alloys that might become glasses from the supercooled liquid state, irrespective of the critical cooling rate needed to avoid crystallization.
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