Atomistic Monte-Carlo simulations of precipitation and B2 ordering in a binary alloy on a BCC lattice via vacancy mechanism are presented. Evolution of simulated patterns is in good agreement with the experimentally observed morphologies. Moreover, it is observed that the very early stages of ordering are strongly dependent on atomic mobility parameters. Depending on the relative exchange frequency of vacancies with A and B atoms, two extreme regimes oiordering are identified, leading either to localized or delocalized ordering.

In this paper, we present the first quantitative determination of the divergence law of the correlation length ξ, when approaching the second order phase transition DO3→B2, by studying the behaviour of the APBs by transmission electron microscopy.

Ordering and grain growth have been studied in a 10 nm thick CoPt alloy film of equiatomic composition annealed in the temperature range 550–700°C by quantifying ordered domain size, volume fraction ordered, grain size, and grain size distribution. Ordering occurs by nucleation and growth of Ll0 ordered domains, with a mean size of 3 nm at 550°C and 19 nm at 700°C. The volume percent ordered shows a dramatic increase from <y1% to approximately 28% between the two extremes of annealing temperature. The mean grain size of the as-deposited films is 5 nm and the entire film is face-centered cubic. Upon annealing in the temperature range 550–600°C, the mean grain size reaches a stagnation limit of 27 nm and the grain size distribution is log-normal. Grain growth resumes beyond 600°C and the mean grain size reaches as high as 55 nm at 700°C. The increase in the coercivity of the annealed films follows the increase in the ordered fraction more closely than the increase in grain size. The shape of the M-H loop shows evidence of coupling between the magnetically hard (ordered) and soft (disordered) regions.

The structure of the σ3 (111)/[110] symmetrical tilt boundary in tungsten was modeled by molecular statics using Finnis-Sinclair type many body potentials. Several multiple structures have been found which are composed of two types of structural units and the interaction energy between these units is negative. Hence, order-disorder structural transitions may occur in the boundary with structures being ordered and/or disordered mixtures of the two units. The uansilion temperature is found to be 1158K if only the internal energy and configurational entropy arc included when evaluating the free energy. However, the transition temperature is 782K if the vibrational entropy is also incorporated. This demonstrates that the vibrational contribution to the entropy may be as important as the configurational contribution when considering the inierfacial transformations.

Ordering kinetics were measured of various alloys in the order-disorder Pt1Co1–xNix (0 ≤ x<0.5) magnetic alloy system.The kinetics of all the investigated alloys were found to be characterized by an Arrhenius temperature dependence. The associated activation energy as a parametric representation of the kinetics was evaluated as a function of the nickel content. This result was correlated with measured values of the saturation magnetization and Curie temperature of these alloys in both the atomically ordered and disordered states. A strong correlation was discovered between the activation energy and the saturation magnetization of the disordered ternary alloys.

Disordered clusters of the intermetallic compounds Ni3Al and Cu3Au have been produced using a high pressure sputtering technique. The clusters are either embedded in a film or studied, in-situ in an UHV electron microscope. The evolution of the ordered structure upon annealing is studied. Using a scanning transmission electron microscope, electron diffraction is obtained from individual clusters. Partial ordering is observed in Cu3Au clusters which have been annealed below the bulk order-disorder transition temperature. Under the experimental conditions, only clusters with sizes of 10–15 nm or larger show ordering.

The effect of heating and cooling on the long-range order transformation in stoichiometric CuAu is investigated by several complementary measuring methods. Measurements of heat flow, resistometry and acoustic emission are done dynamically by linear heating/cooling. It is shown that measuring dynamically yields the expected effect of undercooling, which decreases with decreasing cooling rate. The dependence of undercooling on cooling rate is compared with the concept of continuous cooling for glass forming. A small influence of heating rate on disordering temperature is reported (retro-effect).

Isothermal ‘order-order’ relaxations in Ll2-ordered N76Al24+0.19at.%B were studied by means of residual resistometry. This method made it possible to register very fine changes in the degree of LRO occurring about 1000K below the disordering temperature. The experimental results of two simultaneous processes being involved in these order-order relaxations with a high activation energy of 4.6eV are explained with an atomistic model of atomic jumps to nn vacancies. The parallel processes are connected with selected jumps of atoms to nn vacancies on different sublattices with a high activation energy of vacancy formation being involved.

Two complementary experimental techniques are presented that describe the mechanisms during the combustion synthesis of NiAl and Ti5Si3. The first involves quenching a reacting wedge-shaped sample imbedded in a copper block where the propagating combustion front extinguishes while traveling to the apex. The second technique, time-resolved X-ray diffraction (TRXRD), provides a direct in-situ observation of the sequence of high temperature phase transformations. The information obtained from this investigation will be useful in developing improved process models of combustion synthesis, which can lead to the production of advanced materials with tailored microstructure and properties.

Gadolinium zirconate, Gd2Zr2O7, undergoes an order-disorder transition at ∼1550°C, transforming from a defect fluorite structure (Fm3m) to a pyrochlore structure (Fd3m). Both cations and anions are ordered in the low-temperature, pyrochlore structure. In order to understand the interplay between anion and cation order parameters and ordering rates, the transformation kinetics of Gd2Zr2O7 have been examined via X-ray diffraction. Gadolinium zirconate is of particular interest because the oxygen ion conductivity of the ordered phase is significantly greatly than that of the disordered phase, in contrast to virtually every other known solid electrolyte. This difference in conductivity has provided a second technique for characterizing the transformation kinetics: in situ A.C. impedance spectroscopy. Results of the X-ray diffraction showed the growth of superstructure peak intensity to follow an apparent (time)½ dependence, rather than that expected from a nucleation and growth model. The impedance spectroscopy measurements, on the other hand, showed the conductivity to increase linearly with time. These results suggest the transition is second order in nature.

Using rf sputtering and post-deposition annealing in a differential scanning calorimeter (DSC), we manufactured bulk (4000 nm) films of crystalline Ge0.83Sn0.17. This Sn concentration is much greater than the solid solubility limit of Sn in Ge (x ≤ 0.01). Continued annealing thermally induces Sn phase separation from the alloy, limiting the ultimate attainable grain size in the metastable crystals. We examine, here, the mechanisms and kinetics of the processes limiting the size of the Ge0.83Sn0.17 polycrystals. From a combination of DSC, electron microprobe, and x-ray diffraction (XRD) measurements, we propose phase transformation mechanisms corresponding to crystallization of amorphous Ge0.83Sn0.17, crystallization of an as-yet unidentified phase of Sn, and phase separation of Sn from the Ge1-xSnx crystals. We were unable to observe the unidentified phase of Sn in XRD, but the phase must be present in the material to account for the quantitative discrepancies (as much as 8 at.%) in Sn percentages determined from each of the DSC, XRD, and electron microprobe measurements. Our models for the various transformation kinetics were corroborated by the subsequent phase-separated Sn melting behavior observed in the DSC: two Sn melting endotherms, one of which was 20–100°C lower than the bulk melting temperature of Sn. This depressed temperature endotherm we speculate represents liquefaction of nanometer-sized (β–Sn clusters.

We report the results of Monte Carlo simulations of the kinetics of surface segregation at the (001) face of CuNi and MoW alloys. These two systems were selected because they are based on different lattice structures and show contrasting segregation behavior: CuNi exhibits a monotonie profile, while that of MoW is oscillatory. To describe the energetics we have determined a set of effective cluster interactions (ECI) which govern the ordering or clustering tendencies of these alloys. The ECI were obtained by means of tight-binding electronic structure calculations in which no adjustable or experimentally determined parameters were used. Equilibrium segregation profiles are calculated and a series of quenches are performed. The layer concentrations are studied as a function of time and the existence of metastable phases in the surface region is investigated.

In this study, Si1-xGexO2 was produced by hydrothermal oxidation of Si1-xGex alloys at temperatures of 450–500°C and pressures of 30–40 MPa. The resulting Si1-xGexO2 samples were annealed in forming gas (85/15:N2/H2) and the precipitation and growth of Ge crystallites as a function of oxidation and annealing conditions were investigated using FTIR, Raman spectroscopy, XPS, AFM and high resolution SEM. The particle size distribution through the oxide thickness is accounted for by consideration of the incorporation of hydroxyl groups in the amorphous oxide network and their effect on the rate of diffusion of Ge in the amorphous structure during H2 annealing.

Single crystal Si0.63Ge0.36C0.01 and amorphous Si0.65Ge0.27C0.08 layers have been oxidized in a wet ambient at 700 °C and 900 °C. The oxide growth has been studied using Rutherford backscattering spectrometry and transmission electron microscopy. A reference sample of Si0.63Ge0.37 was also oxidized in order to determine the influence of C on the oxidation behavior. The lower C content alloy behaved similar to the SiGe alloy. Uniform Si1-xGexO2 was obtained at 700 °C whereas SiO2 was formed at 900 °C, and Ge piled up underneath the oxide. In both cases, C was not detected in the oxide layer. The amorphous Si0.65Ge0.27C0.08 alloy behaved significantly different at both oxidation temperatures in comparison with the crystalline Si0.63Ge0.36C0.01 and Si0.63Ge0.37. Negligible oxidation occurred at 700 °C whereas SiO2 was obtained at 900 °C and the rejected Ge distributed uniformly throughout the SiGeC alloy. It is proposed that fast Ge diffusion during oxidation at 900 °C resulted from diffusion at grain boundaries, since crystallization of the amorphous SiGeC layer occurred in conjunction with oxidation, leading to nucleation of ∼5 nm nanocrystals.

Cu(90 nm)/Ti(20 nm) bilayers and Cu(Ti 27 at.%) alloy films were deposited on SiO2 and annealed in an NH3 ambient at temperatures 400–700° C for 30 min. During annealing Ti segregated to both the free surface and the alloy/SiO2 interface. At the surface Ti reacted with NH3 to form TiN, whereas at the interface the Ti reacted with the SiO2 to form a TiO/Ti5Si3 structure. High resolution energy dispersive x-ray analysis revealed the presence of interfacial Cu between the Ti-silicide and Ti-oxide layers at temperatures greater than 450°C. Using Cu-Ti alloy films enhanced the Si02 consumption rate by a factor of 3-4 compared to that of pure Ti. It is suggested that the interfacial Cu is responsible for the increased rate. It is plausible that an interfacial Cu2O component has a catalytic effect on the Ti- SiO2 reaction.

The spray drying of a droplet containing a substance in solution can produce solid particles with a variety of final shapes: hollow, punctured, squashed, as well as solid spheres. The geometry affects the properties of the product. Models are presented here which describe the processes of solvent evaporation and solute crystallisation as drying takes place. The formation of a crust on the surface of the droplet is addressed. It is proposed that such a crust with a thickness of two crystallite diameters can develop into dry hollow shell. Some example calculations of the spray drying of droplets of sodium chloride solution are described.

YSZ samples containing 5 and 10 mol% of Y203 were prepared by controlled hydrolysis of metal alkoxides. The dried powders were calcined at 800°C and then they were uniaxially pressed and sintered at different temperatures and next heated at 1400°C (∼ 5 MPa) or annealed at 1600°C for 24 h. The quantitative analysis of the experimental X-ray diffraction (XRD) spectra was performed by Whole Pattern Fitting (WPF). A Pseudo-Voigt (Thompson-Cox-Hastings) was used as shape profile function. The respective phase fractions (wt %) were fitted for both solid state solutions using the scale factor. The heat treatment induced changes are discussed.

A model of substitutional ionic solid solution is applied for prediction of excess energy and the construction of binary phase diagrams of the systems SrO-MnO, SrO-FeO, SrO-CoO and SrO-NiO.

Transition metal incorporated ZrO2 gel matrices have been prepared by impregnation method and investigated with FTIR/DTA/XRD. The metastable tetragonal - monoclinic -tetragonal - cubic phase transformations are revealed in the DTA heating process up to 1400°C for the studied gels. High-temperature tetragonal to monoclinic transition is also observed in the cooling process. It is found that the diffusing metal cations stabilize the low-temperature tetragonal phase. However, for high-temperature (900°C) calcined gels, both as-prepared and metal-stabilized tetragonal phases are reduced substantially. Correlations between metal diffusion and gel polymorphic stabilities are also demonstrated.

The longitudinal (LO) and transverse (TO) A1 vibrational modes have been measured between 30-1200 cm−1 as a function of temperature (30–1240 K) for CsTiOAsO4 (CTA). The frequencies for all corresponding Raman components shifted to lower frequencies on increasing the temperature, however, there is no typical soft-mode like behavior observed in the measured frequency range. The relative intensities of the low frequency bands increase dramatically with increasing temperature due to high mobility of Cs+ ion. A higher symmetry structure taking place above 940K has been confirmed by changes in the phonon spectra.