Abstract: In the present work, a thermodynamic study was carried out in order to analyze the thermodynamic stability of the and phases in equilibrium with the phase using the calculation of phase diagrams (Calphad) formalism. The two phases and are modelled as substitutional and interstitial solid solutions of boron. The expressions of the chemical potentials of B and Fe are derived in both phases to perform the thermodynamic calculations. A comparison is made between the results provided by the substitutional and interstitial models and good agreement is observed between these two models.
Abstract: The so-called continuity equation derived by Fick is one of the most fundamental and extremely important equations in physics and/or in materials science. As is well known, this partial differential equation is also called the diffusion equation or the heat conduction equation and is applicable to physical phenomena of the conservation system. Incorporating the parabolic law relevant to a random movement into it, Boltzmann obtained the ordinary differential equation (B-equation). Matano then applied the B-equation to the analysis of the nonlinear problem for the interdiffusion experiment. The empirical Boltzmann-Matano (B-M) method has been successful in the metallurgical field. However, the nonlinear B-equation was not mathematically solved for a long time. Recently, the analytical solutions of the B-equation were obtained in accordance with the results of the B-M method. In the present study, an applicable limitation of the B-equation to the interdiffusion problems is investigated from a mathematical point of view.
Abstract: High-temperature creep experiments were performed on a Cu-2.8 ат.% Co solid solution. Cylindrical foils of 18 micrometers thickness were used for this purpose. Creep tests were performed in a hydrogen atmosphere in the temperature range of about from 1233 K to 1343 K and at stresses lower than 0.25 MPa. For comparison, a foil of pure copper and Cu-20 at.% Ni solid solution were investigated on high temperature creep. Measurements on the Cu foil showed classical diffusional creep behavior. The activation energy of creep was defined and turned out to be equal 203 kJ/mol, which is close to the activation energy of bulk self-diffusion of copper. There was a significant increase in activation energy for the Cu-20 at.% Ni solid solution. Its activation energy was about 273 kJ/mol. The creep behavior of Cu-Co solid solution was more complicated. There were two stages of diffusional creep at different temperatures. The extremely large activation energy (about 480 kJ/mol) was determined at relatively low temperature and a small activation energy (about 105 kJ/mol) was found at high temperatures. The creep rate of Cu-Co solid solution was lower than that of pure copper at all temperatures. In addition, the free surface tension of Cu-2.8 ат.% Co was measured at different temperatures from 1242 K to 1352 K. The surface tension increases in this temperature range from 1.6 N/m to 1.75 N/m. There were no features on the temperature dependence of the surface tension.
Abstract: Problems of reactive diffusion at the solid phase and melt contact are studied theoretically. The rate constant is a fundamental parameter characterizing the dissolving rate at a certain configuration of experiment. Relationships between the solid phase dissolving rate, i.e. the solid phase interface boundary movement in the melt, and rates of growth of intermetallic phases in the metal (Cu) are observed. This procedure enables the creation of surface and subsurface layers of regulated thickness in metallic materials by means of reactive diffusion. The main intention was an experimental study of copper dissolving in melts of various solder alloys and the related reactive diffusion. We used Sn, SnCu, SnAgCu, SnZn and SnIn alloys as a solder material. The problems that need to be solved preferentially are emphasized. It concerns especially the determination of the rate constant of dissolving and verifying whether the proposed model equations can be used for this constant determination in cases of cylindrical and planar dissolving. Rapid growth of phases in the metal (Cu) and determination of the thickness of layers with these phases pose considerable time demands to X-ray microanalyses (WDX, EDX, BSE, SEM) of specimens after their long-time heating.
Abstract: The Multiple-Marker (M-M) method is useful because it enables the determination of the intrinsic diffusion coefficients not only at the Kirkendall marker position but also at places where the M-M are located. However, the analysis is not applicable to the alloys with variable molar volume. In this work, a new graphical method that is applicable to the alloys with variable molar volume is proposed.
Abstract: The most important problem at the blast furnace process developing is the great coke consumption decreasing at the minimization of the general energy costs. One of the most effective ways of iron-making technical progress is the iron ore materials and coke physicochemical properties improvement which allows to increase the iron productivity and decrease the specific coke rate without construction of new blast furnaces and concentrating mills. Some of the quality indicators of iron ore raw materials and coke and their influence on the main parameters of a blast furnace smelting are considered in the paper.
Abstract: Molybdenum disilicide (MoSi2) is an interesting material for high-temperature applications. It has a high melting temperature, good thermal and electrical conductivity and an excellent oxidation resistance. For many years the primary use of MoSi2 has been in heating elements, which can be used for temperatures up to 1800°C. Since the 1990s the potential of MoSi2 as a high-temperature structural material has been recognized as well. Its brittleness at lower temperatures and a poor creep resistance above 1200°C have hindered its use as in load-bearing parts. These disadvantages may be offset at least partly by using it together with a second material in a composite or an alloy. Projected applications of MoSi2-based materials include, e.g. stationary hot section components in gas turbine engines and glow plugs in diesel engines. For future research and development directions of MoSi2-based composites diffusion is a crucial property because creep is closely connected with diffusion. This paper is devoted to the basic diffusion and defect properties of MoSi2. Data of Si and Mo as well as Ge diffusion from the Münster laboratory for both principal directions are briefly summarized. For all three kinds of atoms diffusion perpendicular to the tetragonal axis is faster than parallel to it. The diffusivities of Mo in both directions are many orders of magnitude slower than those of Si and Ge. The huge asymmetry between Mo and Si (or Ge) diffusion suggests that atomic motion of each constituent is restricted to its own sublattice. Positron annihilation studies on MoSi2 from the Stuttgart laboratory are reviewed as well. They show that formation of thermal vacancies occurs primarily on the Si sublattice but cannot exclude vacancy formation on the Mo sublattice at higher temperatures. Correlation factors for Si and Mo diffusion via sublattice vacancies in the respective sublattices of MoSi2 have been calculated recently mainly by Monte Carlo simulation techniques and are also briefly described. Diffusion, in particular self-diffusion, is discussed in connection with literature data on high-temperature creep, which is diffusion-controlled. Grain-size effects of creep have been reported and can be attributed to Nabarro-Herring and Coble creep. Power-law creep is attributed to diffusion-controlled dislocation creep. Some details are, however, not completely understood, presumably due to a lack of theoretical concepts for creep in uniaxial, stochiometric compounds and due to missing information on grain-boundary diffusion.
Abstract: With the development of nanotechnologies, the number of industrial processes dealing with the production of nanostructures or nanoobjects is in constant progress (microelectronics, metallurgy). Thus, knowledge of atom mobility and the understanding of atom redistribution in nanoobjects and during their fabrication have become subjects of increasing importance, since they are key parameters to control nanofabrication. Especially, todays materials can be both composed of nanoobjects as clusters or decorated defects, and contain a large number of interfaces as in nanometer-thick film stacking and buried nanowires or nanoislands. Atom redistribution in this type of materials is quite complex due to the combination of different effects, such as composition and stress, and is still not very well known due to experimental issues. For example, it has been shown that atomic transport in nanocrystalline layers can be several orders of magnitude faster than in microcrystalline layers, though the reason for this mobility increase is still under debate. Effective diffusion in nanocrystalline layers is expected to be highly dependent on interface and grain boundary (GB) diffusion, as well as triple junction diffusion. However, experimental measurements of diffusion coefficients in nanograins, nanograin boundaries, triple junctions, and interfaces, as well as investigations concerning diffusion mechanisms, and defect formation and mobility in these different diffusion paths are today still needed, in order to give a complete picture of nanodiffusion and nanosize effects upon atom transport. In this paper, we present recent studies dealing with diffusion in nanocrystalline materials using original simulations combined with usual 1D composition profile measurements, or using the particular abilities of atom probe tomography (APT) to experimentally characterize interfaces. We present techniques allowing for the simultaneous measurement of grain and GB diffusion coefficients in polycrystals, as well as the measurement of nanograin lattice diffusion and triple junction diffusion. We also show that laser-assisted APT microscopy is the ideal tool to study interface diffusion and nanodiffusion in nanostructures, since it allows the determination of 1D, 2D and 3D atomic distributions that can be analyzed using diffusion analytical solutions or numerical simulation.
Abstract: Precipitation effects in age-hardenable Mg-13wt.%Tb alloy were investigated in this work. The solution treated alloy was subjected to isochronal annealing and decomposition of the supersaturated solid solution was investigated by positron annihilation spectroscopy combined with transmission electron microscopy, electrical resistometry, differential scanning calorimetry and microhardness measurements. Peak hardening was observed at 200°C due to precipitation of finely dispersed particles of β phase with the D019 structure. Vacancy-like defects associated with β phase particles were detected by positron annihilation. At higher temperatures precipitation of β and subsequently β phase takes place. Formation of these phases lead to some additional hardening and introduces open volume defects at precipitate/matrix interfaces. To elucidate the effect of plastic deformation on the precipitation sequence we studied also a Mg-13wt.%Tb alloy with ultra fine grained structure prepared by high pressure torsion. In the ultra fine grained alloy precipitation of the β phase occurs at lower temperature compared to the coarse grained material and the peak hardening is shifted to a lower temperature as well. This effect can be explained by enhanced diffusivity of Mg and Tb atoms due to a dense network of grain boundaries and high density of dislocations introduced by severe plastic deformation. Moreover, dislocations and grain boundaries serve also as nucleation sites for precipitates. Hence, precipitation effects are accelerated in the alloy subjected to severe plastic deformation.