Potential in microroughness domain of metal surface employed in cathodic protection mode

This effort presents the results of investigation of cathodic protection process of a section of the main pipeline, which has been operating in cathodic protection mode for a long time and which insulation has completely exfoliated from metal surface, and a cavity between is filled with water and salt impurities. In this case, a decisive factor is a fact that a metal surface is covered with microroughnesses in the form of protrusions with almost conical shape. The surface is immersed in electrolyte. At the electrolyte-metal interface, a potential difference is formed - a corrosion potential, which creates an unstable equilibrium among the potentials of metal and electrolyte. A mathematical model is designed and implemented into a numerical algorithm and computer program. A computational experiment has been carried out to calculate the potential around microroughness. The model describes a change in potential in this area at incomplete and complete cathodic protection of metal surface. The basis of computational model is a selection of one of metal protrusions of material microheterogeneity and placing it in a cylinder, which diameter coincides with that one of the lower base of this protrusion, and its upper part passes through the apex of the protrusion. Mathematical model equations with corresponding boundary conditions and their discrete implementation are presented. The solution of problems is obtained by iterative procedures based on reference values of protective potential taken from practice. The results of computational experiment are presented in the form of graphs: 1) potential distribution in the field of electrolytes; 2) changes in electrolyte potential at the border with protrusion at different values of polarization potential; 3) changes in polarization resistance in the area (calculated). The geometry of computational domain was also varied, and the values of protective potential were determined to ensure the absence of corrosion. Keywords: corrosion, microroughness, protective potential, plastic current density, electrolyte

Simulation of the interaction of plastic zone dislocations with the grain boundary at brittle-plastic transition temperatures in molybdenum

The (DD) method was used to model the formation of the plastic zone of the top of the cracks in polycrystalline molybdenum. Special attention was paid to take into account the interaction of dislocations in the plastic zone with grain boundaries. Structural sensitivity of fracture toughness was analyzed under brittle-ductile condition. Simulations were performed for a range of grain sizes from 400 to 100 μm, at which a sudden increase in fracture toughness with a decrease of grain size was experimentally shown. We calculated the value of K1c taking into account the shielding action of dislocations. The position of all dislocations in the plastic zone at fracture moment was calculated. Based on these data, we obtained the dependences of dislocation density on the distance from the crack tip thereby confirming significant influence of the grain boundaries on plastic zone formation. At large grain sizes, when the plastic zone does not touch the boundary, the distribution of dislocations remained unchanged. As grains reduce their size to size of the plastic zone, they start formating a dislocation pile – up near the boundaries. Dislocations on plastic zone move slightly toward the crack tip, but the density of dislocations in the middle of the grain remains unchanged, and fracture toughness remains almost unchanged. Further reduction of the grain size leads to the Frank-Reed source activation on the grain boundary Forming dislocation pile-up of the neighbor grains. Its stress concentration acts on dislocations of the first grain and causes redistribution of plastic zone dislocations. If the reduction in grain size is not enough to form a strong pile-up, density of dislocations on plastic zone increases slightly and crack resistance increases a few percent. Further reduction of grains promotes strong pile-up, dislocations move to crack tip, and its density on plastic zone increases. Crack is shielded and fracture toughness increases sharply. The calculation showed that the fracture toughness jump is observed at grain sizes of 100—150 μm, in good agreement with the experiment. Keywords: dislocation dynamics simulation, molybdenum, fracture toughness, grain size, plastic zone, brittle-ductile transition.

Extended characterization of materials based on continuous instrumented indentation diagrams

In addition to the traditional determination of hardness and elastic moduli from continuous diagrams of instrumental indentation, it is proposed to determine the yield stress, the characteristic of plasticity, the characteristic relative size of the elastoplastic zone under the indenter, and the volumetric deformation of the material in the area of contact of the indenter with the sample. The indentation diagram shows the transition point to the unconstrained material flow under the indenter. Keywords: indentation, hardness, elastic moduli, contact stiffness, elastic-plastic strains.

Thermodynamic properties and phase equilibria in alloys of Bi—Tm system

The thermochemical properties of the melts of the Bi—Tm system at a temperature of 1100 K in the range of compositions 0 ≤ xTm ≤ 0,2 were determined for the first time by the calorimetry method. It is established that the minimum value of the enthalpy of mixing of these liquid alloys is equal to –75,7 ± 0,5 kJ / mol at xTm = 0,65. = = –150,7 ± 16,7 kJ / mol, = –230,9 ± 21,8 kJ / mol. The activities of the components and molar particles of associates were calculated according to the model of an ideal associated solution (IAR), using data on the thermochemical properties of melts of the Bi—Tm system. It was found that the activities of the components in these metallic solutions show very large negative deviations from ideal solutions with a high content of TmBi and Tm2Bi associates. The obtained dependences of the first i i melts of the Bi—Tm system on temperature showed a large steepness of the Bi Bi curve in contrast to the gradual decrease of exothermic values Tm of Tm. This indicates large changes in the structure of the Bi atom with increasing temperature. Excess integral and partial Gibbs energies of Bi-Tm system melt mixing calculated from component activities The absolute values of G in the whole concentration range are smaller than H (G min = –41,8 kJ / mol at xTm = 0,58), and the function G of is more asymmetric, which is caused by the entropy contribution (entropy of mixing of the studied melts is negative, and Smin min = −30,5 J / mol ∙ K at xTm = 0,65). Keywords: thermochemical properties, compounds, melts, Bi, Tm.

First principle methods for calculating the linear coefficient of thermal expansion of quasi-binary eutectic systems

To calculate the linear coefficient of thermal expansion (LCTE) and its temperature dependence, a combination of the method of a priori pseudopotential and quasi-harmonic approximation (author's methods) is used. After approximating the results obtained for metal-like materials (carbides, borides, silicides), the LCTE is presented in an analytical form. In the case of quasi-binary eutectic systems based on carbides, borides, silicides, to estimate the interaction energy of the elements of two components, the concept of a virtual crystal (with a virtual cell) along the line of contact of two components is introduced. A virtual cell is assigned a volume average between the volume of a unit cell of two components, taking into account their concentration ratio. The components that make up the eutectic retain their crystal structure, their LCTE can be estimated as for pure components. Without taking into account the influence of interphase interaction, the LCTE of the eutectic system is determined using the rule of mixtures based on the LCTE components, taking into account their volume fraction. Taking into account the influence of the interface on thermal expansion is estimated by the virtual cell assigned to it. To determine the LCTE of the eutectic system, a ratio is proposed that connects the LCTE components and the docking boundaries through the concentration ratio. This method more realistically describes the structure of a quasi-binary eutectic. There is a consistency between the calculated and experimental data. Keywords: electron-ion system energy, interatomic interaction potential, quasiharmonic approximation, linear coefficient of thermal expansion, eutectic temperature.

Modeling of influence of planar defects on plasticity of powder materials by computational methods of micromechanics

Based on the energy concept of the critic stress state, a three-parameter model of plasticity of the Cam-Clay type was formulated. For this phenomenological model, the dependences of the determining parameters on the porosity and damage were found by the method of micromechanical averaging on the unit cell corresponding to the porous damaged material of powder origin. The plastic multi-responce (different yield strength in tension and compression) behavior of this material is found by micromechanical averaging on a unit cell. According to the mechanics of composites, the geometry of the cell represents the structure of a heterogeneous material and the boundary conditions on a unit cell make it possible to relate the stress-strain state at the macro- and meso-level. The averaging was carried out by computer simulation using the finite element method with an adaptive mesh, which was automatically condensed in places of a large gradient of the stress-strain state. The structure of the representative cell corresponds to a powder origin material with "imperfect", partially stratified, interparticle contacts. In the proposed model the rheological response of a porous damaged material is specified by three moduli, and the structure of such a material is described by two internal state parameters: porosity and the degree of delamination of interparticle contacts. That is, the rheological moduli are functions of porosity and damage. Accordingly, a number of values of each of the moduli were calculated for a certain discrete range of density and damage. The advantage of this approach is precisely in focusing on powder origin materials and not generally on any damaged materials, which makes it possible to take into account the real structure of the damaged material using the methods of mechanics of microheterogeneous materials. According to the simulation results, in particular, it was found that the yield strength for shear is significantly (30%) less sensitive to damage than the yield strength for uniaxial tension. Keywords: theory of plasticity, powder materials, micromechanics, damaged materials, stress-strain state.

The effect of fuel gas mixtures and air flow rates on electrical properties of solid oxide fuel cell

Fuel Cells are one of the most efficient and environmentally friendly devices for electricity generation, which are developing rapidly and are already in the early stages of commercialization. Solid Oxide Fuel Cells (SOFC) areone of the most promising their types due to the highest efficiency, fuel flexibility (H2, CnHm, CO etc.) and no needs in platinum group catalysts. The performance of SOFC is affected by various polarization losses, which aredependant on selected materials, their structure and SOFC operation parameters. Over the last decade, much attention is given to the study of SOFC’s electrochemical properties at different operating regimes: temperatures, fuels, fuel and oxidantflow rates etc. The work is devoted to studying the influence of the model fuel (5% H2—Ar) and air (oxidant) flow rates on electrical properties of Solid Oxide Fuel Cellat 800 °C to determine the best combination of gas flow rates, which provide the maximum values of specific electric power. The fuel (0,35 l/min) and oxidant (1 l/min)flow rates was found as the optimal operation regime of fuel and air supply for the SOFC tested. The highest electrical densityto be ensured by the model fuel was determined as 34 mW/cm2. The amount / flow rate of oxidant and fuel gases supplied to the fuel cell does not correspond to the ratio of the reagents of the chemical reaction of oxidation of the fuel. This difference is explained by the fact that the SOFC effectiveness of fuel and oxidant utilization depends not only from to the properties structure and materials of each components: anode, cathode, electrolyte, but also from concentration of fuel and oxidant in model fuel or air, which also creates a barrier for oxidant and fuel molecules to reach the reaction zone. Keywords: Solid Oxide Fuel Cell, electrical properties, fuelgasmixtures, hydrogen, oxidant.

Thermodynamic properties of alloys binary In—Pr (Nd) and ternary In—Pr (Nd)—Ni systems

The thermochemical properties of In—Pr system melts in the range of compositions 0 < xIn < 0,4 and In—Nd in the whole concentration range at 1573 ± 1 K were investigated by isoperibolic calorimetry. The obtained data for the In—Pr system melts were extrapolated to the unexplored concentration interval, taking into account that at xPr = 1 the integral and partial mixing for Pr enthalpy are equal to zero. It was found that the first partial for Pr and the minimum enthalpy of mixing are equal to –139 ± 11 and –40,3 ± 0,2 kJ / mol, respectively. For the In—Nd system the first partial for In and Nd, the minimum enthalpy of mixing is equal to −131,7 ± 11, −140,6 ± 12 і –43,3  0,2 kJ / mol, respectively. Comparison of ΔHmin, melts of the five previously studied In—Ln systems from the ordinal number Ln (zLn) together with the data obtained in this work showed that they are described by a single trend line. For ΔHmin of melts of In—Eu (Yb) systems there are very insignificant deviations from the trend line. But for the size factor, these deviations from the trend line are more significant. The enthalpies of formation of some intermetallics of In—Ln systems are known, and most of them belong to the compound LnIn3. But there is no complete agreement between these data. The results of the most modern work show less dependence on the serial number of lanthanide and are more exothermic for heavy lanthanides, compared with other data. Keywords: thermochemical properties, compounds, melts, In, Pr, Nd.

The estimation of energy and elastic properties of TiAlNb materials based on results of first principles calculations

The results of research of isolated TiAlNb clusters are presented. The models of isolated clusters of 27, 59, 65 atoms in size which is fragments of the bcc structure have been constructed. The models stoichiometry imitate α-, γ-, α+γ- and β-phase TiAlNb alloys. The structural, cohesive and electronic properties of these clusters have been investigated within the framework of electronic density functional theory with PBE0 functional with a set of MINI basis functions with application of Gaussian'03 and GAMESS software packages. It was found that upon transition of the cluster structure from the α- to the β-phase, the cohesion energy increases and the crystal lattice period decreases. This corresponds to an increase in the values of the structure strength and density. For the calculation of the bulk modulus were utilized value of changes in energy and volume of cluster, got in research. The bulk modulus of the isolated β-phase TiAlNb cluster is predicted. This bulk modulus near to 142.4 GPa. The result was extended to volumetric structures. The investigation showed that bulk modulus of Ti2AlNb materials near to 163.6 GPa. Comparison of calculation results with experimental values of elastic moduli of materials with similar structure and composition is carried out. The comparison revealed the agreement between the calculated values and the results of experiments. A method is proposed for evaluating the elastic properties of TiAlNb alloys based on the results of first principles calculations. Keywords: cluster, aluminide titanium, bulk modulus, computer material science.

Modelling of shear stress field in glide plane in substitutional solid solutions

The formation of stochastic shear stress field in the glide plane in the substitutional solid solution was investigated by computer simulation. If the atoms in the crystal lattice nodes of the substitutional solid solution are considered as a kind of point defects in the virtual solvent medium, the shear stress distribution in the glide plane can be calculated based on the interaction of edge dislocation and such defects. For concentrated solid solutions, the shear stress will be a normally distributed random value with zero mathematical expectation. The standard deviation of this distribution will be the greater the greater the effective distortion of crystalline lattice of the alloy. In the case of dilute solid solution, where one of the components has a predominant content, the simulation gives shear stress distribution in the glide plane, where large peaks are separated from each other by wide areas of near-zero stresses. Thus, there are separate discrete obstacles in the form of large stress peaks for the edge dislocation in the glide plane in dilute solid solution, and the space between the peaks is practically stress-free. The average distance between large peaks correlates with the average distance between the atoms of those components that are few in solution, if total atomic fraction of these components is considered. Thus, the proposed modeling gives a very realistic shear stress distribution in the glide plane for concentrated and dilute substitutional solid solutions with fcc and bcc structures. This can be useful in further modeling the yield strength in multicomponent alloys. Keywords: dislocation, distorsion, shear stresses.