An examination of a multicomponent diffusion couple

New expressions relating the interdiffusion flux of a component to its own concentration gradient in a multicomponent diffusion couple have been derived and applied to a diffusion couple investigated in the Cu-Ni-Zn system. From these relations, effective interdiffusion coefficients were determined at selected sections in the diffusion zone directly from the locations of the sections relative to the Matano plane. The Cu-Ni-Zn couple was analyzed for interdiffusion fluxes and interdiffusion coefficients with the aid of “MultiDiFlux” program developed for the analysis of interdiffusion in multicomponent systems. The couple was examined for zero-flux plane development, interdiffusion against activity gradients, and diffusion path representation. Diffusion path slopes at selected sections in the diffusion zone were related to the interdiffusion coefficients; slopes at path ends were determined from eigenvectors evaluated from limiting ratios of interdiffusion fluxes. Expressions for internal consistency among the concentration profiles or flux profiles of the individual components were also developed in terms of the terminal alloy compositions and applied to the Cu-Ni-Zn couple in the diffusion zone. This article was presented at the Multicomponent-Multiphase Diffusion Symposium in Honor of Mysore A. Dayananda, which was held during TMS 2006, 135th Annual Meeting and Exhibition, March 12–16, 2006, in San Antonio, TX. The symposium was organized by Yongho Sohn of University of Central Florida, Carelyn E. Campbell of National Institute of Standards and Technology, Richard D. Sisson, Jr., of Worcester Polytechnic Institute, and John E. Morral of Ohio State University.     

Interdiffusion analysis for NiAl versus superalloys diffusion couples

Solid-to-solid diffusion couples, β-NiAl (B2) versus various commercial superalloys (i.e., CM247, GTD-111, IN-939, IN-718, and Waspalloy) were examined to quantify the rate of Al interdiffusion as a function of initial superalloy composition. The diffusion couples were assembled with Invar steel jig encapsulated in Ar by sealing in quartz capsules and annealed at 1050 °C for 96 h. Concentration profiles measured by electron probe microanalysis in the single-phase β-NiAl region were used to determine interdiffusion fluxes and effective interdiffusion coefficients of individual components in the single-phase β-NiAl side of the couple. The values determined using experimental concentration profiles of the single-phase β-NiAl side of the couple were used to predict effective interdiffusion coefficients in multiphase superalloy side of the couple based on mass balance and local continuity of interdiffusion fluxes. Microstructural and compositional stability of protective coatings (e.g., NiCoCrAlY and NiAl) as a function of superalloys composition are discussed based on effective interdiffusion coefficients predicted from diffusion couple studies. This article was presented at the Multicomponent-Multiphase Diffusion Symposium in Honor of Mysore A. Dayananda, which was held during TMS 2006, 135th Annual Meeting and Exhibition, March 12–16, 2006, in San Antonio, TX. The symposium was organized by Yongho Sohn of University of Central Florida, Carelyn E. Campbell of National Institute of Standards and Technology, Richard D. Sisson, Jr., of Worcester Polytechnic Institute, and John E. Morral of Ohio State University.     

Stress-induced destabilization of solidification and melting fronts

The morphological evolution of the initially planar solidification and melting fronts of a thin liquid film in a stressed binary alloy has been investigated when diffusion only proceeds in the liquid phase. A linear stability analysis has been performed and the diffusion-controlled evolution of the shape of both fronts has been characterized. The destabilizing effect of stress on the profiles of the interfaces has been identified for a liquid film at rest when the solid is submitted to constant stress and when it is migrating, due to stress gradient, in the hypothesis where concentration field of solute satisfy Laplace’s equation. The possibility of roughness formation in the early beginning of the development of the solid–liquid interfaces has been finally discussed for alloys in the context of a liquid film migration mechanism.     

Diffusion reaction behaviors of U-Mo/Al dispersion fuel

The uranium (U)-molybdenum (Mo)/aluminum (Al) dispersion fuel that is currently under development for high-performance research reactors has shown complicated diffusion reaction behavior between the U-Mo particles and the Al matrix. Diffusion reactions in U-Mo/Al dispersion fuels were characterized by out-of-pile annealing tests and in-pile irradiation tests in the HANARO research reactor. The effect of the addition of a third element such as silicon (Si), Al, or zirconium (Zr) to U-Mo fuel, and the addition of Si to the Al matrix on the diffusion reaction were also investigated. The growth rate and activation energy for the reaction phases of U-Mo/Al dispersion fuels were obtained. The effect of alloying a small amount of a third element in U-Mo and of Si in the Al matrix on diffusion reaction kinetics was negligible in annealing tests conducted at ∼550 °C. γ phase stability in the U-Mo alloy was enhanced by the addition of 0.1 to 0.2 wt.% Si. The Si accumulated in the interdiffusion layer of U-Mo/Al-Si dispersion fuel annealed at ∼550 °C, whereas Zr migration to the interdiffusion layer of U-Mo-Zr/Al was negligible. This article was presented at the Multicomponent-Multiphase Diffusion Symposium in Honor of Mysore A. Dayananda, which was held during TMS 2006, the 135th Annual Meeting and Exhibition, March 12–16, 2006, in San Antonio, TX. The symposium was organized by Yongho Sohn of University of Central Florida, Carelyn E. Campbell of National Institute of Standards and Technology, Richard D. Sisson, Jr., of Worcester Polytechnic Institute, and John E. Morral of Ohio State University.     

Internal carburization and carbide precipitation in Fe-Ni-Cr alloy tubing retired from ethylene pyrolysis service

The events leading to the failure of an alloy grade HP Nb ethylene pyrolysis heater tubing were examined. X-ray maps indicated that a complex oxide coating, which inhibits carbon (C) diffusion, forms on the process side of the tubing during service. Phase equilibria studies predict that even without process C diffusion, metal carbides will precipitate out of the face centered cubic (FCC_Al) matrix. It was estimated that a 6 mm thick tube operating at 1100 °C would completely carburize in two years if the protective coating is damaged. This article was presented at the Multicomponent-Multiphase Diffusion Symposium in Honor of Mysore A. Dayananda, which was held during TMS 2006, 135th Annual Meeting and Exhibition, March 12–16, 2006, in San Antonio, TX. The symposium was organized by Yongho Sohn of University of Central Florida, Carelyn E. Campbell of National Institute of Standards and Technology, Richard D. Sisson, Jr. of Worcester Polytechnic Institute, and John E. Morral of Ohio State University.     

Phase-field investigation of multicomponent diffusion in single-phase and two-phase diffusion couples

Interdiffusion in hypothetical ternary single-phase and two-phase diffusion couples are examined using a phase-field model by numerically solving the nonlinear Cahn-Hilliard and Ginzburg-Landau equations. For diffusion couples assembled with a regular single-phase solution, constant chemical mobilities were used to examine the development of concentration profiles including uphill diffusion and zero-flux plane. Zero-flux plane for a component was observed to develop for a diffusion couple at the composition that corresponds to the activity of that component in one of the terminal alloys. Experimental thermodynamic parameters and composition-dependent chemical mobilities were used to examine the morphological evolution of the interphase boundary in solid-to-solid, two-phase diffusion couples. Instability at the interphase boundary was introduced initially (t=0) by a small compositional fluctuation at the diffuse interface, and its evolution varied largely as a function of terminal alloys and related composition-dependent chemical mobility. This article was presented at the Multicomponent-Multiphase Diffusion Symposium in Honor of Mysore A. Dayananda, which was held during TMS 2006, the 135th Annual Meeting and Exhibition, March 12–16, 2006, in San Antonio, TX. The symposium was organized by Yongho Sohn of University of Central Florida, Carelyn E. Campbell of National Institute of Standards and Technology, Richard D. Sisson, Jr., of Worcester Polytechnic Institute, and John E. Morral of Ohio State University.     

Interdiffusion in γ (face-centered cubic) Ni-Cr-X (X=Al, Si, Ge, or Pd) alloys at 900 °C

Interdiffusion in nickel (Ni)-chromium (Cr) (face-centered cubic γ phase) alloys with small additions of aluminum (Al), silicon (Si), germanium (Ge), or palladium (Pd) was investigated using solid-to-solid diffusion couples. Ni-Cr-X alloys having compositions of Ni-22at.% Cr, Ni-21at.%Cr-6.2at.%Al, Ni-22at.%Cr-4.0at.%Si, Ni-22at.%Cr-1.6at.%Ge, and Ni-22at.%Cr-1.6at.%Pd were manufactured by arc casting. The diffusion couples were assembled in an Invar steel jig, encapsulated in Ar after several hydrogen purges, and annealed at 900 °C in a three-zone tube furnace for 168 h. Experimental concentration profiles were determined from polished cross sections of these couples by using electron probe microanalysis with pure element standards. Interdiffusion fluxes of individual components were calculated directly from the experimental concentration profiles, and the moments of interdiffusion fluxes were examined to determine the average ternary interdiffusion coefficients. The effects of ternary alloying additions on the diffusional behavior of Ni-Cr-X alloys are presented in the light of the diffusional interactions and the formation of a protective Cr₂O₃ scale. This article was presented at the Multicomponent-Multiphase Diffusion Symposium in Honor of Mysore A. Dayananda, which was held during TMS 2006, the 135th Annual Meeting and Exhibition, March 12–16, 2006, in San Antonio, TX. The symposium was organized by Yongho Sohn of University of Central Florida, Carelyn E. Campbell of National Institute of Standards and Technology, Richard D. Sisson, Jr., of Worcester Polytechnic Institute, and John E. Morral of Ohio State University.     

Steady-state migration of the liquid film along a grain boundary during melting of alloys

We discuss melting of alloys along grain boundaries as a free boundary problem for two moving solid–liquid interfaces. One of them is the melting front and the other is the solidification front. The presence of the triple junction plays an important role in controlling the velocity of this process. The interfaces interact strongly via the diffusion field in the thin liquid layer between them. In the liquid film migration (LFM) mechanism the system chooses a more efficient kinetic path, which is controlled by diffusion in the liquid film over relatively short distances. However, only weak coherency strain energy is the effective driving force for LFM in the case of melting of one-phase alloys. The process with only one melting front would be controlled by the very slow diffusion in the mother solid phase over relatively large distances.     

Adsorption and desorption of oxygen at metal-oxide interfaces: Two-dimensional modeling approaches

A numerical approach is presented for the segregation of atomic oxygen at Ag-MgO interfaces for a system of MgO particles dispersed in an Ag matrix. General segregation kinetics is considered, and the coupled system of partial differential equations is solved using a two-dimensional finite element scheme. An indirect integration procedure for the oxygen surface coverage has been implemented into a commercial code. This numerical approach allows for the consideration of general boundary conditions, specimen sizes, and time- or concentration-dependent material and process parameters. The method is applied to periodic and stochastic model oxide distributions. This article was presented at the Multicomponent-Multiphase Diffusion Symposium in Honor of Mysore A. Dayananda, which was held during TMS 2006, 135th Annual Meeting and Exhibition, March 12–16, 2006, in San Antonio, TX. The symposium was organized by Yongho Sohn of University of Central Florida, Carelyn E. Campbell of National Institute of Standards and Technology, Richard D. Sisson, Jr., of Worcester Polytechnic Institute, and John E. Morral of Ohio State University.     

The aftereffect of cyclic loading on the corrosion of aluminum-based alloys

Effects of bench loading and stresses on the corrosion resistance of д16AT alloy are studied. Complicated effect of the stress intensity and the cyclic loading on the surface morphology and pit concentration is demonstrated. Harmonic character of the loading dependence of the change of corrosion resistance is due to segregation effects. Original Russian Text ? V.Yu. Vasil’ev, V.S. Shapkin, N.V. Barulenkova, M.V. Antonova, and E.N. Antonova, 2006, published in Zashchita Metallov, 2006, Vol. 42, No. 3, pp. 227–232.     

Diffusional analysis of a multiphase oxide scale formed on a Mo-Mo3Si-Mo5-SiB2 alloy

Diffusional analyses were performed to understand the oxidation at 1300 °C of a multiphase Mo-13.2Si-13.2B (at.%) alloy. During oxidation, a protective glass scale formed with an intermediate layer of (Mo+glass) between the base alloy and external glass scale. Compositional profiles across the (Mo+glass) layer and the external glass scale were determined, and interdiffusion fluxes and effective interdiffusion coefficients for the various components were determined by using “MultiDiFlux” software. The motion of the (alloy/Mo+glass) and (Mo+glass/glass) interphase boundaries after passivation was examined. Additionally, vapor-solid diffusion experiments at 1300 °C were carried out with single-phase Mo₃Si and T2 specimens in addition to a multiphase Mo-10Si-10B (at.%) alloy. These specimens were exposed to vacuum to induce silicon loss resulting in the formation of a Mo layer. An average effective interdiffusion coefficient of Si in Mo at 1300 °C was estimated from the Mo₃Si-vapor couple to be in the order of 8×10⁻¹⁷ m²/s. This article was presented at the Multicomponent-Multiphase Diffusion Symposium in Honor of Mysore A. Dayananda, which was held during TMS 2006, 135th Annual Meeting and Exhibition, March 12–16, 2006, in San Antonio, TX. The symposium was organized by Yongho Sohn of University of Central Florida, Carelyn E. Campbell of National Institute of Standards and Technology, Richard D. Sisson, Jr., of Worcester Polytechnic Institute, and John E. Morral of Ohio State University.     

Analysis of interdiffusion data in multicomponent alloys to extract fundamental diffusion information

This paper reviews new procedures based around the random alloy model that have been established recently for analyzing chemical diffusion data in binary and ternary alloy systems. The authors show how atom-vacancy exchange frequency ratios, individual tracer correlation factors, and vacancy-wind factors can be extracted from the chemical diffusion data. Examples are taken from intrinsic diffusion data in the Ag-Cd and Ag-Cd-Zn alloy systems and from interdiffusion data in the Fe-Ni-Cr and Cu-Fe-Ni alloy systems. This article was presented at the Multicomponent-Multiphase Diffusion Symposium in Honor of Mysore A. Dayananda, which was held during TMS 2006, 135th Annual Meeting and Exhibition, March 12–16, 2006, in San Antonio, TX. The symposium was organized by Yongho Sohn of University of Central Florida, Carelyn E. Campbell of National Institute of Standards and Technology, Richard D. Sisson, Jr., of Worcester Polytechnic Institute, and John E. Morral of Ohio State University.     

Carbon diffusion in steels: A numerical analysis based on direct integration of the flux

In the early 1970s, Professor Dayananda developed a technique for the direct integration of fluxes from the concentration profiles in vapor-solid diffusion couples to determine diffusion coefficients and atomic mobilities. As part of a project to control and optimize the industrial carburization process in mild- and low-alloyed steels, a modified integration analysis was applied to determine the mass transfer coefficient in the gas boundary layer and carbon diffusivity in austenite. Because carbon flux and surface carbon content vary with time during single-stage carburizing even with a fixed carbon potential in the atmosphere, a mass balance at the gas-solid interface must serve as a boundary condition. This article discusses the numerical modeling of gas carburizing, and focuses on calculating the mass transfer and carbon diffusivity parameters using the simulated concentration profiles. This approach validates the proposed method by comparing the calculated parameters with those used in simulation. The results were compared with previous determinations and predictions reported in the literature. This article was presented at the Multicomponent-Multiphase Diffusion Symposium in Honor of Mysore A. Dayananda, which was held during TMS 2006, the 135th Annual Meeting and Exhibition, March 12–16, 2006, in San Antonio, TX. The symposium was organized by Yongho Sohn of University of Central Florida, Carelyn E. Campbell of National Institute of Standards and Technology, Richard D. Sisson, Jr., of Worcester Polytechnic Institute, and John E. Morral of Ohio State University.     

Oxygen diffusion through Al-doped amorphous SiO2

Oxygen (O) diffusion through pure and aluminum (Al)-doped amorphous silica is investigated by using secondary ion mass spectrometry to profile the diffusion of an¹⁸O tracer. The oxides are formed by the thermal oxidation of polymer-derived SiCN and SiAlCN ceramics. The authors demonstrate that a small amount of Al dopant can significantly inhibit both the interstitial and network diffusion of O. The activation energy of O network diffusion for Al-doped silica is two times higher than that for pure silica. The results are discussed in terms of the modification of Al doping on the network structure of the otherwise pure silica. This article was presented at the Multicomponent-Multiphase Diffusion Symposium in Honor of Mysore A. Dayananda, which was held during TMS 2006, the 135th Annual Meeting and Exhibition, March 12–16, 2006, in San Antonio, TX. The symposium was organized by Yongho Sohn of University of Central Florida, Carelyn E. Campbell of National Institute of Standards and Technology, Richard D. Sisson, Jr., of Worcester Polytechnic Institute, and John E. Morral of Ohio State University.     

A transfer-matrix method for analysis of multicomponent diffusion with any number of components

A transfer-matrix method (TMM) is presented for the development of concentration and flux profiles in multicomponent diffusion involving any numbern of components. From interdiffusion fluxes or concentration gradients available at an initial positionx _s, the authors derive expressions for the transfer matrix and its integral so that the concentrations or interdiffusion fluxes of the components can be obtained at any coordinatex. The TMM requires data for interdiffusion coefficients, which are obtained as average values over selected regions by the method of moments developed by Dayananda. Expressions for the concentrations are also obtained from initial conditions on the fluxes or the concentration gradients. The method is also applicable to the case when all the concentrations are known at two ends of a region over which the diffusion coefficients are considered constant. The integration of the fluxes over time, or over the coordinatex, can be evaluated using the transfer-matrix approach, provided the value of the interdiffusion flux is given at a given coordinate. The TMM is applicable to any number of components and can be regarded as a compact generalization of the solutions available for ternary diffusion couples with constant interdiffusion coefficients. An application of the method is illustrated with the experimental data for a ternary Cu-Ni-Zn diffusion couple, and the results are compared with those based on the Fujita-Gosting solution. This article was presented at the Multicomponent-Multiphase Diffusion Symposium in Honor of Mysore A. Dayananda, which was held during TMS 2006, 135th Annual Meeting and Exhibition, March 12–16, 2006, in San Antonio, TX. The symposium was organized by Yongho Sohn of University of Central Florida, Carelyn E. Campbell of National Institute of Standards and Technology, Richard D. Sisson, Jr., of Worcester Polytechnic Institute, and John E. Morral of Ohio State University.     

The characteristics of gold films deposited on ceramic substrate

A large quantity of gold (approximately 10 tonnes yearly) is consumed, all over the world, just to decorate ceramic and glassware. Due to their advanced chemical stability gold films are used for different high technology applications. The technologies for obtaining the best “liquid bright gold” were intensively studied, but the quality of the decor coatings (films) were empirically assessed. We proposed a scientific investigation of the characteristics of gold films, deposited on ceramic substrates, from “liquid bright golds”. The composition of the film has been determined by EDS (Energy Dispersive X-ray Spectrometry). The distribution of the elements was determined at the surface of the film and in cross-section. The surface distribution of the elements was uniform. The diffusion process of the film into substrate and the migration of the substrate elements at the interface region and into the film have been highlighted.     

Reactive interdiffusion in the binary system Ni-Si: Morphology of the Ni3Si2 phase

In binary multiphase diffusion, it is generally admitted that interfaces between phases are necessarily plane. However, a few cases exist, as the binary diffusion couples Ni-Si, Mo-Si, and Fe-Al, for which an intermediate phase of each system grows with an irregular needlelike morphology. To characterize the nonplanar growth of Ni₃Si₂ in bulk samples, the authors studied the behavior of intermetallic compound formation by optical microscopy and x-ray microtomography, for different annealing times. They show that both the average height and the tip radius of curvature grow as the square root of time with two diffusion coefficients separated by orders of magnitude. Moreover, x-ray diffraction indicates that the needles are aligned along the crystallographicc-axis. These results could be consistently explained by an anisotropic diffusion model. This article was presented at the Multicomponent-Multiphase Diffusion Symposium in Honor of Mysore A. Dayananda, which was held during TMS 2006, 135th Annual Meeting and Exhibition, March 12–16, 2006, in San Antonio, TX. The symposium was organized by Yongho Sohn of University of Central Florida, Carelyn E. Campbell of National Institute of Standards and Technology, Richard D. Sisson, Jr., of Worcester Polytechnic Institute, and John E. Morral of Ohio State University.     

Chemical diffusion in the iridium-richA1 andL12 phases in the Ir-Nb system

The diffusion in iridium-rich Ir-Nb alloys has been studied by single-phase interdiffusion experiments. The chemical diffusion coefficient has been measured for the primary fcc solid-solution and theL1₂ ordered compound Ir₃Nb in the temperature range between 1650 and 1950 °C, using Ir/Ir-8Nb and Ir-26Nb/Ir-28Nb diffusion couples, respectively (numbers indicate mol%). While the chemical diffusion coefficient in the solid-solution phase is close to the tracer self-diffusion coefficient of pure iridium, the diffusion in the compound phase is extremely slow: the chemical diffusion coefficient is 1/40 to 1/50 of that in the solid solution. The low diffusion rate in the compound must be beneficial for high-temperature performance of refractory superalloys based on the Ir-Nb system. This article was presented at the Multicomponent-Multiphase Diffusion Symposium in Honor of Mysore A. Dayananda, which was held during TMS 2006, 135th Annual Meeting and Exhibition, March 12–16, 2006, in San Antonio, TX. The symposium was organized by Yongho Sohn of University of Central Florida, Carelyn E. Campbell of National Institute of Standards and Technology, Richard D. Sisson, Jr., of Worcester Polytechnic Institute, and John E. Morral of Ohio State University.     

Modeling of kinetics of diffusive phase transformation in binary systems with multiple stoichiometric phases

The thermodynamic extremal principle is used for the treatment of the evolution of a binary system under the assumption that all phases in the system are nearly stoichiometric with no sources and sinks for vacancies in the bulk. The interfaces between the individual phases are assumed to act as ideal sources and sinks for vacancies, and to have an infinite mobility. Furthermore, it is assumed that several phases are nucleated in the contact plane of the diffusion couple at the beginning of the computer experiment. Then, it is shown that the number of newly nucleated phases determines the maximum number of polyfurcations (i.e., branching of a single configuration into several distinct configurations) of the initial contact (Kirkendall) plane. The model is demonstrated on a hypothetical binary system with four stoichiometric phases. The inverse problem, namely, the determination of the tracer diffusion coefficients in newly nucleated phases from the thicknesses of new phases and the positions of polyfurcated Kirkendall planes, is treated too. This article was presented at the Multicomponent-Multiphase Diffusion Symposium in Honor of Mysore A. Dayananda, which was held during TMS 2006, the 135th Annual Meeting and Exhibition, March 12–16, 2006, in San Antonio, TX. The symposium was organized by Yongho Sohn of University of Central Florida, Carelyn E. Campbell of National Institute of Standards and Technology, Richard D. Sisson, Jr., of Worcester Polytechnic Institute, and John E. Morral of Ohio State University.