Papers by Keyword: Grain Boundary Segregation

Abstract: The effect of B, Si, P, Cr, Ni, Zr and Mg on cohesive properties of Al and the special grain boundary (GB) Σ5 (210)[100], as well as their segregation behavior at the GB and the (210) surface are studied by first principles method. The analysis of these parameters allows us to single out Ni as the best and phosphorus as the worst interatomic bond strengthening alloying elements.

Abstract: Microstructure development during sintering in 3 mol% Y2O3-stabilized tetragonal ZrO2 polycrystal (Y-TZP) was systematically investigated in two sintering conditions: (a) 1100-1650°C for 2 h and (b) 1300°C for 0-50 h. In the sintering condition (a), the density and grain size in Y-TZP increased with the increasing sintering temperature. Scanning transmission electron microscopy (STEM) and nanoprobe X-ray energy dispersive spectroscopy (EDS) measurements revealed that the Y3+ ion distribution was nearly homogeneous up to 1300°C, i.e., most of grains were the tetragonal phase, but cubic-phase regions with high Y3+ ion concentration were clearly formed in grain interiors adjacent to the grain boundaries at 1500°C. High-resolution transmission electron microscopy (HRTEM) and nanoprobe EDS measurements revealed that no amorphous or second phase is present along the grain-boundary faces, and Y3+ ions segregated not only along the tetragonal-tetragonal phase boundaries but also along tetragonal-cubic phase boundaries over a width below about 10 nm, respectively. These results indicate that the cubic-phase regions are formed from the grain boundaries and/or the multiple junctions in which Y3+ ions segregated. We termed this process a “grain boundary segregation-induced phase transformation (GBSIPT)” mechanism. In the sintering condition (b), the density was low and the grain-growth rate was much slow. In the specimen sintered at 1300°C for 50 h, the cubic-phase regions were clearly formed in the grain interiors adjacent to the grain boundaries. This behavior shows that the cubic-phase regions were formed without grain growth, which can be explained by the GBSIPT model.

Abstract: A phase-field model is described for predicting the diffusional phase transformation process in elastically inhomogeneous polycrystals. The elastic interactions are incorporated by solving the mechanical equilibrium equation using the Fourier-spectral iterative-perturbation scheme taking into account elastic modulus inhomogeneity. A number of examples are presented, including grain boundary segregation, precipitation of second-phase particles in a polycrystal, and interaction between segregation at a grain boundary and coherent precipitates inside grains. It is shown that the local pressure distribution due to coherent precipitates leads to highly inhomogeneous solute distribution along grain boundaries.

Abstract: It was shown more recently in our Laboratory [1,2,3] that having a substrate/diffusant/thin-film/cap-layer structure (the thin film was typically several 10 nm thick, with the same order of magnitude of grain size; the refractory metal cap layer was used just to avoid the oxidation), first the diffusant atoms migrated very fast across the thin film and segregated at the film/cap-layer interface. The accumulated atoms at the film/cap layer interface form a secondary diffusion reservoir and atoms diffuse back to the layer. Later on, the thin film was gradually filled up with the diffusing atoms and composition depth profiles, determined by Secondary Neutral Mass Spectroscopy (SNMS), showed a maximum at the cap layer-thin film interface. The accumulated atoms at this interface formed a secondary diffusion reservoir and atoms diffused back to the layer. These observations can be interpreted supposing a bimodal grain boundary structure with different (fast and low) diffusivities. The observed grain boundary diffusion phenomena can be classified as C-type diffusion. The appearance of the peak observed at the cap layer interface can be used as a tool to determine the grain boundary diffusivity along the fast boundaries. Because the fast boundaries were saturated in the first stage of the process, this back-diffusion took place along the low-diffusivity boundaries only. Thus the SNMS depth-profiling is a good method to determine grain boundary diffusivities in a bimodal structure. In addition, from the overall impurity content inside the film the segregation can also be estimated, if the bulk solubility is low and the GB density is known. Numerical simulations of C-type GB diffusion in thin films with a bimodal structure confirmed that the interpretation of the result depicted above is reasonable [4]. In order to estimate roughly the GB diffusion data we determined the fast diffusivity using the first appearance method. The lower diffusivity was determined from the time evolution of the broadening of the diffusant/thin film interface. In addition both (slow and fast) diffusivities were also estimated from fitting numerical solutions obtained in [4] too.

Abstract: It was recently shown [1] that EMPA-WDS (Electron Probe MicroAnalysis by Wavelength Dispersive X-ray Spectroscopy) can be used to detect and to accurately quantify monolayer surface and grain boundary segregation. This paper presents the last developments of this application. It focuses on the measurement of sulphur grain boundary segregation in nickel on fractured surfaces. A special attention was paid to the quantification of the sulphur coverage, taking into account the non-normal incidence of the electron beam on a fracture surface. Sulphur grain boundary segregation kinetics was measured at 750°C in nickel to document the quantitative possibilities of the technique.

Abstract: Thermodynamics of the atomic complexes formation in a grain boundary (GB) is discussed applying to AB complex. It is shown that the AB complex formation leads to the nonlinearity of segregation isothermes. Consequently, the concentration profiles for GB diffusion are nonlinear. The total (free and bound into complexes) concentration of diffusant B decreases at the given depth as the molar fraction of the complexes increases.

Abstract: Two Al alloys (AA1570 and AA6061) in the solutionized state have been processed by HPT at room temperature to achieve a homogeneous UFG structure. After HPT, the grain size was found to have a mean value about 100 nm for both alloys. Measured yield stress values of HPT-produced UFG alloys being plotted in terms of the Hall-Petch relationship were found to exceed the plot predictions for the range of ultrafine grain size. For both alloys, Atom Probe Tomography measurements allowed to reveal segregation of solute elements along grain boundaries. The origin of the extremely high strength of the alloys nanostructured by HPT is discussed with a special attention to the influence of such segregations on the emission and the mobility of dislocations.

Abstract: Based on a novel defactants (defect acting agents) concept (R. Kirchheim, Acta Materialia 55 (2007) 5129 and 5139), a novel method of understanding and synthesizing NC material was proposed by introducing defactants (segregating solute atoms) into the materials to ease the formation of grain boundaries (GBs) and enhance the formation ability of nanocrystalline (NC) structures. The iron-carbon system was chosen as a model system where carbon acts as the so-called defactant. Iron powders mixed with different amount of graphite were ball milled to prepare NC iron-carbon alloys with different carbon concentrations (C0). After ball milling, the as-milled powder with relatively low carbon concentration was annealed at a certain temperature to achieve saturation of GBs by carbon atoms. The microstructures of the powders were investigated by means of transmission electron microscopy (TEM) and X-ray diffraction (XRD) methods. The mean grain sizes (D) of the powders were determined by analyzing TEM dark field images and X-ray line profiles. The results indicated that once the saturation of GBs is achieved, D of the NC iron-carbon powders will be strongly dependent on C0 and will follow a simple mass balance of carbon in a closed system, i.e. D=3ΓgbVm/(C0-Cg) with Cg the carbon concentration in grains, Γgb the grain boundary excess, and Vm the molar volume of iron. Based on the experimental results, the formation of NC iron-carbon alloys was treated in detail within the framework of the defactant concept. The increase of C0 significantly reduces the formation energy of GBs, leading to a substantial decrease of D.

Abstract: Literature data on grain boundary properties show surprisingly in some cases reversed courses of the structural dependences than expected, or directly prove their qualitative changes with changing temperature. This “reversed anisotropy” is demonstrated for example of grain boundary segregation. It is shown that this reversed anisotropy of grain boundary properties can be explained by the enthalpy–entropy compensation effect. Serious consequences of altered structural dependence of grain boundary properties for Grain Boundary Engineering are discussed.

Abstract: Yielding of polycrystalline low carbon steel is characterized by a clear yield point followed by unstable Lüders deformation and such a yielding behavior is taken over to fine grained steel with the grain size of 1μm or less. Yield strength of ferritic steel is increased with grain refinement standing on the Hall-Petch relation. The following equation is realized up to 0.2μm grain size in the relation between yield strength y and grain size d: y [MPa]= 100+600×d[μm]-1/2. In low carbon steel, it might be concluded that the Hall-Petch coefficient (ky) is around 600MPa•μm1/2. However, the ky value of interstitial free steels is substantially small as 130-180MPa•μm1/2 and it can be greatly increased by a small amount of solute carbon less than 20ppm. It was also cleared that the disappearance of yield point by purifying is due to the decrease in the ky value. On the other hand, the ky value is changeable depending on heat treatment conditions such as cooling condition from an elevated temperature and aging treatment at 90°C. These results suggest the contribution of carbon segregation at grain boundary in terms of the change in the ky value. On the contrary, substitutional elements such as Cr and Si do not give large influence to the ky value in comparison with the effect by carbon.