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At least 109 records · Page 6

Smoothed Boundary Method for simulating bulk and grain boundary transport in complex polycrystalline microstructures

Grain boundaries have a major impact on material properties, but explicit consideration of the complex geometries of grain structures in simulations poses a challenge. In this paper, we present a general method for incorporating the effect of grain boundaries based on the Smoothed Boundary Method (SBM). By using multiple domain parameters to define the domains of different grains, this method circumvents time-consuming mesh generation steps that are associated with finite element calculations involving complex microstructures. To validate the approach, we evaluate the accuracy of the SBM against the sharp interface method. The capabilities of this approach were demonstrated through simulations of surface and grain boundary diffusion, as well as those of electrochemical impedance spectroscopy. We conclude this method is applicable to many material systems in which grain boundaries play a crucial role.

36 MATERIALS SCIENCE↗

Scaling microstructural processes in the sintering of ionic ceramics

A multi-scale framework, combining a multiphase field formulation and large deformation mechanics, was developed as a stepping stone to perform the data analytics of the microstructural level kinetics of a sintering solid. Relevant microstructural information from this framework, such as grain, stress, and porosity statistics, was scaled up to describe the macroscopic level sintering kinetics. Here, the developed formulation was applied to describe the electric field assisted sintering of Y 2 O 3 . Microstructural inhomogeneities in a multi-granular solid result in the formation of a field of compressive stress networks, which interleave with low compression and weakly tensile regions, defining a scaffolding for sintering concentration regions to develop. A Poisson effect-induced lateral stress network is also naturally self-induced as a result of the mechanical constraints imposed by the sintering apparatus. For long sintering times, localized shear stresses enhancing mass flow along grain boundaries and internal surfaces develop. Three-sided pores are removed by either vacancy transport to the surrounding pores, or move towards the external surfaces through grain boundary diffusion. Four- and higher order-sided pores stabilize because an equal amount of vacancies are gained and lost through the connecting grain boundaries. Grain dewetting contributes to pore coalescence, suggesting that pore kinetics and grain growth are coupled and should be analyzed in concert. The combined sintering and grain growth kinetics define six regimes of sintering behavior: (1) T, the transient regime; (2) E$_Υ$, the surface energy dominated, early sintering regime, where the grain growth exponent, p = 1, and the stress concentration factor, $f$ ~ $1/\hat{ρ}^{4.6}$; (3) E S , the stress dominated, early sintering regime, where p = 1 and $f$ ~ $1/\hat{ρ}^{4}$; (4) I$_Υ$, the surface energy dominated, intermediate sintering regime, where p = 2 and $f$ ~ $1/\hat{ρ}^{4.6}$; (5) I S , the stress dominated, intermediate sintering regime, where p = 2 and $f$ ~ $1/\hat{ρ}^{4}$; and (6) L, the late sintering regime, where p = 3 and $f$ ~ 1. At the macroscopic level, the rapid densification and suppression of grain growth observed in the electric field assisted sintering process is a consequence of the compounding effects of the underlying stress-, transport-, and interfacial-energy-induced energy minimization kinetics, as predicted by the multi-scale framework.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Two types of diffusions at the cathode/electrolyte interface in IT-SOFCs

Analytical transmission electron microscopy, in particular with the combination of energy dispersive X-ray spectroscopy (EDX) and electron energy-loss spectroscopy (EELS), has been performed to investigate the microstructure and microchemistry of the interfacial region between the cathode (La{sub 0.6}Sr{sub 0.4}Co{sub 0.8}Fe{sub 0.2}O{sub 3}, LSCF) and the electrolyte (Gd-doped ceria, GDC). Two types of diffusions, mutual diffusion between cathode and electrolyte as well as the diffusion along grain boundaries, have been clarified. These diffusions suggest that the chemical stability of LSCF and GDC are not as good as previously reported. The results are more noteworthy if we take into consideration the fact that such interdiffusions occur even during the sintering process of cell preparation. - Graphical Abstract: Two types of diffusions, the mutual diffusion and the diffusion along grain boundaries, occurred at the cathode/electrolyte interface of intermediate temperature solid state fuel cells, during cell preparation. The mutual diffusion is denoted by black arrows and the diffusion along grain boundaries assigned by pink arrows. Highlights: > All the cations in cathode (LSCF) and electrolyte (GDC) can mutually diffuse into each other. > Diffusing elements will segregate at grain boundaries or triple junctions around the cathode/electrolyte interface. > Two types of diffusions, the mutual diffusion and diffusion along grain boundaries, have been clarified thereafter.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of Ag3Sn nanoparticles and temperature on Cu6Sn5 IMC growth in Sn-xAg/Cu solder joints

Highlights: • The number density of Ag{sub 3}Sn grains precipitated upon Cu{sub 6}Sn{sub 5}, increases with Ag content and reflow temperature (T). • Raising of wt. % of Ag in solder and lowering of T can cause an increase in grain diameter of Ag{sub 3}Sn nanoparticles. • The blockading effect of Ag{sub 3}Sn particles on Cu{sub 6}Sn{sub 5} IMC growth is more pronounced in Sn-3Ag and Sn-3.5Ag alloys. • IMC suppressing nanoparticles can be utilized for solder materials design. - Abstract: The growing importance of Pb-free Sn-xAg solders and high cost of Ag has attracted the attention of researchers to perform experiment with solders with varied content of Ag element. In this study, Sn-xAg(0,1,2,3.5) solder balls on Cu substrate have been reflowed at 250/275/300 °C for 60 s and air cooled. Finite element method has been utilized to simulate the concentration and temperature during cooling. The experimental results suggest that the Cu flux through grain boundary diffusion is the dominant mechanism for Cu{sub 6}Sn{sub 5} intermetallic compound growth in Pure Sn and Sn-1Ag solders. When the Ag content is increased, as in case of Sn-3Ag and Sn-3.5Ag alloys; the shielding effect of Ag{sub 3}Sn nanoparticles is the determinant factor for affecting the thickness of Cu{sub 6}Sn{sub 5} IMC. Both Cu influx rate and shielding effect of Ag{sub 3}Sn nanoparticles are enhanced with the raise in pre-cooled isothermal reflow temperature. Sn-1Ag solder is observed to have the thickest Cu{sub 6}Sn{sub 5} IMC.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The Effect of High Temperature Annealing on the Grain Characteristics of a Thin Chemical Vapor Deposition Silicon Carbide Layer.

The unique combination of thermo-mechanical and physiochemical properties of silicon carbide (SiC) provides interest and opportunity for its use in nuclear applications. One of the applications of SiC is as a very thin layer in the TRi-ISOtropic (TRISO) coated fuel particles for high temperature gas reactors (HTGRs). This SiC layer, produced by chemical vapor deposition (CVD), is designed to withstand the pressures of fission and transmutation product gases in a high temperature, radiation environment. Various researchers have demonstrated that macroscopic properties can be affected by changes in the distribution of grain boundary plane orientations and misorientations [1 - 3]. Additionally, various researchers have attributed the release behavior of Ag through the SiC layer as a grain boundary diffusion phenomenon [4 - 6]; further highlighting the importance of understanding the actual grain characteristics of the SiC layer. Both historic HTGR fission product release studies and recent experiments at Idaho National Laboratory (INL) [7] have shown that the release of Ag-110m is strongly temperature dependent. Although the maximum normal operating fuel temperature of a HTGR design is in the range of 1000-1250°C, the temperature may reach 1600°C under postulated accident conditions. The aim of this specific study is therefore to determine the magnitude of temperature dependence on SiC grain characteristics, expanding upon initial studies by Van Rooyen et al, [8; 9].

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

A diffusion source for sodium and potassium in the atmospheres of Mercury and the moon

Deep grain-boundary diffusion and regolith diffusion through a fractured crust and regolith can account not only for the Na/K ratios observed in the Mercurian and lunar atmospheres, but the large Na abundance enhancement of Mercury over lunar levels. A hot component of Na and K at Mercury is noted to be smaller in proportion to the total abundances of these two constituents than at the moon; this hot component is consistent with a population of meteoritic substances similar to lunar ones, as well as with a surface composition which has undergone no greater K depletion than that of the moon.

Sprague, Ann L.↗

Preparation and testing of corrosion and spallation-resistant coatings

This Energy & Environmental Research Center (EERC) project is designed to determine if plating APMT, a specific highly oxidation-resistant oxide dispersion-strengthened FeCrAl alloy made by Kanthal, onto nickel-based superalloy turbine parts is a viable method for substantially improving the lifetimes and maximum use temperatures of the parts. The method for joining the APMT plate to the superalloys is called evaporative metal bonding. It involves placing a thin foil of zinc (Zn) between the plate and the superalloy, clamping them together, and heating in an atmosphere-controlled furnace. Upon heating, the Zn melts and dissolves the oxide skins of the alloys at the bond line, allowing the two alloys to diffuse into each other. The Zn then diffuses through the alloys and evaporates from their surfaces. Laboratory testing has shown that the diffusion rate of Zn through the FeCrAl alloy is much faster than through the nickel superalloys. This means that the FeCrAl will serve as a sink for the Zn bonding alloy during the evaporative metal bonding process. Also, the testing has shown that the Zn diffusion mechanism is bulk diffusion, and not intergranular. This is a surprise. However, it means that quantification of the Zn diffusivities in these samples will be significantly simpler than would have been the case if grain boundary diffusion dominated. In addition to the laboratory testing, gas impinger and particulate samples are being collected from a combustor firing syngas and natural gas to determine what types of microcontaminants may reach a turbine firing syngas. The syngas is created in one of two different pilot-scale pressurized coal gasifiers. The initial analysis of the impinger solutions was for standard U.S. Environmental Protection Agency (EPA) Method 29 determination of hazardous metals and did not include major element analysis. When syngas is fired, the amount of Mn in the combustor gas increases substantially. Halogens (Br2 and Cl2) and hydrogen halides (HF, HCl, and HBr) are present in amounts close to or below 1 ppm. In the near future, the solutions will be reanalyzed for major elements. SEM analysis showed that the particulate matter is primarily nonstoichiometric iron sulfate. Most of the particles were 3 μm in diameter or less. Elements such as O, Fe, S, Cr, and Si make up the majority of the compositions of 3089 particles analyzed on the filter surface. The concentrations of O and S are high in almost all particles. The concentrations of S and Fe tend to be higher in the larger particles than in the smaller. In contrast the concentrations of O showed the reverse trend. We currently believe that the high values of Fe and Cr come from a reaction of the syngas with the stainless steel pipes used to transport the syngas, most likely by forming a vapor-phase carbonyl. During combustion, the carbonyls form nonstoichiometric sulfate particles. The excess Si is most likely coming from the coal ash, possibly through the formation of a silicon monoxide fume.

Electric↗

Impact of grain boundary and surface diffusion on predicted fission gas bubble behavior and release in UO 2 fuel

In this work, we quantify the impact of grain boundary (GB) and surface diffusion on fission gas bubble evolution and fission gas release in UO 2 nuclear fuel using simulations with a hybrid phase field/cluster dynamics model. Here, we begin with a comprehensive literature review of uranium vacancy and xenon atom diffusivity in UO 2 through the bulk, along GBs, and along surfaces. In our model we represent fast GB and surface diffusion using a heterogeneous diffusivity that is a function of the order parameters that represent bubbles and grains. We find that the GB diffusivity directly impacts the rate of gas release via GB transport, and that the GB diffusivity is likely below 104 times the lower value from Olander and van Uffelen. We also find that the surface diffusivity impacts bubble coalescence and mobility, and that the bubble surface diffusivity is likely below 10 -4 times the value from Zhou and Olander.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Microstructure, impurity and metal cap effects on Cu electromigration

Electromigration (EM) lifetimes and void growth of pure Cu, Cu(Mn) alloy, and pure Cu damascene lines with a CoWP cap were measured as a function of grain structure (bamboo, near bamboo, and polycrystalline) and sample temperature. The bamboo grains in a bamboo-polycrystalline grained line play the key role in reducing Cu mass flow. The variation in Cu grain size distribution among the wafers was achieved by varying the metal line height and wafer annealing process step after electroplating Cu and before or after chemical mechanical polishing. The Cu grain size was found to have a large impact on Cu EM lifetime and activation energy, especially for the lines capped with CoWP. The EM activation energy for pure Cu with a CoWP cap from near-bamboo, bamboo-polycrystalline, mostly polycrystalline to polycrystalline only line grain structures was reduced from 2.2 ± 0.2 eV, to 1.7 ± 0.1 eV, to 1.5 ± 0.1 eV, to 0.72 ± 0.05 eV, respectively. The effect of Mn in Cu grain boundary diffusion was found to be dependent on Mn concentration in Cu. The depletion of Cu at the cathode end of the Cu(Mn) line is preceded by an incubation period. Unlike pure Cu lines with void growth at the cathode end and hillocks at the anode end of the line, the hillocks grew at a starting position roughly equal to the Blech critical length from the cathode end of the Cu(Mn) polycrystalline line. The effectiveness of Mn on Cu grain boundary migration can also be qualitatively accounted for by a simple trapping model. The free migration of Cu atoms at grain boundaries is reduced by the presence of Mn due to Cu-solute binding. A large binding energy of 0.5 ± 0.1 eV was observed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

An electrostatic spectral neighbor analysis potential for lithium nitride

Machine-learned interatomic potentials based on local environment descriptors represent a transformative leap over traditional potentials based on rigid functional forms in terms of prediction accuracy. However, a challenge in their application to ionic systems is the treatment of long-ranged electrostatics. Here, we present a highly accurate electrostatic Spectral Neighbor Analysis Potential (eSNAP) for ionic α-Li 3 N, a prototypical lithium superionic conductor of interest as a solid electrolyte or coating for rechargeable lithium-ion batteries. We show that the optimized eSNAP model substantially outperforms traditional Coulomb–Buckingham potential in the prediction of energies and forces, as well as various properties, such as lattice constants, elastic constants, and phonon dispersion curves. We also demonstrate the application of eSNAP in long-time, large-scale Li diffusion studies in Li 3 N, providing atomistic insights into measures of concerted ionic motion (e.g., the Haven ratio) and grain boundary diffusion. This work aims at providing an approach to developing quantum-accurate force fields for multi-component ionic systems under the SNAP formalism, enabling large-scale atomistic simulations for such systems.

36 MATERIALS SCIENCE↗

Oxygen isotope thermometry using quartz inclusions in garnet

Oxygen isotope ratios of quartz inclusions (QI) within garnet from granulite and amphibolite facies gneisses in the Adirondack Mountains, NY were analysed and used to determine metamorphic temperatures. Primary QI for eight of 12 samples have δ 18 O values significantly lower than matrix quartz (MQ). The primary QI retain δ 18 O values representative of thermal conditions during garnet crystallization, whereas the δ 18 O values of MQ were raised by diffusive exchange with other matrix minerals (e.g. mica and feldspar) during cooling. The δ 18 O differences between QI and MQ show that garnet (a mineral with slow diffusion of oxygen) can armour QI from isotopic exchange with surrounding matrix, even during slow cooling. These differences between δ 18 O in MQ and QI can further be used to test cooling rates by Fast Grain Boundary diffusion modelling. Criteria for identifying QI that preserve primary compositions and are suitable for thermometry were developed based on comparative tests. Relations between δ 18 O and inclusion size, distance of inclusion to host–garnet rim, core–rim zonation of individual inclusions, and presence or absence of petrological features (healed cracks in QI, inclusions in contact with garnet cracks lined by secondary minerals, and secondary minerals along the inclusion grain boundary) were investigated. In this study, 61% of QI preserve primary δ 18 O and 39% were associated with features that were linked to reset δ 18 O values. If δ 18 O in garnet is homogeneous and inclusions are removed, laser-fluorination δ 18 O values of bulk garnet are more precise, more accurate, and best for thermometry. Intragrain δ 18 O(Grt) profiles measured in situ by ion microprobe show no δ 18 O zonation. Almandine–rich garnet (Alm 60–75 ) from each sample was measured by laser-fluorination mass-spectrometry (LF-MS) for δ 18 O and compared with ion microprobe measurements of δ 18 O in QI for thermometry. The Δ 18 OO(Qz–Grt) values for Adirondack samples range from 2.66 to 3.24‰, corresponding to temperatures of 640–740 °C (A[Qz–Alm] = 2.71). Out of 12 samples that were used for thermometry, nine are consistent with previous estimates of peak temperature (625–800 °C) based on petrological and carbon–isotope thermometry for regional granulite and upper amphibolite facies metamorphism. The three samples that disagree with independent thermometry for peak metamorphism are from the anorthosite–mangerite–charnockite–granite suite in the central Adirondacks and yield temperatures of 640–665 °C, ~100 °C lower than previous estimates. Finally, these low temperatures could be interpreted as thermal conditions during late (post-peak) crystallization of garnet on the retrograde path.

58 GEOSCIENCES↗

Effects of Phosphorous-doping and High Temperature Annealing on CVD grown 3C-SiC

The integrity and property behavior of the SiC layer of the Tri-isotropic (TRISO) coated particle (CP) for high temperature reactors (HTR) are very important as the SiC layer is the main barrier for gaseous and metallic fission product release. This study describes the work done on un-irradiated SiC samples prepared with varying phosphorus levels to simulate the presence of phosphorus due to transmutation. 30Si transmutes to phosphorous (31P) and other transmutation products during irradiation, which may affect the integrity of the SiC layer. The P-doping levels of the SiC samples used in this study cover the range from 1.1x1015 to 1.2x1019 at/cm3 and are therefore relevant to the PBMR operating conditions. Annealing from 1000 C to 2100 C was performed to study the possible changes in nanostructures and various properties due to temperature. Characterization results by X-ray diffraction (XRD), secondary ion mass spectrometry (SIMS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM), are reported in this article. As grain boundary diffusion is identified as a possible mechanism by which 110mAg, one of the fission activation products, might be released through intact SiC layer, grain size measurements is also included in this study. Temperature is evidently one of the factors/parameters amongst others known to influence the grain size of SiC and therefore it is important to investigate the effect of high temperature annealing on the SiC grain size. The ASTM E112 method as well as electron back scatter diffraction (EBSD) was used to determine the grain size of various commercial SiC samples and the SiC layer in experimental PBMR Coated Particles (CPs) after annealing at temperatures ranging from 1600 C to 2100 C. The HRTEM micrograph of the decomposition of SiC at 2100 C are shown and discussed. Nanotubes were not identified during the TEM and HRTEM analysis although graphitic structures were identified. The preliminary conclusion reached is that the P-content at these experimental levels (1.1x1015 - 1.2x1019 atom/cm3) does not have a significant influence on the nanostructure of SiC at high temperatures without irradiation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

A detailed study of the Al 3 Ni formation reaction using nanocalorimetry

In this study, the Al 3 Ni formation reaction was examined at 11 heating rates ranging from 1000 K/s to 100,000 K/s using high-rate nanocalorimetry, time-resolved electron microscopy, isoconversional analysis, and combined kinetic analysis. Two main reaction steps are identified. In the first, interdiffusion occurs between reactants without product nucleation. The estimated activation energy for this process, 113 kJ/mol ± 4 kJ/mol, suggests grain boundary diffusion as the most likely controlling mechanism. In the second step, the Al 3 Ni product phase nucleates and grows. Here, the estimated activation energy of 137 kJ/mol ± 4 kJ/mol suggests that growth is enabled by diffusion of Ni through bulk Al. Combined kinetic analysis of the growth regime yields an Avrami reaction model with an exponent of 0.5, implying 1D diffusion-limited growth from a fixed number of randomly distributed nuclei. Finally, combining the results for the two regimes, we propose a mechanism where the Al 3 Ni product initially nucleates along the grain boundaries and then grows laterally until the reactants are consumed.

36 MATERIALS SCIENCE↗

Book of Extended Abstracts IWCE 2014

It is well known that Cu plays an important role in CdTe solar cell performance as a dopant. In this work, a finitedifference method is developed and used to simulate Cu diffusion in CdTe solar cells. In the simulations, which are done on a twodimensional (2D) domain, the CdTe is assumed to be polycrystalline, with the individual grains separated by grain boundaries. When used to fit experimental Cu concentration data, bulk and grain boundary diffusion coefficients and activation energies for CdTe can be extracted. In the past, diffusion coefficients have been typically obtained by fitting data to simple functional forms of limited validity. By doing full simulations, the simplifying assumptions used in those analytical models are avoided and diffusion parameters can thus be determined more accurately.

14 SOLAR ENERGY↗

Modeling Copper Diffusion in Polycrystalline CdTe Solar Cells

It is well known that Cu plays an important role in CdTe solar cell performance as a dopant. In this work, a finite-difference method is developed and used to simulate Cu diffusion in CdTe solar cells. In the simulations, which are done on a two-dimensional (2D) domain, the CdTe is assumed to be polycrystalline, with the individual grains separated by grain boundaries. When used to fit experimental Cu concentration data, bulk and grain boundary diffusion coefficients and activation energies for CdTe can be extracted. In the past, diffusion coefficients have been typically obtained by fitting data to simple functional forms of limited validity. By doing full simulations, the simplifying assumptions used in those analytical models are avoided and diffusion parameters can thus be determined more accurately

14 SOLAR ENERGY↗

Permeation of oxygen through high purity, large grain silver

The permeation of high purity, large grain Ag membranes by oxygen has been studied over the temperature range 400 to 800 C. The permeability was found to be quite linear and repeatable, but the magnitude was 3.2 times smaller than that determined by past research. Since previous investigators studied substantially less pure Ag and conducted experiments within much poorer vacuum environments (which indicates that their grain boundary density was much greater), the data presented here suggest oxygen transport through the membrane is primarily by grain boundary diffusion. The diffusivity measurements were found to exhibit two distinct linear regions, one above and one below a critical temperature of 630 C. The high-temperature data have an activation energy (11.1 kcal/mole) similar to that reported by others, but the low-temperature data have a higher activation energy (15.3 kcal/mole), which can be explained by impurity trapping in the grain boundaries. Vacuum desorption of the oxygen-saturated Ag was found to occur at a threshold of 630 C, which is consistent with the onset of increased mobility within the grain boundaries.

Outlaw, R. A.↗

On Techniques to Characterize and Correlate Grain Size, Grain Boundary Orientation and the Strength of the SiC Layer of TRISO Coated Particles: A Preliminary Study

The mechanical properties of the silicon carbide (SiC) layer of the TRi-ISOtropic (TRISO) coated particle (CP) for high temperature gas reactors (HTGR) are performance parameters that have not yet been standardized by the international HTR community. Presented in this paper are the results of characterizing coated particles to reveal the effect of annealing temperature (1000 to 2100°C) on the strength and grain size of unirradiated coated particles. This work was further expanded to include possible relationships between the grain size and strength values. The comparative results of two strength measurement techniques and grain size measured by the Lineal intercept method are included. Preliminary grain boundary characterization results determined by electron backscatter diffraction (EBSD) are included. These results are also important for future fission product transport studies, as grain boundary diffusion is identified as a possible mechanism by which 110mAg, one of the fission activation products, might be released through intact SiC layers. Temperature is a parameter known to influence the grain size of SiC and therefore it is important to investigate the effect of high temperature annealing on the SiC grain size. Recommendations and future work will also be briefly discussed.

99 GENERAL AND MISCELLANEOUS↗

Extracting Cu Diffusion Parameters in Polycrystalline CdTe

It is well known that Cu plays an important role in CdTe solar cell performance as a dopant. In this work, a finite-difference method is developed and used to simulate Cu diffusion in CdTe solar cells. In the simulations, which are done on a two-dimensional (2D) domain, the CdTe is assumed to be polycrystal-line, with the individual grains separated by grain boundaries. When used to fit experimental Cu concentration data, bulk and grain boundary diffusion coefficients and activation energies for CdTe can be extracted. In the past, diffusion coefficients have been typically obtained by fitting data to simple functional forms of limited validity. By doing full simulations, the simplifying assumptions used in those analytical models are avoided and diffusion parameters can thus be determined more accurately.

14 SOLAR ENERGY↗