Microstructure, microtexture and precipitation in the ultrafine-grained surface layer of an Al-Zn-Mg-Cu alloy processed by sliding friction treatment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Yanxia

2017-01-15

Precipitate redistribution and texture evolution are usually two concurrent aspects accompanying grain refinement induced by various surface treatment. However, the detailed precipitate redistribution characteristics and process, as well as crystallographic texture in the surface refined grain layer, are still far from full understanding. In this study, we focused on the microstructural and crystallographic features of the sliding friction treatment (SFT) induced surface deformation layer in a 7050 aluminum alloy. With the combination of transmission electron microscopy (TEM) and high angle angular dark field scanning TEM (HAADF-STEM) observations, a surface ultrafine grain (UFG) layer composed of both equiaxed and lamellar ultrafinemore » grains and decorated by high density of coarse grain boundary precipitates (GBPs) were revealed. Further precession electron diffraction (PED) assisted orientation mapping unraveled that high angle grain boundaries rather than low angle grain boundaries are the most favorable nucleation sites for GBPs. The prominent precipitate redistribution can be divided into three successive and interrelated stages, i.e. the mechanically induced precipitate dissolution, solute diffusion and reprecipitation. The quantitative prediction based on pipe diffusion along dislocations and grain boundary diffusion proved the distribution feasibility of GBPs around UFGs. Based on PED and electron backscatter diffraction (EBSD) analyses, the crystallographic texture of the surface UFG layer was identified as a shear texture composed of major rotated cube texture (001) 〈110〉 and minor (111) 〈112〉, while that of the adjoining lamellar coarse grained matrix was pure brass. The SFT induced surface severe shear deformation is responsible for texture evolution. - Highlights: •The surface ultrafine grain layer in a 7050 aluminum alloy was focused. •Precipitate redistribution and texture evolution were discussed. •The quantitative prediction proved the distribution feasibility of GBPs. •Precession electron diffraction orientation mapping showed a shear texture.« less

Plastic strain and grain size effects in the surface roughening of a model aluminum alloy

NASA Astrophysics Data System (ADS)

Moore, Eric Joseph

To address issues surrounding improved automotive fuel economy, an experiment was designed to study the effect of uniaxial plastic tensile deformation on surface roughness and on slip and grain rotation. Electron backscatter diffraction (EBSD) and scanning laser confocal microscopy (SLCM) were used to track grain size, crystallographic texture, and surface topography as a function of incremental true strain for a coarse-grained binary alloy that is a model for AA5xxx series aluminum alloys. One-millimeter thick sheets were heat treated at 425°C to remove previous rolling texture and to grow grains to sizes in the range ˜10-8000 mum. At five different strain levels, 13 sample regions, containing 43 grains, were identified in both EBSD and SLCM micrographs, and crystallographic texture and surface roughness were measured. After heat treatment, a strong cube texture matrix emerged, with bands of generally non-cube grains embedded parallel to the rolling direction (RD). To characterize roughness, height profiles from SLCM micrographs were extracted and a filtered Fourier transform approach was used to separate the profiles into intergranular (long wavelength) and intragranular (short wavelength) signatures. The commonly-used rms roughness parameter (Rq) characterized intragranular results. Two important parameters assess intergranular results in two grain size regimes: surface tilt angle (Deltatheta) and surface height discontinuity (DeltazH) between neighboring grains at a boundary. In general, the magnitude of Rq and Deltatheta increase monotonically with strain and indicate that intergranular roughness is the major contributor to overall surface roughness for true strains up to epsilon = 0.12. Surface height discontinuity DeltazH is defined due to exceptions in surface tilt angle analyses. The range of observed Deltatheta= 1-10° are consistent with the observed 3-12° rotation of individual grains as measured with EBSD. For some grain boundaries with Deltatheta< 4°, the surface height discontinuity DeltazH characterizes the response of adjacent grains in which one or more are large (˜1000-2000 mum), making a 3-12° rotation of the grain highly unlikely. This can be understood by postulating that the energy associated with rotating large grains would exceed the energy to shear along the boundary. Slip and grain boundary shearing are the active mechanisms in these instances.

Segregation Behavior of Sulfur and Other Impurities Onto the Free Surfaces of ED-Ni Deposits

NASA Technical Reports Server (NTRS)

Panda, Binayak; Jerman, Gregory; Gentz, Steven J. (Technical Monitor)

2000-01-01

Most researchers attribute grain boundary embrittlement in electro-deposited Nickel (ED-Ni) to the presence of small quantities of Sulfur as an impurity. It occurs in a highly mobile form that segregates to the grain boundaries. Evaluation of Sulfur segregation requires that a sample be fractured through the grain boundaries. However, this action may not always be possible. ED-Ni is inherently tough at ambient temperature, especially if a low level of Sulfur was intentionally maintained. A new method was developed to study Sulfur and other migrant species to the grain boundaries, which also migrate to free surfaces. A test specimen is heated by a quartz lamp within the sample preparation chamber, allowing the mobile species to migrate to polished free surfaces. There the mobile species are analyzed using X-ray photoelectron spectroscopy (XPS) also known as Electron Spectroscopy for Chemical Analysis (ESCA).

Segregation Behavior of Sulfur and Other Impurities onto the Free Surfaces of ED-NI Deposits

NASA Technical Reports Server (NTRS)

Panda, B.; Jerman, G.

2001-01-01

Most researchers attribute grain boundary embrittlement in electro-deposited nickel (ED-Ni) to the presence of small quantities of sulfur as an impurity. It occurs in a highly mobile form that segregates to the grain boundaries. Evaluation of sulfur segregation requires that a sample be fractured through the grain boundaries. However, this action may not always be possible. ED-Ni is inherently tough at ambient temperature, especially if a low level of sulfur was intentionally maintained. A new method was developed to study sulfur and other migrant species to the grain boundaries, which also migrate to free surfaces. A test specimen is heated by a quartz lamp within the sample preparation chamber, allowing the mobile species to migrate to polished free surfaces. There the mobile species are analyzed using X-ray photoelectron spectroscopy (XPS) also known as Electron Spectroscopy for Chemical Analysis (ESCA).

Nanocrystalline copper films are never flat

NASA Astrophysics Data System (ADS)

Zhang, Xiaopu; Han, Jian; Plombon, John J.; Sutton, Adrian P.; Srolovitz, David J.; Boland, John J.

2017-07-01

We used scanning tunneling microscopy to study low-angle grain boundaries at the surface of nearly planar copper nanocrystalline (111) films. The presence of grain boundaries and their emergence at the film surface create valleys composed of dissociated edge dislocations and ridges where partial dislocations have recombined. Geometric analysis and simulations indicated that valleys and ridges were created by an out-of-plane grain rotation driven by reduction of grain boundary energy. These results suggest that in general, it is impossible to form flat two-dimensional nanocrystalline films of copper and other metals exhibiting small stacking fault energies and/or large elastic anisotropy, which induce a large anisotropy in the dislocation-line energy.

Atomisti modeling of the microstructure and transport properties of lead-free solder alloys

NASA Astrophysics Data System (ADS)

Sellers, Michael S.

Damage mechanics models of lead-free solder joints in nanoelectronics continue to improve, and in doing so begin to utilize quantitative values describing processes at the atomic level, governing phenomena like electromigration and thermomigration. In particular, knowledge of the transport properties of specific microstructures helps continuum level models fully describe these larger-scale damage phenomena via multi-scale analysis. For example, diffusivities for different types of grain boundaries (fast diffusion paths for solvent and solute atoms, and vacancies), and a description of the boundary structure as a function of temperature, are critical in modeling solder microstructure evolution and, consequently, joint behavior under extreme temperature and electric current. Moreover, for damage that develops at larger length scales, surface energies and diffusivities play important roles in characterizing void stability and morphology. Unfortunately, experiments that investigate these kind of damage phenomena in the atomistic realm are often inconsistent or unable to directly quantify important parameters. One case is the particular transport and structural properties of grain boundaries in Sn (the main component in lead-free solder alloys) and their behavior in the presence of Ag and Cu impurities. This information is crucial in determining accurate diffusivity values for the common SnAgCu (SAC) type solder. Although an average grain boundary diffusivity has been reported for polycrystalline Sn in several works, the value for grain boundary width is estimated and specific diffusivities for boundaries known to occur in Sn have not been reported, to say nothing of solute effects on Sn diffusivity and grain boundary structure. Similarly, transport properties of Sn surfaces remain relatively uninvestigated as well. These gaps and inconsistencies in atomistic data must be remedied for micro- and macro-scale modeling to improve. As a complement to experimental work and possessing the ability to fill in the gaps, molecular simulation serves to reinforce experimental predictions and provide insight into the atomistic processes that govern studied phenomena. In the present body of work, we employ molecular statics and dynamics simulations in the characterization and computation of betaSn surface energies and surface diffusivities, the determination of diffusivities and structural properties of specific betaSn grain boundaries, and the investigation of Cu and Ag solute effects on betaSn grain boundaries. In our study of betaSn surfaces, energies for low number Miller index surfaces are computed and the (100) plane is found to have the lowest un-relaxed energy. We then find that two simple hopping mechanisms dominate adatom diffusion transitions on this surface. For each, we determine hopping rates of the adatom and compute its tracer diffusivity. Our work on grain boundaries investigates the self-diffusion properties and structure of several betaSn symmetric tilt grain boundaries using molecular dynamics simulations. We find that larger diffusive widths are exhibited by higher excess potential energy grain boundaries. Diffusivities in the directions parallel to the interface plane are also computed and activation energies are found with the Arrhenius relation. These are shown to agree well with experimental data. Finally, we examine the effect that solute atoms of Ag and Cu have on the microstructure of betaSn. Excess energies of the (101) symmetric tilt betaSn grain boundary are computed as a function of solute concentration at the interface, and we show that Ag lowers the energy at a greater rate than Cu. We also quantify segregation enthalpies and critical solute concentrations (where the excess energy of the boundary is reduced to zero). The effect of solute type on shear stress is also examined, and we show that solute has a strong effect on the stabilization of higher energy grain boundaries under shear stress. We then look at the self-diffusivity of Sn in the (101) symmetric tilt betaSn grain boundary and show that adding both Ag or Cu decrease the grain boundary self-diffusivity of Sn as solute amount in the interface increases. Effects of larger concentrations of Cu in particular are also investigated.

Diffusion of volatile organics through porous snow: impact of surface adsorption and grain boundaries

NASA Astrophysics Data System (ADS)

Bartels-Rausch, T.; Wren, S. N.; Schreiber, S.; Riche, F.; Schneebeli, M.; Ammann, M.

2013-07-01

Release of trace gases from surface snow on earth drives atmospheric chemistry, especially in the polar regions. The gas-phase diffusion of methanol and of acetone through the interstitial air of snow was investigated in a well-controlled laboratory study in the temperature range of 223 to 263 K. The aim of this study was to evaluate how the structure of the snowpack, the interaction of the trace gases with the snow surface, and the grain boundaries influence the diffusion on timescales up to 1 h. The diffusive loss of these two volatile organics into packed snow samples was measured using a chemical ionization mass spectrometer. The structure of the snow was analysed by means of X-ray-computed micro-tomography. The observed diffusion profiles could be well described based on gas-phase diffusion and the known structure of the snow sample at temperatures ≥ 253 K. At colder temperatures, surface interactions start to dominate the diffusive transport. Parameterizing these interactions in terms of adsorption to the solid ice surface, i.e. using temperature-dependent air-ice partitioning coefficients, better described the observed diffusion profiles than the use of air-liquid partitioning coefficients. No changes in the diffusive fluxes were observed by increasing the number of grain boundaries in the snow sample by a factor of 7, indicating that for these volatile organic trace gases, uptake into grain boundaries does not play a role on the timescale of diffusion through porous surface snow. For this, a snow sample with an artificially high amount of ice grains was produced and the grain boundary surface measured using thin sections. In conclusion, we have shown that the diffusivity can be predicted when the structure of the snowpack and the partitioning of the trace gas to solid ice is known.

Origin of the relatively low transport mobility of graphene grown through chemical vapor deposition

PubMed Central

Song, H. S.; Li, S. L.; Miyazaki, H.; Sato, S.; Hayashi, K.; Yamada, A.; Yokoyama, N.; Tsukagoshi, K.

2012-01-01

The reasons for the relatively low transport mobility of graphene grown through chemical vapor deposition (CVD-G), which include point defect, surface contamination, and line defect, were analyzed in the current study. A series of control experiments demonstrated that the determinant factor for the low transport mobility of CVD-G did not arise from point defects or surface contaminations, but stemmed from line defects induced by grain boundaries. Electron microscopies characterized the presence of grain boundaries and indicated the polycrystalline nature of the CVD-G. Field-effect transistors based on CVD-G without the grain boundary obtained a transport mobility comparative to that of Kish graphene, which directly indicated the detrimental effect of grain boundaries. The effect of grain boundary on transport mobility was qualitatively explained using a potential barrier model. Furthermore, the conduction mechanism of CVD-G was also investigated using the temperature dependence measurements. This study can help understand the intrinsic transport features of CVD-G. PMID:22468224

Crystalline orientation dependent photoresponse and heterogeneous behaviors of grain boundaries in perovskite solar cells

NASA Astrophysics Data System (ADS)

Jiang, Chuanpeng; Zhang, Pengpeng

2018-02-01

Using photoconductive atomic force microscopy and Kelvin probe force microscopy, we characterize the local electrical properties of grains and grain boundaries of organic-inorganic hybrid perovskite (CH3NH3PbI3) thin films on top of a poly(3,4-ethylenedioxythiophene)-polystyrene sulfonate (PEDOT:PSS)/ITO substrate. Three discrete photoconductivity levels are identified among perovskite grains, likely corresponding to the crystal orientation of each grain. Local J-V curves recorded on these grains further suggest an anti-correlation behavior between the short circuit current (JSC) and open circuit voltage (VOC). This phenomenon can be attributed to diffusion-limited surface recombination at the non-selective perovskite-tip contact, where a higher carrier mobility established in the perovskite grain results in an enhanced surface recombination and thus a lower VOC. In addition, the photoresponse of perovskite films displays a pronounced heterogeneity across the grain boundaries, with the boundaries formed between grains of the same photoconductivity level displaying even enhanced photocurrent and open circuit voltage compared to those of the adjacent grain interiors. These observations highlight the significance of controlling the microstructure of perovskite thin films, which will be a necessary route for further improving the efficiency of perovskite solar cells.

Nanostructural evolution and behavior of H and Li in ion-implanted γ-LiAlO 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Weilin; Zhang, Jiandong; Edwards, Danny J.

In-situ He+ ion irradiation is performed under a helium ion microscope to study nanostructural evolution in polycrystalline gamma-LiAlO2 pellets. Various locations within a grain, across grain boundaries and at a cavity are selected. The results exhibit He bubble formation, grain-boundary cracking, nanoparticle agglomeration, increasing surface brightness with dose, and material loss from the surface. Similar brightening effects at grain boundaries are also observed under a scanning electron microscope. Li diffusion and loss from polycrystalline gamma-LiAlO2 is faster than its monocrystalline counterpart during H2+ ion implantation at elevated temperatures. There is also more significant H diffusion and release from polycrystalline pelletsmore » during thermal annealing of 300 K implanted samples. Grain boundaries and cavities could provide a faster pathway for H and Li diffusion. H release is slightly faster from the 573 K implanted monocrystalline gamma-LiAlO2 during annealing at 773 K. Metal hydrides could be formed preferentially along the grain boundaries to immobilize hydrogen.« less

Design principles for high efficiency small-grain polysilicon solar cells, with supporting experimental studies

NASA Technical Reports Server (NTRS)

Lindholm, F. A.; Neugroschel, A.; Sah, C. T.

1982-01-01

Design principles suggested here aim toward high conversion efficiency (greater than 15 percent) in polysilicon cells. The principles seek to decrease the liabilities of both intragranular and grain-boundary-surface defects. The advantages of a phosphorus atom concentration gradient in a thin (less than 50 microns) base of a p(+)/n(x)/n(+) drift-field solar cell, which produces favorable gradients in chemical potential, minority-carrier mobility and diffusivity, and recombination lifetime (via phosphorus gettering) are suggested. The degrading effects of grain boundaries are reduced by these three gradients and by substituting atoms (P, H, F or Li) for vacancies on the grain-boundary surface. From recent experiments comes support for the benefits of P diffusion down grain boundaries and, for quasi-grain-boundary-free and related structures. New analytic solutions for the n(x)-base include the effect of a power-law dependence between P concentration and lifetime. These provide an upper-bound estimate on the open circuit voltage. Finite-difference numerical solutions of the six Shockley equations furnish complete information about all solar-cell parameters and add insight concerning design.

Electromigration-Induced Surface Drift and Slit Propagation in Polycrystalline Interconnects: Insights from Phase-Field Simulations

NASA Astrophysics Data System (ADS)

Mukherjee, Arnab; Ankit, Kumar; Selzer, Michael; Nestler, Britta

2018-04-01

We employ the phase-field method to assess electromigration (EM) damage in wide polycrystalline interconnects due to grain-boundary grooving. An interplay of surface and grain-boundary diffusion is shown to drastically influence the mode of progressive EM damage. Rapid atomic transport along the surface leads to shape-preserving surface drift reminiscent of Blech drift-velocity experiments. On the other hand, a comparatively faster grain-boundary transport localizes the damage, resulting in the proliferation of intergranular slits with a shape-preserving tip. At steady state, the two regimes exhibit exponents of 1 and 3 /2 , respectively, in Black's law. While surface drift obeys an inverse scaling with grain size, slits exhibit a direct relationship at small sizes, with the dependence becoming weaker at larger ones. Furthermore, we explain the influence of curvature- or EM-mediated healing fluxes running along the surface on groove replenishment. Insights derived from phase-field simulations of EM in bicrystals are extended to investigate the multiphysics of mixed-mode damage of a polycrystalline interconnect line that is characterized by a drift of small grain surfaces, slit propagation, and coarsening. The triple and quadruple junctions are identified as prominent sites of failure.

Influence of growth temperature on bulk and surface defects in hybrid lead halide perovskite films.

PubMed

Peng, Weina; Anand, Benoy; Liu, Lihong; Sampat, Siddharth; Bearden, Brandon E; Malko, Anton V; Chabal, Yves J

2016-01-21

The rapid development of perovskite solar cells has focused its attention on defects in perovskites, which are gradually realized to strongly control the device performance. A fundamental understanding is therefore needed for further improvement in this field. Recent efforts have mainly focused on minimizing the surface defects and grain boundaries in thin films. Using time-resolved photoluminescence spectroscopy, we show that bulk defects in perovskite samples prepared using vapor assisted solution process (VASP) play a key role in addition to surface and grain boundary defects. The defect state density of samples prepared at 150 °C (∼10(17) cm(-3)) increases by 5 fold at 175 °C even though the average grains size increases slightly, ruling out grain boundary defects as the main mechanism for the observed differences in PL properties upon annealing. Upon surface passivation using water molecules, the PL intensity and lifetime of samples prepared at 200 °C are only partially improved, remaining significantly lower than those prepared at 150 °C. Thus, the present study indicates that the majority of these defect states observed at elevated growth temperatures originates from bulk defects and underscores the importance to control the formation of bulk defects together with grain boundary and surface defects to further improve the optoelectronic properties of perovskites.

Defect mapping system

DOEpatents

Sopori, Bhushan L.

1995-01-01

Apparatus for detecting and mapping defects in the surfaces of polycrystalline materials in a manner that distinguishes dislocation pits from grain boundaries includes a laser for illuminating a wide spot on the surface of the material, a light integrating sphere with apertures for capturing light scattered by etched dislocation pits in an intermediate range away from specular reflection while allowing light scattered by etched grain boundaries in a near range from specular reflection to pass through, and optical detection devices for detecting and measuring intensities of the respective intermediate scattered light and near specular scattered light. A center blocking aperture or filter can be used to screen out specular reflected light, which would be reflected by nondefect portions of the polycrystalline material surface. An X-Y translation stage for mounting the polycrystalline material and signal processing and computer equipment accommodate rastor mapping, recording, and displaying of respective dislocation and grain boundary defect densities. A special etch procedure is included, which prepares the polycrystalline material surface to produce distinguishable intermediate and near specular light scattering in patterns that have statistical relevance to the dislocation and grain boundary defect densities.

Defect mapping system

DOEpatents

Sopori, B.L.

1995-04-11

Apparatus for detecting and mapping defects in the surfaces of polycrystalline materials in a manner that distinguishes dislocation pits from grain boundaries includes a laser for illuminating a wide spot on the surface of the material, a light integrating sphere with apertures for capturing light scattered by etched dislocation pits in an intermediate range away from specular reflection while allowing light scattered by etched grain boundaries in a near range from specular reflection to pass through, and optical detection devices for detecting and measuring intensities of the respective intermediate scattered light and near specular scattered light. A center blocking aperture or filter can be used to screen out specular reflected light, which would be reflected by nondefect portions of the polycrystalline material surface. An X-Y translation stage for mounting the polycrystalline material and signal processing and computer equipment accommodate rastor mapping, recording, and displaying of respective dislocation and grain boundary defect densities. A special etch procedure is included, which prepares the polycrystalline material surface to produce distinguishable intermediate and near specular light scattering in patterns that have statistical relevance to the dislocation and grain boundary defect densities. 20 figures.

Grain Boundary Character Distributions In Isostructural Materials

NASA Astrophysics Data System (ADS)

Ratanaphan, Sutatch

Anisotropic grain boundary character distributions (GBCDs), which influence macroscopic materials properties, are thought to be controlled by the grain boundary energy anisotropy. Structurally, grain boundary could be viewed as two free surfaces joined together. Grain boundary energy could be simply defined by the total excess energy for creating two free surfaces minus the energy gained when new bonds are formed between these surfaces. This implies that different crystal structure should have different GBEDs and GBCDs. It was recently discovered that grain boundary energy distributions (GBED) in isostructural materials, a class of materials that share the same crystal structure, are directly related to one another. This suggests that GBCDs in isostructural materials might also be related in a similar way. To test this hypothesis, electron backscatter diffraction (EBSD) was used to map grain orientations in Ag, Au, Cu, Fe, and Mo. The GBCDs were determined from the stereological interpretation of EBSD maps containing on the order of 100,000 grains. It was found that the GBCDs of face-centered cubic (FCC) metals are statistically correlated, while the GBCDs of body-centered cubic (BCC) Fe and Mo are not correlated to the GBCD of FCC metals. The degree of the correlations among the FCC metals is weaker if there are significant differences in grain shape or texture. For example, Ag has the weakest correlation to the other FCC materials and also has quantitatively different grain shapes and texture. The relationship between the populations and energies of grain boundaries was also studied. By comparing the GBCDs of Al, Au, Cu, and Ni to the energies of 388 grain boundaries previously calculated by the Embedded Atom Method (EAM), we observed a moderately inverse correlation between the relative areas of grain boundaries and their energies. Interestingly, there are strong inverse correlations between the energies and populations of the most common grain boundaries (Sigma3, Sigma9, and Sigma27). Because the enhancement of twin related boundaries due to the prevalence Sigma3 boundaries results in a decrease in the grain boundary populations for the other boundary types, this inverse correlation is influenced by the crystallographic constraints at triple junctions. In other words, having an anisotropic misorientation distribution with strong maxima for certain boundaries biases the inverse correlation between grain boundary population and energy for other boundaries and causes different slopes at each misorientation. Interestingly, the inverse correlation at each misorientation is consistent with the Boltzmann distribution. Based on our results, it is possible to predict the GBCDs and GBEDs in isostructural polycrystalline materials by using a single GBCD and GBED. This principle is demonstrated by predicting the GBCD and GBED of Actinium (Ac). To investigate the GBED in the isostructural BCC metals, the energies of 408 grain boundaries in Fe and Mo were computed using atomistic simulations based on the embedded-atom method (EAM) potential. We found that the calculated boundary energies in Fe and Mo were strongly correlated and scaled with the ratio of the cohesive energy divided by the square of the lattice constant (Ecoh/a02). We would expect that the GBCD of Fe and Mo might be correlated in a similar manner to that of FCC metals. To test this hypothesis, we compared the GBCDs of Fe and Mo. We found that the GBCDs of Fe and Mo are moderately and strongly correlated when all boundary types and only Sigma3 boundaries were considered, respectively. In this thesis, the results demonstrated that the GBCDs of isostructural materials are correlated with one another and the magnitudes of correlation coefficients varied. Reduced correlations were observed when there were differences in the microstructure and crystallographic texture. The inverse relationship between grain boundary population and energy is more strongly correlated at each misorientation than over the entire five macroscopic parameters of grain boundary, especially when there is significant misorientation texture. This relationship leads to GBCDs of isostructural materials that are also more strongly correlated at each misorientation than over the entire grain boundary space.

Characterisation of Ga-coated and Ga-brazed aluminium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferchaud, E.; Christien, F., E-mail: frederic.christien@univ-nantes.fr; Barnier, V.

This work is devoted to the brazing of aluminium using liquid gallium. Gallium was deposited on aluminium samples at {approx} 50 Degree-Sign C using a liquid gallium 'polishing' technique. Brazing was undertaken for 30 min at 500 Degree-Sign C in air. EDS (Energy Dispersive X-ray Spectroscopy) and AES (Auger Electron Spectroscopy) characterisation of Ga-coated samples has shown that the Ga surface layer thickness is of ten (or a few tens of) nanometres. Furthermore, aluminium oxide layer (Al{sub 2}O{sub 3}) was shown to be 'descaled' during Ga deposition, which ensures good conditions for further brazing. Cross-section examination of Ga-coated samples showsmore » that liquid gallium penetrates into the aluminium grain boundaries during deposition. The thickness of the grain boundary gallium film was measured using an original EDS technique and is found to be of a few tens of nanometres. The depth of gallium grain boundary penetration is about 300 {mu}m at the deposition temperature. The fracture stress of the brazed joints was measured from tensile tests and was determined to be 33 MPa. Cross-section examination of brazed joints shows that gallium has fully dissolved into the bulk and that the joint is really autogenous. - Highlights: Black-Right-Pointing-Pointer Aluminium can be brazed using liquid gallium deposited by a 'polishing' technique. Black-Right-Pointing-Pointer The aluminium oxide layer is 'descaled' during liquid Ga 'polishing' deposition. Black-Right-Pointing-Pointer EDS can be used for determination of surface and grain boundary Ga film thickness. Black-Right-Pointing-Pointer The surface and grain boundary Ga film thickness is of a few tens of nm. Black-Right-Pointing-Pointer Surface and grain boundary gallium dissolves in the bulk during brazing.« less

The noncontinuum crack tip deformation behavior of surface microcracks

NASA Astrophysics Data System (ADS)

Morris, W. L.

1980-07-01

The crack tip opening displacement (CTOD) of small surface fatigue cracks (lengths of the grain size) in Al 2219-T851 depends upon the location of a crack relative to the grain boundaries. Both CTOD and crack tip closure stress are greatest when the crack tip is a large distance from the next grain boundary in the direction of crack propagation. Contrary to behavioral trends predicted by continuum fracture mechanics, crack length has no detectable effect on the contribution of plastic deformation to CTOD. It is apparent from these observations that the region of significant plastic deformation is confined by the grain boundaries, resulting in a plastic zone size that is insensitive to crack length and to external load.

Analysis of the electron-beam-induced current of a polycrystalline p-n junction when the diffusion lengths of the material on either side of a grain boundary differ

NASA Technical Reports Server (NTRS)

Von Roos, O.; Luke, K. L.

1984-01-01

The short circuit current generated by the electron beam of a scanning electron microscope in p-n junctions is reduced by enhanced recombination at grain boundaries in polycrystalline material. Frequently, grain boundaries separate the semiconductor into regions possessing different minority carrier life times. This markedly affects the short circuit current I(sc) as a function of scanning distance from the grain boundary. It will be shown theoretically that (1) the minimum of the I(sc) in crossing the grain boundary with the scanning electron beam is shifted away from the grain boundary toward the region with smaller life time (shorter diffusion length), (2) the magnitude of the minimum differs markedly from those calculated under the assumption of equal diffusion lengths on either side of the grain boundary, and (3) the minimum disappears altogether for small surface recombination velocities (s less than 10,000 cm/s). These effects become negligible, however, for large recombination velocities s at grain boundaries. For p-type silicon this happens for s not less than 100,000 cm/s.

Stress dependence of microstructures in experimentally deformed calcite

NASA Astrophysics Data System (ADS)

Platt, John P.; De Bresser, J. H. P.

2017-12-01

Optical measurements of microstructural features in experimentally deformed Carrara marble help define their dependence on stress. These features include dynamically recrystallized grain size (Dr), subgrain size (Sg), minimum bulge size (Lρ), and the maximum scale length for surface-energy driven grain-boundary migration (Lγ). Taken together with previously published data Dr defines a paleopiezometer over the range 15-291 MPa and temperature over the range 500-1000 °C, with a stress exponent of -1.09 (CI -1.27 to -0.95), showing no detectable dependence on temperature. Sg and Dr measured in the same samples are closely similar in size, suggesting that the new grains did not grow significantly after nucleation. Lρ and Lγ measured on each sample define a relationship to stress with an exponent of approximately -1.6, which helps define the boundary between a region of dominant strain-energy-driven grain-boundary migration at high stress, from a region of dominant surface-energy-driven grain-boundary migration at low stress.

Surface spins enhanced magnetoelectric coefficient and impedance spectroscopy of BaFe{sub 0.01}Ti{sub 0.99}O{sub 3} and BaFe{sub 0.015}Ti{sub 0.985}O{sub 3} nanorods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Verma, Kuldeep Chand, E-mail: kuldeep0309@yahoo.co.in; Akal School of Physics, Eternal University, Baru Sahib, Himachal Pradesh 173101; Tripathi, S.K.

2015-08-15

Highlights: • Multiferroic Fe-doped BaTiO{sub 3} nanorods. • Sol–gel. • Magnetoelectric coefficient. • Transmission electron microscopy. • Cole–Cole plots. - Abstract: Multiferroic BaFe{sub 0.01}Ti{sub 0.99}O{sub 3} (BFT1) and BaFe{sub 0.015}Ti{sub 0.985}O{sub 3} (BFT15) nanorods were prepared by a sol–gel synthesis and annealed at 700 °C/2 h. The tetragonal phase and nano dimensions of BFT samples are identified by X-ray diffraction and transmission electron microscopy. The enhancement in ferroelectricity depends upon low porosity, tetragonal phase, space charge field, larger surface area and oriented growth. The ferromagnetism depends upon partially filled inner shells, surface spins and oxygen vacancies. The magnetoelectric coefficient ismore » explained on the basis of surface spins, short-range interactions near surface boundary, compressive stress and twin structure contributed by nano grains which can reside stress near grain boundaries. The frequency dependent real (Z′) and imaginary (Z″) parts of impedance spectra are confirmed by the variations that observed in dielectric properties. The values of resistance of grain boundaries, R{sub gb} is higher than grains, R{sub g} indicating that the effect of grain boundaries is dominant in BFT nanorods.« less

Growth rate models for short surface cracks in AI 2219-T851

NASA Astrophysics Data System (ADS)

Morris, W. L.; James, M. R.; Buck, O.

1981-01-01

Rates of fatigue propagation of short Mode I surface cracks in Al 2219-T851 are measured as a function of crack length and of the location of the surface crack tips relative to the grain boundaries. The measured rates are then compared to values predicted from crack growth models. The crack growth rate is modeled with an underlying assumption that slip responsible for early propagation does not extend in significant amounts beyond the next grain boundary in the direction of crack propagation. Two models that contain this assumption are combined: 1) cessation of propagation into a new grain until a mature plastic zone is developed; 2) retardation of propagation by crack closure stress, with closure stress calculated from the location of a crack tip relative to the grain boundary. The transition from short to long crack growth behavior is also discussed.

Nonlinear Dynamics of Vortices in Different Types of Grain Boundaries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sheikhzada, Ahmad

As a major component of linear particle accelerators, superconducting radio-frequency (SRF) resonator cavities are required to operate with lowest energy dissipation and highest accelerating gradient. SRF cavities are made of polycrystalline materials in which grain boundaries can limit maximum RF currents and produce additional power dissipation sources due to local penetration of Josephson vortices. The essential physics of vortex penetration and mechanisms of dissipation of vortices driven by strong RF currents along networks of grain boundaries and their contribution to the residual surface resistance have not been well understood. To evaluate how GBs can limit the performance of SRF materials,more » particularly Nb and Nb3Sn, we performed extensive numerical simulations of nonlinear dynamics of Josephson vortices in grain boundaries under strong dc and RF fields. The RF power due to penetration of vortices both in weakly-coupled and strongly-coupled grain boundaries was calculated as functions of the RF field and frequency. The result of this calculation manifested a quadratic dependence of power to field amplitude at strong RF currents, an illustration of resistive behavior of grain boundaries. Our calculations also showed that the surface resistance is a complicated function of field controlled by penetration and annihilation of vortices and antivortices in strong RF fields which ultimately saturates to normal resistivity of grain boundary. We found that Cherenkov radiation of rapidly moving vortices in grain boundaries can produce a new instability causing generation of expanding vortex-antivortex pair which ultimately drives the entire GB in a resistive state. This effect is more pronounced in polycrystalline thin film and multilayer coating structures in which it can cause significant increase in power dissipation and results in hysteresis effects in I-V characteristics, particularly at low temperatures.« less

Electron Microscopy Characterizations and Atom Probe Tomography of Intergranular Attack in Alloy 600 Exposed to PWR Primary Water

NASA Astrophysics Data System (ADS)

Olszta, Matthew J.; Schreiber, Daniel K.; Thomas, Larry E.; Bruemmer, Stephen M.

Detailed examinations of intergranular attack (IGA) in alloy 600 were performed after exposure to simulated PWR primary water at 325°C for 500 h. High-resolution analyses of IGA characteristics were conducted on specimens with either a 1 µm diamond or 1200-grit SiC surface finish using scanning electron microscopy, transmission electron microscopy and atom probe tomography techniques. The diamond-polish finish with very little preexisting subsurface damage revealed attack of high-energy grain boundaries that intersected the exposed surface to depths approaching 2 µm. In all cases, IGA from the surface is localized oxidation consisting of porous, nanocrystalline MO-structure and spinel particles along with regions of faceted wall oxidation. Surprisingly, this continuous IG oxidation transitions to discontinuous, discrete Cr-rich sulfide particles up to 50 nm in diameter. In the vicinity of the sulfides, the grain boundaries were severely Cr depleted (to <1 at%) and enriched in S. The 1200 grit SiC finish surface exhibited a preexisting highly strained recrystallized layer of elongated nanocrystalline matrix grains. Similar IG oxidation and leading sulfide particles were found, but the IGA depth was typically confined to the near-surface ( 400 nm) recrystallized region. Difference in IGA for the two surface finishes indicates that the formation of grain boundary sulfides occurs during the exposure to PWR primary water. The source of S remains unclear, however it is not present as sulfides in the bulk alloy nor is it segregated to bulk grain boundaries.

Defect structures in ordered intermetallics; grain boundaries and surfaces in FeAl, NiAl, CoAl and TiAl

NASA Astrophysics Data System (ADS)

Mutasa, Batsirai Manyara

Ordered intermetallics based on transition metal aluminides have been proposed as structural materials for advanced aerospace applications. The development of these materials, which have the advantages of low density and high operating temperatures, have been focused on the aluminides of titanium, nickel and iron. Though these materials exhibit attractive properties at elevated temperatures, their utilization is limited due to their propensity for low temperature fracture and susceptibility to decreased ductility due to environmental effects. A major embrittlement mechanism at ambient temperatures in these aluminides has been by the loss of cohesive strength at the interfaces (intergranular failure). This study focuses on this mechanism of failure, by undertaking a systematic study of the energies and structures of specific grain boundaries in some of these compounds. The relaxed atomistic grain boundary structures in B2 aluminides, FeAl, NiAl and CoAl and L10 gamma-TiAl were investigated using molecular statics and embedded atom potentials in order to explore general trends for a series of B2 compounds as well as TiAl. The potentials used correctly predict the proper mechanism of compositional disorder of these compounds. Using these potentials, point defects, free surface energies and various grain boundary structures of similar energies in three B2 compounds, FeAl, NiAl and CoAl were studied. These B2 alloys exhibited increasing anti-phase boundary energies respectively. The misorientations chosen for detailed study correspond to the Sigma5(310) and Sigma5(210) boundaries. These boundaries were investigated with consideration given to possible variations in the local chemical composition. The effects of both boundary stoichiometry and bulk stoichiometry on grain boundary energetics were also considered. Defect energies were calculated for boundaries contained in both stoichiometric and off-stoichiometric bulk. The surface energies for these aluminides were also calculated so that trends concerning the cohesive energy of the boundaries could be studied. The implications of stoichiometry, the multiplicity of the boundary structures and possible transformations between them for grain boundary brittleness are also discussed.

Electromigration-induced void grain-boundary interactions: The mean time to failure for copper interconnects with bamboo and near-bamboo structures

NASA Astrophysics Data System (ADS)

Ogurtani, Tarik Omer; Oren, Ersin Emre

2004-12-01

A well-posed moving boundary-value problem, describing the dynamics of curved interfaces and surfaces associated with voids and/or cracks that are interacting with grain boundaries, is obtained. Extensive computer simulations are performed for void configuration evolution during intergranular motion, under the actions of capillary and electromigration forces in thin-film metallic interconnects with bamboo structures. The analysis of experimental data, utilizing the mean time to failure formulas derived in this paper, gives consistent values for the interface diffusion coefficients and enthalpies of voids. 5.85×10-5exp(-0.95eV/kT)m2s-1 is the value obtained for voids that form in the interior of the copper interconnects avoiding any surface contamination. 1.80×10-4exp(-1.20eV/kT)m2s-1 is obtained for those voids that nucleate either at triple junctions or at the grain-boundary technical surface intersections (grain-boundary groove), where the chemical impurities such as Si, O, S, and even C are segregated during the metallization and annealing processes and may act as trap centers for hopping vacancies.

Oxygen diffusion in nanocrystalline yttria-stabilized zirconia: the effect of grain boundaries.

PubMed

De Souza, Roger A; Pietrowski, Martha J; Anselmi-Tamburini, Umberto; Kim, Sangtae; Munir, Zuhair A; Martin, Manfred

2008-04-21

The transport of oxygen in dense samples of yttria-stabilized zirconia (YSZ), of average grain size d approximately 50 nm, has been studied by means of 18O/16O exchange annealing and secondary ion mass spectrometry (SIMS). Oxygen diffusion coefficients (D*) and oxygen surface exchange coefficients (k*) were measured for temperatures 673

Diffusion-coupled cohesive interface simulations of stress corrosion intergranular cracking in polycrystalline materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pu, Chao; Gao, Yanfei; Wang, Yanli

To study the stress corrosion intergranular cracking mechanism, a diffusion-coupled cohesive zone model (CZM) is proposed for the simulation of the stress-assisted diffusional process along grain boundaries and the mechanical response of grain boundary sliding and separation. This simulation methodology considers the synergistic effects of impurity diffusion driven by pressure gradient and degradation of grain boundary strength by impurity concentration. The diffusion-coupled CZM is combined with crystal plasticity finite element model (CPFEM) to simulate intergranular fracture of polycrystalline material under corrosive environment. Significant heterogeneity of the stress field and extensive impurity accumulation is observed at grain boundaries and junction points.more » Deformation mechanism maps are constructed with respect to the grain boundary degradation factor and applied strain rate, which dictate the transition from internal to near-surface intergranular fracture modes under various strain amplitudes and grain sizes.« less

Three-dimensional study of grain boundary engineering effects on intergranular stress corrosion cracking of 316 stainless steel in high temperature water

NASA Astrophysics Data System (ADS)

Liu, Tingguang; Xia, Shuang; Bai, Qin; Zhou, Bangxin; Zhang, Lefu; Lu, Yonghao; Shoji, Tetsuo

2018-01-01

The intergranular cracks and grain boundary (GB) network of a GB-engineered 316 stainless steel after stress corrosion cracking (SCC) test in high temperature high pressure water of reactor environment were investigated by two-dimensional and three-dimensional (3D) characterization in order to expose the mechanism that GB-engineering mitigates intergranular SCC. The 3D microstructure shown that the essential characteristic of the GB-engineered microstructure is formation of many large twin-boundaries as a result of multiple-twinning, which results in the formation of large grain-clusters. The large grain-clusters played a key role to the improvement of intergranular SCC resistance by GB-engineering. The main intergranular cracks propagated in a zigzag along the outer boundaries of these large grain-clusters because all inner boundaries of the grain-clusters were twin-boundaries (∑3) or twin-related boundaries (∑3n) which had much lower susceptibility to SCC than random boundaries. These large grain-clusters had tree-ring-shaped topology structure and very complex morphology. They got tangled so that difficult to be separated during SCC, resulting in some large crack-bridges retained in the crack surface.

Recombination activity of grain boundaries in high-performance multicrystalline Si during solar cell processing

NASA Astrophysics Data System (ADS)

Adamczyk, Krzysztof; Søndenâ, Rune; Stokkan, Gaute; Looney, Erin; Jensen, Mallory; Lai, Barry; Rinio, Markus; Di Sabatino, Marisa

2018-02-01

In this work, we applied internal quantum efficiency mapping to study the recombination activity of grain boundaries in High Performance Multicrystalline Silicon under different processing conditions. Wafers were divided into groups and underwent different thermal processing, consisting of phosphorus diffusion gettering and surface passivation with hydrogen rich layers. After these thermal treatments, wafers were processed into heterojunction with intrinsic thin layer solar cells. Light Beam Induced Current and Electron Backscatter Diffraction were applied to analyse the influence of thermal treatment during standard solar cell processing on different types of grain boundaries. The results show that after cell processing, most random-angle grain boundaries in the material are well passivated, but small-angle grain boundaries are not well passivated. Special cases of coincidence site lattice grain boundaries with high recombination activity are also found. Based on micro-X-ray fluorescence measurements, a change in the contamination level is suggested as the reason behind their increased activity.

Subsurface Grain Morphology Reconstruction by Differential Aperture X-ray Microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eisenlohr, Philip; Shanthraj, Pratheek; Vande Kieft, Brendan R.

A multistep, non-destructive grain morphology reconstruction methodology that is applicable to near-surface volumes is developed and tested on synthetic grain structures. This approach probes the subsurface crystal orientation using differential aperture x-ray microscopy on a sparse grid across the microstructure volume of interest. Resulting orientation data are clustered according to proximity in physical and orientation space and used as seed points for an initial Voronoi tessellation to (crudely) approximate the grain morphology. Curvature-driven grain boundary relaxation, simulated by means of the Voronoi implicit interface method, progressively improves the reconstruction accuracy. The similarity between bulk and readily accessible surface reconstruction errormore » provides an objective termination criterion for boundary relaxation.« less

Morphologies of tungsten nanotendrils grown under helium exposure.

PubMed

Wang, Kun; Doerner, R P; Baldwin, M J; Meyer, F W; Bannister, M E; Darbal, Amith; Stroud, Robert; Parish, Chad M

2017-02-14

Nanotendril "fuzz" will grow under He bombardment under tokamak-relevant conditions on tungsten plasma-facing materials in a magnetic fusion energy device. We have grown tungsten nanotendrils at low (50 eV) and high (12 keV) He bombardment energy, in the range 900-1000 °C, and characterized them using electron microscopy. Low energy tendrils are finer (~22 nm diameter) than high-energy tendrils (~176 nm diameter), and low-energy tendrils have a smoother surface than high-energy tendrils. Cavities were omnipresent and typically ~5-10 nm in size. Oxygen was present at tendril surfaces, but tendrils were all BCC tungsten metal. Electron diffraction measured tendril growth axes and grain boundary angle/axis pairs; no preferential growth axes or angle/axis pairs were observed, and low-energy fuzz grain boundaries tended to be high angle; high energy tendril grain boundaries were not observed. We speculate that the strong tendency to high-angle grain boundaries in the low-energy tendrils implies that as the tendrils twist or bend, strain must accumulate until nucleation of a grain boundary is favorable compared to further lattice rotation. The high-energy tendrils consisted of very large (>100 nm) grains compared to the tendril size, so the nature of the high energy irradiation must enable faster growth with less lattice rotation.

Intrinsic Compressive Stress in Polycrystalline Films is Localized at Edges of the Grain Boundaries.

PubMed

Vasco, Enrique; Polop, Celia

2017-12-22

The intrinsic compression that arises in polycrystalline thin films under high atomic mobility conditions has been attributed to the insertion or trapping of adatoms inside grain boundaries. This compression is a consequence of the stress field resulting from imperfections in the solid and causes the thermomechanical fatigue that is estimated to be responsible for 90% of mechanical failures in current devices. We directly measure the local distribution of residual intrinsic stress in polycrystalline thin films on nanometer scales, using a pioneering method based on atomic force microscopy. Our results demonstrate that, at odds with expectations, compression is not generated inside grain boundaries but at the edges of gaps where the boundaries intercept the surface. We describe a model wherein this compressive stress is caused by Mullins-type surface diffusion towards the boundaries, generating a kinetic surface profile different from the mechanical equilibrium profile by the Laplace-Young equation. Where the curvatures of both profiles differ, an intrinsic stress is generated in the form of Laplace pressure. The Srolovitz-type surface diffusion that results from the stress counters the Mullins-type diffusion and stabilizes the kinetic surface profile, giving rise to a steady compression regime. The proposed mechanism of competition between surface diffusions would explain the flux and time dependency of compressive stress in polycrystalline thin films.

Intrinsic Compressive Stress in Polycrystalline Films is Localized at Edges of the Grain Boundaries

NASA Astrophysics Data System (ADS)

Vasco, Enrique; Polop, Celia

2017-12-01

The intrinsic compression that arises in polycrystalline thin films under high atomic mobility conditions has been attributed to the insertion or trapping of adatoms inside grain boundaries. This compression is a consequence of the stress field resulting from imperfections in the solid and causes the thermomechanical fatigue that is estimated to be responsible for 90% of mechanical failures in current devices. We directly measure the local distribution of residual intrinsic stress in polycrystalline thin films on nanometer scales, using a pioneering method based on atomic force microscopy. Our results demonstrate that, at odds with expectations, compression is not generated inside grain boundaries but at the edges of gaps where the boundaries intercept the surface. We describe a model wherein this compressive stress is caused by Mullins-type surface diffusion towards the boundaries, generating a kinetic surface profile different from the mechanical equilibrium profile by the Laplace-Young equation. Where the curvatures of both profiles differ, an intrinsic stress is generated in the form of Laplace pressure. The Srolovitz-type surface diffusion that results from the stress counters the Mullins-type diffusion and stabilizes the kinetic surface profile, giving rise to a steady compression regime. The proposed mechanism of competition between surface diffusions would explain the flux and time dependency of compressive stress in polycrystalline thin films.

A study of fractography in the low-temperature brittle fracture of an 18Cr-18Mn-0.7N austenitic steel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, S.C.; Hashida, T.; Takahashi, H.

1998-03-01

The fracture mode and crack propagation behavior of brittle fracture at 77 and 4 K in an 18Cr-18Mn-0.7N austenitic stainless were investigated using optical and scanning electron microscopy. The fracture path was examined by observing the side surface in a partially ruptured specimen. The relationship of the fracture facets to the microstructures were established by observing the fracture surface and the adjacent side surface simultaneously. Three kinds of fracture facets were identified at either temperature. The first is a smooth curved intergranular fracture facet with characteristic parallel lines on it. The second is a fairly planar facet formed by partingmore » along an annealing twin boundary, a real {l_brace}111{r_brace} plane. There are three sets of parallel lines on the facet and the lines in different sets intersect at 60 deg. The third is a lamellar transgranular fracture facet with sets of parallel steps on it. Fracture propagated by the formation of microcracks on a grain boundary, annealing twin boundary, and coalescence of these cracks. The observation suggests that the ease of crack initiation and propagation along the grain boundary and the annealing twin boundary may be the main reason for the low-temperature brittleness of this steel. A mechanism for grain boundary cracking, including annealing twin boundary parting, has been discussed based on the stress concentration induced by impinging planar deformation structures on the grain boundaries.« less

The Formation, Transport Properties and Microstructure of 45 Degrees (001) Tilt Grain Boundaries in Yttrium BARIUM(2) COPPER(3) OXYGEN(7-X) Thin Films

NASA Astrophysics Data System (ADS)

Vuchic, Boris Vukan

1995-01-01

Most high angle grain boundaries in high-T _{c} superconductors exhibit weak link behavior. The Josephson-like properties of these grain boundaries can be used for many device applications such as superconducting quantum interference devices (SQUIDs). The structure-property relationship of different types of 45 ^circ (001) YBa_2 Cu_3O_{7-x} thin film grain boundary junctions are examined to study their weak link nature. A technique, termed sputter-induced epitaxy, is developed to form 45^circ (001) tilt grain boundaries in YBa_2Cu _3O_{7-x} thin films on (100) MgO substrates. A low voltage ion bombardment pre-growth substrate treatment is used to modify the epitaxial orientation relationship between the thin film and the substrate in selected regions. By modifying the orientation of the thin film, grain boundary junctions can be placed in any configuration on the substrate. A variety of pre-growth sputtering conditions in conjunction with atomic force microscopy and Rutherford backscatter spectrometry are used to determine the role of the ions in modifying the substrate surface. Sputter-induced epitaxy is extended to a multilayer MgO/LaAlO_3 substrate, allowing integration of the sputter -induced epitaxy junctions into multilayer structures. The low temperature transport properties of the sputter-induced epitaxy junctions and a set of bi-epitaxial grain boundaries are studied. Individual grain boundaries are isolated and characterized for resistance vs. temperature, current vs. voltage as a function of temperature and magnetic field behavior. Resistive and superconducting grain boundaries are compared. Microstructural analysis is performed using scanning electron microscopy, transmission electron microscopy and high resolution electron microscopy (HREM). Marked differences are observed in the microstructure of resistive and superconducting grain boundaries. HREM studies suggest the importance of the local atomic scale structure of the grain boundary in transport properties. A phenomenological grain boundary model is proposed to describe the structure -property relationship of the boundaries.

Nanocrystalline copper films are never flat.

PubMed

Zhang, Xiaopu; Han, Jian; Plombon, John J; Sutton, Adrian P; Srolovitz, David J; Boland, John J

2017-07-28

We used scanning tunneling microscopy to study low-angle grain boundaries at the surface of nearly planar copper nanocrystalline (111) films. The presence of grain boundaries and their emergence at the film surface create valleys composed of dissociated edge dislocations and ridges where partial dislocations have recombined. Geometric analysis and simulations indicated that valleys and ridges were created by an out-of-plane grain rotation driven by reduction of grain boundary energy. These results suggest that in general, it is impossible to form flat two-dimensional nanocrystalline films of copper and other metals exhibiting small stacking fault energies and/or large elastic anisotropy, which induce a large anisotropy in the dislocation-line energy. Copyright © 2017 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Imaging the Hydrogen Absorption Dynamics of Individual Grains in Polycrystalline Palladium Thin Films in 3D

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yau, Allison; Harder, Ross J.; Kanan, Matthew W.

Defects such as dislocations and grain boundaries often control the properties of polycrystalline materials. In nanocrystalline materials, investigating this structure-function relationship while preserving the sample remains challenging because of the short length scales and buried interfaces involved. Here we use Bragg coherent diffractive imaging to investigate the role of structural inhomogeneity on the hydriding phase transformation dynamics of individual Pd grains in polycrystalline films in three-dimensional detail. In contrast to previous reports on single- and polycrystalline nanoparticles, we observe no evidence of a hydrogen-rich surface layer and consequently no size dependence in the hydriding phase transformation pressure over a 125-325more » nm size range. We do observe interesting grain boundary dynamics, including reversible rotations of grain lattices while the material remains in the hydrogen-poor phase. The mobility of the grain boundaries, combined with the lack of a hydrogen-rich surface layer, suggests that the grain boundaries are acting as fast diffusion sites for the hydrogen atoms. Such hydrogen-enhanced plasticity in the hydrogen poor phase provides insight into the switch from the size-dependent behavior of single-crystal nanoparticles to the lower transformation pressures of polycrystalline materials and may play a role in hydrogen embrittlement.« less

Hexamethylenetetramine-mediated growth of grain-boundary-passivation CH3NH3PbI3 for highly reproducible and stable perovskite solar cells

NASA Astrophysics Data System (ADS)

Zheng, Yan-Zhen; Li, Xi-Tao; Zhao, Er-Fei; Lv, Xin-Ding; Meng, Fan-Li; Peng, Chao; Lai, Xue-Sen; Huang, Meilan; Cao, Guozhong; Tao, Xia; Chen, Jian-Feng

2018-02-01

Simultaneously achieving the long-term device stability and reproducibility has proven challenging in perovskite solar cells because solution-processing produced perovskite film with grain boundary is sensitive to moisture. Herein, we develop a hexamethylenetetramine (HMTA)-mediated one-step solution-processing deposition strategy that leads to the formation of high-purity and grain-boundary-passivation CH3NH3PbI3 film and thereby advances cell optoelectronic performance. Through morphological and structural characterizations and theoretical calculations, we demonstrate that HMTA fully occupies the moisture-exposed surface to build a bridge across grain boundary and coordinates with Pb ions to inhibit the formation of detrimental PbI2. Such HMTA-mediated grown CH3NH3PbI3 films achieves a decent augmentation of power conversion efficiency (PCE) from 12.70% to 17.87%. A full coverage of PbI2-free CH3NH3PbI3 surface on ZnO also boosts the device's stability and reproducibility.

Stress Dependence of Microstructures in Experimentally Deformed Calcite

NASA Astrophysics Data System (ADS)

Platt, J. P.; De Bresser, J. H. P.

2017-12-01

Measurements of dynamically recrystallized grain size (Dr), subgrain size (Sg), minimum bulge size (Blg), and the maximum scale length for surface-energy driven grain-boundary migration (γGBM) in experimentally deformed Cararra marble help define the dependence of these microstructural features on stress and temperature. Measurements were made optically on ultra-thin sections in order to allow these features to be defined during measurement on the basis of microstructural setting and geometry. Taken together with previously published data Dr defines a paleopiezometer with a stress exponent of -1.09. There is no discernible temperature dependence over the 500°C temperature range of the experiments. Recrystallization occured mainly by bulging and subgrain rotation, and the two processes operated together, so that it is not possible to separate grains nucleated by the two mechanisms. Sg and Dr measured in the same samples are closely similar in size, suggesting that new grains do not grow significantly after nucleation, and that subgrain size is likely to be the primary control on recrystallized grain size. Blg and γGBM measured on each sample define a relationship to stress with an exponent of approximately -1.6, which helps define the boundary in stress - grain-size space between a region of dominant strain-energy-driven grain-boundary migration at high stress, from a region of dominant surface-energy-driven grain-boundary migration at low stress.

Deformation and erosion of f.c.c. metals and alloys under cavitation attack

NASA Technical Reports Server (NTRS)

Rao, B. C. S.; Buckley, D. H.

1984-01-01

Experimental investigations have been conducted to determine the early stages of cavitation attack on 6061-T6 aluminum alloy, electrolytic tough pitch copper, brass, and bronze, all having polycrystalline fcc matrices. The surface profiles and scanning electron micrographs show that the pits are initially formed at the grain boundaries, while the grain surfaces are progressively roughened by multiple slip and twinning. The initial erosion is noted to have occurred from the material in the grain boundaries, as well as by fragmentation of part of the grains. Further erosion occurred by shearing and necking of the surface undulations caused by plastic deformation. The mean penetration depth, computed on the basis of mass loss, was lowest on the bronze and greatest on the copper. Attention is given to the relation of cavitation attack to grain size, glide stress and stacking fault energy.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frolov, T.; Setyawan, W.; Kurtz, R. J.

We report a computational discovery of novel grain boundary structures and multiple grain boundary phases in elemental bcc tungsten. While grain boundary structures created by the - surface method as a union of two perfect half crystals have been studied extensively, it is known that the method has limitations and does not always predict the correct ground states. Here, we use a newly developed computational tool, based on evolutionary algorithms, to perform a grand-canonical search of high-angle symmetric tilt boundary in tungsten, and we find new ground states and multiple phases that cannot be described using the conventional structural unitmore » model. We use MD simulations to demonstrate that the new structures can coexist at finite temperature in a closed system, confirming these are examples of different GB phases. The new ground state is confirmed by first-principles calculations.Evolutionary grand-canonical search predicts novel grain boundary structures and multiple grain boundary phases in elemental body-centered cubic (bcc) metals represented by tungsten, tantalum and molybdenum.« less

Microstructural characterization of ultrasonic impact treated aluminum-magnesium alloy

NASA Astrophysics Data System (ADS)

Tran, Kim Ngoc Thi

Aluminum 5456-H116 has high as-welded strength, is formable, and highly corrosion resistant, however, it can become sensitized when exposed to elevated temperatures for a prolonged time. Sensitization results in the formation of a continuous β phase at the grain boundaries that is anodic to the matrix. Thus the grain boundaries become susceptible to stress corrosion cracking (SCC) and intergranular corrosion cracking (IGC). Cracking issues on aluminum superstructures have prompted the use of a severe plastic deformation processes, such as ultrasonic impact treatment (UIT), to improve SCC resistance. This study correlated the effects of UIT on the properties of 5456-H116 alloy to the microstructural evolution of the alloy and helped develop a fundamental understanding of the mechanisms that cause the microstructural evolution. Ultrasonic impact treatment produces a deformed layer at the surface ˜ 10 to 18 µm thick that is characterized by micro-cracks, tears, and voids. Ultrasonic impact treatment results in grain refinement within the deformation layer and extending below the deformed layer. The microstructure exhibits weak crystallographic texture with larger fraction of high angle grain boundaries. Nanocrystalline grains within the deformation layer vary in size from 2 to 200 nm in diameter and exhibit curved or wavy grain boundaries. The nanocrystalline grains are thermally stable up to 300°C. Above 300°C, grain growth occurs with an activation energy of ˜ 32 kJ/mol. Below the deformation layer, the microstructure is characterized by submicron grains, complex structure of dislocations, sub-boundaries, and Moiré fringes depicting overlapping grains. The deformation layer does not exhibit the presence of a continuous β phase, however below the deformation layer; a continuous β phase along the grain boundaries is present. In general the highest hardness and yield strength is at the UIT surface which is attributed to the formation of nanocrystalline grains. Although the highest hardness and yield strength was observed at the UIT surface, the results were mixed with some lower values. The lower hardness and yield strength values at the UIT surface are attributed to the voids and micro cracking/micro voids observed in the deformation layer. The fracture mode was transgranular ductile fracture with micro void coalescence and dimples. Both UIT and untreated material exhibit similar levels of intergranular corrosion susceptibility. Corrosive attack was intergranular with slightly deeper attack in the untreated material. Numerical simulation modeling showed that the calculated residual stress under the tool, ˜80 MPa, is of the same order of magnitude as the compressive residual stresses measured by XRD measurements near the surface. Modeling also showed that high effective strains were induced almost immediately. The UIT process also resulted in rapid localized heating to a maximum temperature of ˜32°C during the first eleven pin tool cycles. The model also showed that during UIT processing, the material undulates as the pin tool impacts and retracts from the surface of the material. The undulations represent the elastic response of the surface to the compressive stresses built up during a pin tool cycle.

Finite element modelling of creep cavity filling by solute diffusion

NASA Astrophysics Data System (ADS)

Versteylen, C. D.; Szymański, N. K.; Sluiter, M. H. F.; van Dijk, N. H.

2018-04-01

In recently discovered self healing creep steels, open-volume creep cavities are filled by the precipitation of supersaturated solute. These creep cavities form on the grain boundaries oriented perpendicular to the applied stress. The presence of a free surface triggers a flux of solute from the matrix, over the grain boundaries towards the creep cavities. We studied the creep cavity filling by finite element modelling and found that the filling time critically depends on (i) the ratio of diffusivities in the grain boundary and the bulk, and (ii) on the ratio of the intercavity distance and the cavity size. For a relatively large intercavity spacing 3D transport is observed when the grain boundary and volume diffusivities are of a similar order of magnitude, while a 2D behaviour is observed when the grain boundary diffusivity is dominant. Instead when the intercavity distance is small, the transport behaviour tends to a 1D behaviour in all cases, as the amount of solute available in the grain boundary is insufficient. A phase diagram with the transition lines is constructed.

Morphologies of tungsten nanotendrils grown under helium exposure

DOE PAGES

Wang, Kun; Doerner, R. P.; Baldwin, Matthew J.; ...

2017-02-14

Nanotendril “fuzz” will grow under He bombardment under tokamak-relevant conditions on tungsten plasma-facing materials in a magnetic fusion energy device. We have grown tungsten nanotendrils at low (50 eV) and high (12 keV) He bombardment energy, in the range 900–1000 °C, and characterized them using electron microscopy. Low energy tendrils are finer (~22 nm diameter) than high-energy tendrils (~176 nm diameter), and low-energy tendrils have a smoother surface than high-energy tendrils. Cavities were omnipresent and typically ~5–10 nm in size. Oxygen was present at tendril surfaces, but tendrils were all BCC tungsten metal. Electron diffraction measured tendril growth axes andmore » grain boundary angle/axis pairs; no preferential growth axes or angle/axis pairs were observed, and low-energy fuzz grain boundaries tended to be high angle; high energy tendril grain boundaries were not observed. We speculate that the strong tendency to high-angle grain boundaries in the low-energy tendrils implies that as the tendrils twist or bend, strain must accumulate until nucleation of a grain boundary is favorable compared to further lattice rotation. Finally, the high-energy tendrils consisted of very large (>100 nm) grains compared to the tendril size, so the nature of the high energy irradiation must enable faster growth with less lattice rotation.« less

Morphologies of tungsten nanotendrils grown under helium exposure

PubMed Central

Wang, Kun; Doerner, R. P.; Baldwin, M. J.; Meyer, F. W.; Bannister, M. E.; Darbal, Amith; Stroud, Robert; Parish, Chad M.

2017-01-01

Nanotendril “fuzz” will grow under He bombardment under tokamak-relevant conditions on tungsten plasma-facing materials in a magnetic fusion energy device. We have grown tungsten nanotendrils at low (50 eV) and high (12 keV) He bombardment energy, in the range 900–1000 °C, and characterized them using electron microscopy. Low energy tendrils are finer (~22 nm diameter) than high-energy tendrils (~176 nm diameter), and low-energy tendrils have a smoother surface than high-energy tendrils. Cavities were omnipresent and typically ~5–10 nm in size. Oxygen was present at tendril surfaces, but tendrils were all BCC tungsten metal. Electron diffraction measured tendril growth axes and grain boundary angle/axis pairs; no preferential growth axes or angle/axis pairs were observed, and low-energy fuzz grain boundaries tended to be high angle; high energy tendril grain boundaries were not observed. We speculate that the strong tendency to high-angle grain boundaries in the low-energy tendrils implies that as the tendrils twist or bend, strain must accumulate until nucleation of a grain boundary is favorable compared to further lattice rotation. The high-energy tendrils consisted of very large (>100 nm) grains compared to the tendril size, so the nature of the high energy irradiation must enable faster growth with less lattice rotation. PMID:28195125

Fluid distribution in grain boundaries of natural fine-grained rock salt deformed at low differential stress (Qom Kuh salt fountain, central Iran): Implications for rheology and transport properties

NASA Astrophysics Data System (ADS)

Desbois, Guillaume; Urai, Janos L.; de Bresser, Johannes H. P.

2012-10-01

We used a combination of broad ion beam cross-sectioning and cryogenic SEM to image polished surfaces and corresponding pairs of fractured grain boundaries in an investigation of grain boundary microstructures and fluid distribution in naturally deformed halite from the Qom Kuh salt glacier (central Iran). At the scale of observations, four types of fluid-filled grain boundary can be distinguished by morphology (from straight to wavy), thickness (from 5000 to 50 nm) and the presence of fluid inclusions. The mobility of the brine is shown after cutting the inclusions by broad ion beam (BIB) in vacuum and fine-grained halite forms efflorescence and precipitates on internal walls of inclusions. At cryogenic temperature, grain boundary brine is shown either as continuous film or in isolated inclusions. The halite-halite grain boundary between isolated fluid inclusions is interpreted to have formed by fluid-assisted grain boundary healing. Preliminary experiments on the samples at shear stress conditions of natural salt glacier show very slow strain rates (7.4 × 10-10 s-1 and 1 × 10-9 s-1), which are less than expected for pressure solution creep. Both microstructures and deformation experiments suggest interfacial energy-driven grain boundary healing and therefore rendering inactive the pressure solution creep in our samples. This result disagrees with previous microstructural studies of the same sample, which showed microstructural evidence for pressure solution (and dislocation creep). Different explanations are discussed, which imply that both healing and reactivation of grain boundaries are important in salt glaciers, leading to heterogeneous distribution of deformation mechanisms and strain rates in both space and time.

Microstructural effects on damage evolution in shocked copper polycrystals

DOE PAGES

Lieberman, Evan J.; Lebensohn, Ricardo A.; Menasche, David B.; ...

2016-07-01

Three-dimensional crystal orientation fields of a copper sample, characterized before and after shock loading using High Energy Diffraction Microscopy, are used for input and validation of direct numerical simulations using a Fast Fourier Transform (FFT)-based micromechanical model. The locations of the voids determined by X-ray tomography in the incipiently-spalled sample, predominantly found near grain boundaries, were traced back and registered to the pre-shocked microstructural image. Using FFT-based simulations with direct input from the initial microstructure, micromechanical fields at the shock peak stress were obtained. Statistical distributions of micromechanical fields restricted to grain boundaries that developed voids after the shock aremore » compared with corresponding distributions for all grain boundaries. Distributions of conventional measures of stress and strain (deviatoric and mean components) do not show correlation with the locations of voids in the post-shocked image. Neither does stress triaxiality, surface traction or grain boundary inclination angle, in a significant way. On the other hand, differences in Taylor factor and accumulated plastic work across grain boundaries do correlate with the occurrence of damage. As a result, damage was observed to take place preferentially at grain boundaries adjacent to grains having very different plastic response.« less

Graphene quantum dot incorporated perovskite films: passivating grain boundaries and facilitating electron extraction.

PubMed

Fang, Xiang; Ding, Jianning; Yuan, Ningyi; Sun, Peng; Lv, Minghang; Ding, Guqiao; Zhu, Chong

2017-02-22

Organic-inorganic halide perovskites have emerged as attractive materials for use in photovoltaic cells. Owing to the existence of dangling bonds at the grain boundaries between perovskite crystals, minimizing the charge recombination at the surface or grain boundaries by passivating these trap states has been identified to be one of the most important strategies for further optimization of device performance. Previous reports have mainly focused on surface passivation by inserting special materials such as graphene or fullerene between the electron transfer layer and the perovskite film. Here, we report an enhanced efficiency of mesoscopic perovskite solar cells by using graphene quantum dots (GQDs) to passivate the grain boundaries of CH 3 NH 3 PbI 3 . The highest efficiency (17.62%) is achieved via decoration with 7% GQDs, which is an 8.2% enhancement with respect to a pure perovskite based device. Various analyses including electrochemical impedance spectroscopy, time-resolved photoluminescence decay and open-circuit voltage decay measurements are employed in investigating the mechanism behind the improvement in device performance. The findings reveal two important roles played by GQDs in promoting the performance of perovskite solar cells - that GQDs are conducive to facilitating electron extraction and can effectively passivate the electron traps at the perovskite grain boundaries.

Effect of hot extrusion, other constituents, and temperature on the strength and fracture of polycrystalline MgO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rice, R.W.

Improved agreement was confirmed between the Petch intercept and single-crystal yield stresses at 22 C. Hot-extruded MgO crystal specimens stressed parallel with the resultant axial texture (1) gave the highest and least-scattered strength-grain size results at 22 C, (2) showed direct fractographic evidence of microplastic initiated fracture at 22 C and showed macroscopic yield at 1,315 and especially 1,540 C, and (3) fractured entirely via transgranular cleavage, except for intergranular failure initiation from one or a few grain boundary surfaces exposed on the subsequent fracture surface, mainly at 1,540 C. Hot-extruded, hot-pressed MgO billets gave comparable strength when fracture initiatedmore » transgranularly, but lower strength when fracture initiated from one or especially a few grain boundary surfaces exposed on the fracture. The extent and frequency of such boundary fracture increased with test temperature. While oxide additions of [<=] 5% or impurities in hot-pressed or hot-extruded MgO can make limited strength increases at larger grain sizes, those having limited solubility can limit strength at finer grain sizes, as can coarser surface finish. Overall, MgO strength is seen as a balance between flaw and microplastic controlled failure, with several parameters shifting the balance.« less

Surface diffusivity measurements on 8mol.% yttrium oxide-zirconia bicrystals via grain boundary grooving experiments

NASA Astrophysics Data System (ADS)

Nassirou, Maissarath

Thermal grooving at grain boundaries (GBs) is a capillary-driven evolution of surface topography in the region where the grain boundary emerges at a free surface. The study of these topographic changes can provide insight into surface energetics, and in our particular case, the measurement of surface diffusivity. We have measured the surface diffusion coefficient of 8mol% Y 2O3-ZrO2 by studying the formation of thermal grooves. We studied a total of five bicrystals, with well defined orientation relationships; random [110] -60°, random [001] -30°, Sigma13 [001]/{510}, Sigma13 [001]/{320}, Sigma5 [001]/{210}. Our calculations employed the Herring relation (1951), in which the variation in the chemical potential is related to changes in topography. The samples were annealed at 1300°C and 1400°C for various period of time. Atomic Force Microscopy was used to determine the exact geometry of the thermal grooves. A first approach consisted of estimating the diffusion coefficient by using Mullins' equation. yx=0= dsDs1/ 4gb2g s12G 5/4( WkTgs) 1/4t 1/4 Where y(x =0) is the groove depth at the GB triple junction, O is the atomic volume, gs is the surface tension, gb is the grain boundary surface energy, ds is the thickness of the diffusion layer, t is the annealing time, and Ds is the surface diffusion coefficient. In Mullins' derivation, the atomic structure of the surface was ignored and it was assumed that the surface energy is independent of crystallographic orientation. In the case of zirconia, the surface energy is anisotropic. We will describe in this work a new approach to measuring surface diffusivity which accounts for the surface energy anisotropy. The study of these bicrystals will emphasize the effect of grain boundary structure on the surface diffusion coefficient, and it is for that purpose that we selected bicrystals with different tilt axes and angles. The results obtained using the equation set we have developed will be compared to those obtained by Mullins, and we show that the anisotropic groove evolution, even when perfectly symmetrical, is much slower than the corresponding isotropic case.

Packed bed carburization of tantalum and tantalum alloy

DOEpatents

Lopez, Peter C.; Rodriguez, Patrick J.; Pereyra, Ramiro A.

1999-01-01

Packed bed carburization of a tantalum or tantalum alloy object. A method for producing corrosion-resistant tantalum or tantalum alloy objects is described. The method includes the steps of placing the object in contact with a carburizing pack, heating the packed object in vacuum furnace to a temperature whereby carbon from the pack diffuses into the object forming grains with tantalum carbide along the grain boundaries, and etching the surface of the carburized object. This latter step removes tantalum carbides from the surface of the carburized tantalum object while leaving the tantalum carbide along the grain boundaries.

Packed bed carburization of tantalum and tantalum alloy

DOEpatents

Lopez, P.C.; Rodriguez, P.J.; Pereyra, R.A.

1999-06-29

Packed bed carburization of a tantalum or tantalum alloy object is disclosed. A method for producing corrosion-resistant tantalum or tantalum alloy objects is described. The method includes the steps of placing the object in contact with a carburizing pack, heating the packed object in vacuum furnace to a temperature whereby carbon from the pack diffuses into the object forming grains with tantalum carbide along the grain boundaries, and etching the surface of the carburized object. This latter step removes tantalum carbides from the surface of the carburized tantalum object while leaving the tantalum carbide along the grain boundaries. 4 figs.

YSZ thin films with minimized grain boundary resistivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mills, Edmund M.; Kleine-Boymann, Matthias; Janek, Juergen

2016-03-31

In recent years, interface engineering of solid electrolytes has been explored to increase their ionic conductivity and improve the performance of solid oxide fuel cells and other electrochemical power sources. It has been observed that the ionic conductivity of epitaxially grown thin films of some electrolytes is dramatically enhanced, which is often attributed to effects (e. g. strain-induced mobility changes) at the heterophase boundary with the substrate. Still largely unexplored is the possibility of manipulation of grain boundary resistivity in polycrystalline solid electrolyte films, clearly a limiting factor in their ionic conductivity. Here we report that the ionic conductivity ofmore » yttria stabilized zirconia thin films with nano-­ columnar grains grown on a MgO substrate nearly reaches that of the corresponding single crystal when the thickness of the films becomes less than roughly 8 nm (smaller by a factor of three at 500°C). Using impedance spectroscopy, the grain boundary resistivity was probed as a function of film thickness. The resistivity of the grain boundaries near the film- substrate interface and film surface (within 4 nm of each) was almost entirely eliminated. This minimization of grain boundary resistivity is attributed to Mg2+ diffusion from the MgO substrate into the YSZ grain boundaries, which is supported by time of flight secondary ion mass spectroscopy measurements. We suggest grain boundary “design” as an attractive method to obtain highly conductive solid electrolyte thin films.« less

YSZ thin films with minimized grain boundary resistivity

DOE PAGES

Mills, Edmund M.; Kleine-Boymann, Matthias; Janek, Juergen; ...

2016-03-31

In recent years, interface engineering of solid electrolytes has been explored to increase their ionic conductivity and improve the performance of solid oxide fuel cells and other electrochemical power sources. It has been observed that the ionic conductivity of epitaxially grown thin films of some electrolytes is dramatically enhanced, which is often attributed to effects (e.g. strain-induced mobility changes) at the heterophase boundary with the substrate. Still largely unexplored is the possibility of manipulation of grain boundary resistivity in polycrystalline solid electrolyte films, clearly a limiting factor in their ionic conductivity. Here in this paper, we report that the ionicmore » conductivity of yttria stabilized zirconia thin films with nano-columnar grains grown on a MgO substrate nearly reaches that of the corresponding single crystal when the thickness of the films becomes less than roughly 8 nm (smaller by a factor of three at 500 °C). Using impedance spectroscopy, the grain boundary resistivity was probed as a function of film thickness. The resistivity of the grain boundaries near the film–substrate interface and film surface (within 4 nm of each) was almost entirely eliminated. This minimization of grain boundary resistivity is attributed to Mg 2+ diffusion from the MgO substrate into the YSZ grain boundaries, which is supported by time of flight secondary ion mass spectroscopy measurements. We suggest grain boundary “design” as an attractive method to obtain highly conductive solid electrolyte thin films.« less

Room-Temperature and High-Temperature Tensile Mechanical Properties of TA15 Titanium Alloy and TiB Whisker-Reinforced TA15 Matrix Composites Fabricated by Vacuum Hot-Pressing Sintering

PubMed Central

Feng, Yangju; Zhang, Wencong; Zeng, Li; Cui, Guorong; Chen, Wenzhen

2017-01-01

In this paper, the microstructure, the room-temperature and high-temperature tensile mechanical properties of monolithic TA15 alloy and TiB whisker-reinforced TA15 titanium matrix composites (TiBw/TA15) fabricated by vacuum hot-pressing sintering were investigated. The microstructure results showed that there were no obvious differences in the microstructure between monolithic TA15 alloy and TiBw/TA15 composites, except whether or not the grain boundaries contained TiBw. After sintering, the matrix microstructure presented a typical Widmanstätten structure and the size of primary β grain was consistent with the size of spherical TA15 titanium metallic powders. This result demonstrated that TiBw was not the only factor limiting grain coarsening of the primary β grain. Moreover, the grain coarsening of α colonies was obvious, and high-angle grain boundaries (HAGBs) were distributed within the primary β grain. In addition, TiBw played an important role in the microstructure evolution. In the composites, TiBw were randomly distributed in the matrix and surrounded by a large number of low-angle grain boundaries (LAGBs). Globularization of α phase occurred prior, near the TiBw region, because TiBw provided the nucleation site for the equiaxed α phase. The room-temperature and high-temperature tensile results showed that TiBw distributed at the primary β grain boundaries can strengthen the grain boundary, but reduce the connectivity of the matrix. Therefore, compared to the monolithic TA15 alloy fabricated by the same process, the tensile strength of the composites increased, and the tensile elongation decreased. Moreover, with the addition of TiBw, the fracture mechanism was changed to a mixture of brittle fracture and ductile failure (composites) from ductile failure (monolithic TA15 alloy). The fracture surfaces of TiBw/TA15 composites were the grain boundaries of the primary β grain where the majority of TiB whiskers distributed, i.e., the surfaces of the spherical TA15 titanium metallic powders. PMID:28772786

Room-Temperature and High-Temperature Tensile Mechanical Properties of TA15 Titanium Alloy and TiB Whisker-Reinforced TA15 Matrix Composites Fabricated by Vacuum Hot-Pressing Sintering.

PubMed

Feng, Yangju; Zhang, Wencong; Zeng, Li; Cui, Guorong; Chen, Wenzhen

2017-04-18

In this paper, the microstructure, the room-temperature and high-temperature tensile mechanical properties of monolithic TA15 alloy and TiB whisker-reinforced TA15 titanium matrix composites (TiBw/TA15) fabricated by vacuum hot-pressing sintering were investigated. The microstructure results showed that there were no obvious differences in the microstructure between monolithic TA15 alloy and TiBw/TA15 composites, except whether or not the grain boundaries contained TiBw. After sintering, the matrix microstructure presented a typical Widmanstätten structure and the size of primary β grain was consistent with the size of spherical TA15 titanium metallic powders. This result demonstrated that TiBw was not the only factor limiting grain coarsening of the primary β grain. Moreover, the grain coarsening of α colonies was obvious, and high-angle grain boundaries (HAGBs) were distributed within the primary β grain. In addition, TiBw played an important role in the microstructure evolution. In the composites, TiBw were randomly distributed in the matrix and surrounded by a large number of low-angle grain boundaries (LAGBs). Globularization of α phase occurred prior, near the TiBw region, because TiBw provided the nucleation site for the equiaxed α phase. The room-temperature and high-temperature tensile results showed that TiBw distributed at the primary β grain boundaries can strengthen the grain boundary, but reduce the connectivity of the matrix. Therefore, compared to the monolithic TA15 alloy fabricated by the same process, the tensile strength of the composites increased, and the tensile elongation decreased. Moreover, with the addition of TiBw, the fracture mechanism was changed to a mixture of brittle fracture and ductile failure (composites) from ductile failure (monolithic TA15 alloy). The fracture surfaces of TiBw/TA15 composites were the grain boundaries of the primary β grain where the majority of TiB whiskers distributed, i.e., the surfaces of the spherical TA15 titanium metallic powders.

Grain boundary diffusion of Dy films prepared by magnetron sputtering for sintered Nd–Fe–B magnets

NASA Astrophysics Data System (ADS)

Chen, W.; Luo, J. M.; Guan, Y. W.; Huang, Y. L.; Chen, M.; Hou, Y. H.

2018-05-01

Dy films, deposited on the surface of sintered Nd–Fe–B magnets by magnetron sputtering, were employed for grain boundary diffusion source. High coercivity sintered Nd–Fe–B magnets were successfully prepared. Effects of sputtering power and grain boundary diffusion processes (GBDP) on the microstructure and magnetic properties were investigated in detail. The dense and uniform Dy films were beneficial to prepare high coercivity magnets by GBDP. The maximum coercivity value of 1189 kA m‑1 could be shown, which was an amplification of 22.3%, compared with that of as-prepared Nd–Fe–B magnet. Furthermore, the improved remanence and maximum energy product were also achieved through tuning grain boundary diffusion processes. Our results demonstrated that the formation of (Nd, Dy)2Fe14B shell surrounding Nd2Fe14B grains and fine, uniform and continuous intergranular RE-rich phases jointly contribute to the improved coercivity.

Atom probe study of grain boundary segregation in technically pure molybdenum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Babinsky, K., E-mail: katharina.babinsky@stud.unileoben.ac.at; Weidow, J., E-mail: jonathan.weidow@chalmers.se; Knabl, W., E-mail: wolfram.knabl@plansee.com

2014-01-15

Molybdenum, a metal with excellent physical, chemical and high-temperature properties, is an interesting material for applications in lighting-technology, high performance electronics, high temperature furnace construction and coating technology. However, its applicability as a structural material is limited because of the poor oxidation resistance at high temperatures and a brittle-to-ductile transition around room temperature, which is influenced by the grain size and the content of interstitial impurities at the grain boundaries. Due to the progress of the powder metallurgical production during the last decades, the amount of impurities in the current quality of molybdenum has become so small that surface sensitivemore » techniques are not applicable anymore. Therefore, the atom probe, which allows the detection of small amounts of impurities as well as their location, seems to be a more suitable technique. However, a site-specific specimen preparation procedure for grain boundaries in refractory metals with a dual focused ion beam/scanning electron microscope is still required. The present investigation describes the development and successful application of such a site-specific preparation technique for grain boundaries in molybdenum, which is significantly improved by a combination with transmission electron microscopy. This complimentary technique helps to improve the visibility of grain boundaries during the last preparation steps and to evidence the presence of grain and subgrain boundaries without segregants in atom probe specimens. Furthermore, in industrially processed and recrystallized molybdenum sheets grain boundary segregation of oxygen, nitrogen and potassium is successfully detected close to segregated regions which are believed to be former sinter pores. - Highlights: • First study of grain boundary segregation in molybdenum by atom probe • Site-specific preparation technique by FIB and TEM successfully developed • Grain boundary segregation of oxygen, nitrogen and potassium found • Segregation in former sinter-pores detected • Presence of grain boundaries without segregation evidenced.« less

Abnormal grain growth in iron-silicon

NASA Astrophysics Data System (ADS)

Bennett, Tricia A.

Abnormal grain growth (AGG) was studied in an Fe-1%Si alloy using automated Electron Backscattered Diffraction (EBSD) to determine the driving force for this phenomenon. Experiments were performed with the knowledge that there are several possible driving forces and, the intent to determine the true driving force by elimination of the other potential candidates. These potential candidates include surface energy anisotropy, anisotropic grain boundary properties and the stored energy of deformation. In this work, surface energy and grain boundary anisotropies as well as the stored energy of deformation were investigated as the possible driving forces for AGG. Accordingly, industrially processed samples that were temper rolled to 1.5% and 8% were annealed in air for various times followed by quenching in water. The results obtained were compared to those from heat treatments performed in wet 15%H2-85%N2 at a US Steel facility. In addition, for a more complete study of the effect of surface energy anisotropies on AGG, the 1.5% temper-rolled material was heat-treated in other atmospheres such as 5%H2-95%Ar, 98%H2-2%He, 98%H2-2%H 2S, and 98%H2-2%N2 for 1 hour followed by quenching in water. The character of the grain boundaries in the materials was also examined for each set of experiments conducted, while the influence of stored energy was evaluated by examining intragranular orientation gradients. AGG occurred regardless of annealing atmosphere though the most rapid progression was observed in samples annealed in air. In general, grains of varying orientations grew abnormally. One consistently observed trend in all the detailed studies was that the matrix grains remained essentially static and either did not grow or only grew very slowly. On the other hand, the abnormally large grains (ALG), on average, were approximately 10 times the size of the matrix. Analysis of the grain boundary character of the interfaces between abnormal grains and the matrix showed no significant variation from the overall population of boundaries. This suggested that grain boundary character was not a factor in controlling AGG. When the effect of stored energy differences was considered, it was observed that grains that experienced AGG had low orientation gradients. Based on these results and cross comparison of all classes of experiments performed, it was determined that stored energy differences were the main driving force for AGG in this Fe-1%Si alloy.

First principles determination of dislocation properties.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hamilton, John C.

2003-12-01

This report details the work accomplished on first principles determination of dislocation properties. It contains an introduction and three chapters detailing three major accomplishments. First, we have used first principle calculations to determine the shear strength of an aluminum twin boundary. We find it to be remarkably small ({approx}17 mJ/m{sup 2}). This unexpected result is explained and will likely pertain for many other grain boundaries. Second, we have proven that the conventional explanation for finite grain boundary facets is wrong for a particular aluminum grain boundary. Instead of finite facets being stabilized by grain boundary stress, we find them tomore » originate from kinetic effects. Finally we report on a new application of the Frenkel-Kontorova model to understand reconstructions of (100) type surfaces. In addition to the commonly accepted formation of rectangular dislocation arrays, we find numerous other possible solutions to the model including hexagonal reconstructions and a clock-rotated structure.« less

Grain boundary grooving induced by the anisotropic surface drift diffusion driven by the capillary and electromigration forces: Simulations

NASA Astrophysics Data System (ADS)

Akyildiz, Oncu; Omer Ogurtani, Tarik

2011-08-01

The morphological evolution kinetics of a bicrystal thin film induced by anisotropic surface drift diffusion and driven by the applied electrostatic field is investigated via self consistent dynamical computer simulations. The physico-mathematical model, which is based upon the irreversible thermodynamic treatment of surfaces and interfaces with singularities [T. O. Ogurtani, J. Chem. Phys. 124, 144706 (2006)], provided us with auto-control on the otherwise free-motion of the triple junction at the intersection of the grooving surface and the grain boundary, without having any a priori assumption on the equilibrium dihedral angles. The destruction of the symmetry of the freshly formed grain boundary grooves under the anisotropic surface diffusion driven by the concurrent action of the capillarity and electromigration is observed. After prolonged exposure times the applied electric field above the well defined threshold level modifies Mullins' familiar stationary state time law as, t¯1/4, and causes the premature termination of the groove penetration because of the current crowding at the tips of counteracting grain boundary-grooves initiated on both sides of the test modulus. That finding indicates that the electromigration plays the same role as a healing agent [T. O. Ogurtani, J. Appl. Phys. 106, 053503 (2009)] in arresting the thermal grooving, thereby avoiding the premature interconnect failure as in the case of surface roughening and crack initiation caused by compressive stress gradients. The role of the electromigration and wetting parameter on the ridge/slit formations are thoroughly investigated in this study and the prerequisite conditions are also identified.

The cause of ‘weak-link’ grain boundary behaviour in polycrystalline Bi2Sr2CaCu2O8 and Bi2Sr2Ca2Cu3O10 superconductors

NASA Astrophysics Data System (ADS)

Wang, Guanmei; Raine, Mark J.; Hampshire, Damian P.

2018-02-01

The detrimental effects of grain boundaries have long been considered responsible for the low critical current densities ({J}{{c}}) in high temperature superconductors. In this paper, we apply the quantitative approach used to identify the cause of the ‘weak-link’ grain boundary behaviour in YBa2Cu3O7 (Wang et al 2017 Supercond. Sci Technol. 30 104001), to the Bi2Sr2CaCu2O8 and Bi2Sr2Ca2Cu3O10 materials that we have fabricated. Magnetic and transport measurements are used to characterise the grain and grain boundary properties of micro- and nanocrystalline materials. Magnetisation measurements on all nanocrystalline materials show non-Bean-like behaviour and are consistent with surface pinning. Bi2Sr2CaCu2O8: our microcrystalline material has very low grain boundary resistivity ({ρ }{{GB}}), which is similar to that of the grains ({ρ }{{G}}) such that {ρ }{{GB}}≈ {ρ }{{G}}=2× {10}-5 {{Ω }}{{m}} (assuming a grain boundary thickness (d) of 1 nm) equivalent to an areal resistivity of {ρ }{{G}}=2× {10}-14 {{{Ω }}{{m}}}2. The transport {J}{{c}} values are consistent with well-connected grains and very weak grain boundary pinning. However, unlike low temperature superconductors (LTS) in which decreasing grain size increases the pinning along the grain boundary channels, any increase in pinning produced by making the grains in our Bi2Sr2CaCu2O8 materials nanocrystalline was completely offset by a decrease in the depairing current density of the grain boundaries caused by their high resistivity. We suggest a different approach to increasing {J}{{c}} from that used in LTS materials, namely incorporating additional strong grain and grain boundary pinning sites in microcrystalline materials to produce high {J}{{c}} values. Bi2Sr2Ca2Cu3O10: both our micro- and nanocrystalline samples have {ρ }{{GB}}/{ρ }{{G}} of at least 103. This causes strong suppression of {J}{{c}} across the grain boundaries, which explains the low transport {J}{{c}} values we find experimentally. Our calculations show that low {J}{{c}} in untextured polycrystalline Bi2Sr2Ca2Cu3O10 material is to be expected and the significant effort in the community in texturing samples and removing grain boundaries altogether is well-founded.

Coercivity enhancement of sintered Nd-Fe-B magnets by chemical bath deposition of TbCl{sub 3}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo, Shuai, E-mail: gshuai@nimte.ac.cn; Zhang, Xiaofeng; Ding, Guangfei

2014-05-07

The chemical bath deposition (CBD) and the grain boundary diffusion method were combined to diffuse the heavy rare earth for obtain the thick magnets with high coercivity and low heavy rare earth. The jet mill powders were soaked into the alcohol solution of 0.2 wt. % TbCl{sub 3}. A thin layer of TbCl{sub 3} was wrapped to the surface of (PrNd){sub 2}Fe{sub 14}B powder particles. The coercivity of magnet is increased from 11.89 kOe to 14.72 kOe without significant reduction of remanence after grain boundary diffusion in the sintering and the annealing processes. The temperature coefficients of the remanence and themore » coercivity are improved by the substitution of PrNd by Tb in the surface of grains. The highly accelerated temperature/humidity stress test (HAST) results indicate that the CBD magnet has poor corrosion resistance, attributing to the present of Cl atoms in the grain boundaries.« less

Nanoscale Investigation of Grain Growth in RF-Sputtered Indium Tin Oxide Thin Films by Scanning Probe Microscopy

NASA Astrophysics Data System (ADS)

Lamsal, B. S.; Dubey, M.; Swaminathan, V.; Huh, Y.; Galipeau, D.; Qiao, Q.; Fan, Q. H.

2014-11-01

This work studied the electronic characteristics of the grains and grain boundaries of indium tin oxide (ITO) thin films using electrostatic and Kelvin probe force microscopy. Two types of ITO films were compared, deposited using radiofrequency magnetron sputtering in pure argon or 99% argon + 1% oxygen, respectively. The average grain size and surface roughness increased with substrate temperature for the films deposited in pure argon. With the addition of 1% oxygen, the increase in the grain size was inhibited above 150°C, which was suggested to be due to passivation of the grains by the excess oxygen. Electrostatic force microscopy and Kelvin probe force microscopy (KPFM) images confirmed that the grain growth was defect mediated and occurred at defective interfaces at high temperatures. Films deposited at room temperature with 1% oxygen showed crystalline nature, while films deposited with pure argon at room temperature were amorphous as observed from KPFM images. The potential drop across the grain and grain boundary was determined by taking surface potential line profiles to evaluate the electronic properties.

Electronic and elemental properties of the Cu2ZnSn(S,Se)4 surface and grain boundaries

NASA Astrophysics Data System (ADS)

Haight, Richard; Shao, Xiaoyan; Wang, Wei; Mitzi, David B.

2014-01-01

X-ray and femtosecond UV photoelectron spectroscopy, secondary ion mass spectrometry and photoluminescence imaging were used to investigate the electronic and elemental properties of the CZTS,Se surface and its oxides. Oxide removal reveals a very Cu poor and Zn rich surface relative to bulk composition. O and Na are observed at the surface and throughout the bulk. Upward bending of the valence bands indicates the presence of negative charge in the surface region and the Fermi level is found near the band gap center. The presence of point defects and the impact of these findings on grain boundary properties will be described.

Microstructural investigation of current barriers in high temperature superconducting tapes and coated conductors

NASA Astrophysics Data System (ADS)

Reeves, Jodi Lynn

Microstructural barriers to supercurrent occur on many length scales in all high temperature oxide superconductors. Eliminating microstructural barriers is key to making these potentially valuable materials more favorable for commercial applications. In silver-sheathed Bi2Sr2CaCu 2Ox (Bi-2212) tapes and multifilaments, the principal barriers on the scale of 10--100's of micrometers are bubbling, porosity, second phase particles, and poorly aligned grains. In state-of-the-art YBa2 Cu3Ox (YBCO) coated conductors, supercurrent barriers on the 0.1--100mum scale are grain boundaries. This thesis work clarifies the role of grain boundaries in the nickel substrate of RABiTS (Rolling Assisted Biaxially Textured Substrate) coated conductors. Plan-view SEM imaging, focused ion beam cutting, magneto-optical imaging and grain orientation mapping were used to determine barriers to supercurrent. Experiments showed enhanced magnetic flux penetration, and hence reduced Jc, in the YBCO above nearly all nickel grain boundaries with misorientation angles (theta) greater than 5°, independent of the rotation axis. Monochromatic backscattered electron Kikuchi pattern percolation maps imply there is a fully connected current path through the YBCO microstructure within the chosen tolerance angle criterion of the map. However, it is the grain boundary map that displays the constrictions of the current path. Therefore, grain boundary maps are better tools for illustrating supercurrent barriers than percolation maps. Grain boundary maps and grain orientation maps were used to investigate how the texture of the substrate was transferred to the buffer layers and to the superconductor. Most grasp boundaries in the nickel were replicated in the buffer and superconductor layers with the same misorientation angle. Anisotropic growth and/or surface energy minimization may be responsible for the improvement in c-axis alignment in the YBCO over the buffer layer. However, the YBCO mosaic spread did not eliminate high angle grain boundaries, since >5° boundaries were still seen in YBCO grain boundary maps. The results of this study on microstructural current barriers show that Jc improvements in RABiTS-type coated conductors require eliminating theta > 5° boundaries in the nickel substrate.

Diffusion induced atomic islands on the surface of Ni/Cu nanolayers

NASA Astrophysics Data System (ADS)

Takáts, Viktor; Csik, Attila; Hakl, József; Vad, Kálmán

2018-05-01

Surface islands formed by grain-boundary diffusion has been studied in Ni/Cu nanolayers by in-situ low energy ion scattering spectroscopy, X-ray photoelectron spectroscopy, scanning probe microscopy and ex-situ depth profiling based on ion sputtering. In this paper a new experimental approach of measurement of grain-boundary diffusion coefficients is presented. Appearing time of copper atoms diffused through a few nanometer thick nickel layer has been detected by low energy ion scattering spectroscopy with high sensitivity. The grain-boundary diffusion coefficient can be directly calculated from this appearing time without using segregation factors in calculations. The temperature range of 423-463 K insures the pure C-type diffusion kinetic regime. The most important result is that surface coverage of Ni layer by Cu atoms reaches a maximum during annealing and stays constant if the annealing procedure is continued. Scanning probe microscopy measurements show a Volmer-Weber type layer growth of Cu layer on the Ni surface in the form of Cu atomic islands. Depth distribution of Cu in Ni layer has been determined by depth profile analysis.

Effects of polycrystallinity in nano patterning by ion-beam sputtering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yoon, Sun Mi; Kim, J.-S., E-mail: jskim@sm.ac.kr; Yoon, D.

Employing graphites with distinctly different mean grain sizes, we study the effects of polycrystallinity on the pattern formation by ion-beam sputtering. The grains influence the growth of the ripples in a highly anisotropic fashion; both the mean uninterrupted ripple length along the ridges and the surface width depend on the mean size of the grains, which is attributed to the large sputter yield at the grain boundary compared with that on the terrace. In contrast, the ripple wavelength does not depend on the mean size of the grains, indicating that the mass transport across the grain boundaries should efficiently proceedmore » by both thermal diffusion and ion-induced processes.« less

STEM and APT characterization of scale formation on a La,Hf,Ti-doped NiCrAl model alloy.

PubMed

Unocic, Kinga A; Chen, Yimeng; Shin, Dongwon; Pint, Bruce A; Marquis, Emmanuelle A

2018-06-01

A thermally grown scale formed on a cast NiCrAl model alloy doped with lanthanum, hafnium, and titanium was examined after isothermal exposure at 1100 °C for 100 h in dry flowing O 2 to understand the dopant segregation along scale grain boundaries. The complex scale formed on the alloy surface was composed of two types of substrates: phase-dependent, thin (<250 nm) outer layers and a columnar-grained ∼3.5 μm inner alumina layer. Two types of oxides formed between the inner and outer scale layers: small (3-15 nm) La 2 O 3 and larger (≤50 nm) HfO 2 oxide precipitates. Nonuniform distributions of the hafnium, lanthanum, and titanium dopants were observed along the inner scale grain boundaries, with hafnium dominating in most of the grain boundaries of α-Al 2 O 3. The concentration of reactive elements (RE) seemed to strongly depend on the grain boundary structure. The level of titanium grain boundary segregation in the inner scale decreased toward the model alloy (substrate), confirming the fast outward diffusion of titanium. Hafnium was also observed at the metal-scale interface and in the γ' (Ni 3 Al) phase of the alloy. High-resolution scanning transmission electron microscopy (STEM) confirmed the substitution of REs for aluminum atoms at the scale grain boundaries, consistent with both the semiconducting band structure and the site-blocking models. Both STEM and atom probe tomography allowed quantification of REs along the scale grain boundaries across the scale thickness. Analysis of the scale morphology after isothermal exposure in flowing oxygen revealed a myriad of new precipitate phases, RE segregation dependence on grain boundary type, and atomic arrangement along scale grain boundaries, which is expected to influence the scale growth rate, stability, and mechanical properties. Copyright © 2018 Elsevier Ltd. All rights reserved.

Direct Observation of Sink-Dependent Defect Evolution in Nanocrystalline Iron under Irradiation

DOE PAGES

El Atwani, Osman; Nathaniel, James; Leff, Asher C.; ...

2017-05-12

Crystal defects generated during irradiation can result in severe changes in morphology and an overall degradation of mechanical properties in a given material. Nanomaterials have been proposed as radiation damage tolerant materials, due to the hypothesis that defect density decreases with grain size refinement due to the increase in grain boundary surface area. The lower defect density should arise from grain boundary-point defect absorption and enhancement of interstitial-vacancy annihilation. In this study, low energy helium ion irradiation on free-standing iron thin films were performed at 573 K. Interstitial loops of a 0 /2 [111] Burgers vector were directly observed asmore » a result of the displacement damage. Loop density trends with grain size demonstrated an increase in the nanocrystalline (<100 nm) regime, but scattered behavior in the transition from the nanocrystalline to the ultra-fine regime (100–500 nm). To examine the validity of such trends, loop density and area for different grains at various irradiation doses were compared and revealed efficient defect absorption in the nanocrystalline grain size regime, but loop coalescence in the ultra-fine grain size regime. Lastly, a relationship between the denuded zone formation, a measure of grain boundary absorption efficiency, grain size, grain boundary type and misorientation angle is determined.« less

Direct Observation of Sink-Dependent Defect Evolution in Nanocrystalline Iron under Irradiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

El Atwani, Osman; Nathaniel, James; Leff, Asher C.

Crystal defects generated during irradiation can result in severe changes in morphology and an overall degradation of mechanical properties in a given material. Nanomaterials have been proposed as radiation damage tolerant materials, due to the hypothesis that defect density decreases with grain size refinement due to the increase in grain boundary surface area. The lower defect density should arise from grain boundary-point defect absorption and enhancement of interstitial-vacancy annihilation. In this study, low energy helium ion irradiation on free-standing iron thin films were performed at 573 K. Interstitial loops of a 0 /2 [111] Burgers vector were directly observed asmore » a result of the displacement damage. Loop density trends with grain size demonstrated an increase in the nanocrystalline (<100 nm) regime, but scattered behavior in the transition from the nanocrystalline to the ultra-fine regime (100–500 nm). To examine the validity of such trends, loop density and area for different grains at various irradiation doses were compared and revealed efficient defect absorption in the nanocrystalline grain size regime, but loop coalescence in the ultra-fine grain size regime. Lastly, a relationship between the denuded zone formation, a measure of grain boundary absorption efficiency, grain size, grain boundary type and misorientation angle is determined.« less

Measurements of stress fields near a grain boundary: Exploring blocked arrays of dislocations in 3D

DOE PAGES

Guo, Y.; Collins, D. M.; Tarleton, E.; ...

2015-06-24

The interaction between dislocation pile-ups and grain boundaries gives rise to heterogeneous stress distributions when a structural metal is subjected to mechanical loading. Such stress heterogeneity leads to preferential sites for damage nucleation and therefore is intrinsically linked to the strength and ductility of polycrystalline metals. To date the majority of conclusions have been drawn from 2D experimental investigations at the sample surface, allowing only incomplete observations. Our purpose here is to significantly advance the understanding of such problems by providing quantitative measurements of the effects of dislocation pile up and grain boundary interactions in 3D. This is accomplished throughmore » the application of differential aperture X-ray Laue micro-diffraction (DAXM) and high angular resolution electron backscatter diffraction (HR-EBSD) techniques. Our analysis demonstrates a similar strain characterization capability between DAXM and HR-EBSD and the variation of stress intensity in 3D reveals that different parts of the same grain boundary may have different strengths in resisting slip transfer, likely due to the local grain boundary curvature.« less

Diffusion of volatile organics through porous snow: impact of surface adsorption and grain boundaries

NASA Astrophysics Data System (ADS)

Bartels-Rausch, T.; Wren, S. N.; Schreiber, S.; Riche, F.; Schneebeli, M.; Ammann, M.

2013-03-01

Release of trace gases from surface snow on Earth drives atmospheric chemistry, especially in the polar regions. The gas-phase diffusion of methanol and of acetone through the interstitial air of snow was investigated in a well-controlled laboratory study in the temperature range of 223 to 263 K. The aim of this study was to evaluate how the structure of the snowpack, the interaction of the trace gases with the snow surface, and the grain boundaries influence the diffusion on timescales up to 1 h. The diffusive loss of these two volatile organics into packed snow samples was measured using a chemical ionization mass spectrometer. The structure of the snow was analyzed by means of X-ray computed micro-tomography. The observed diffusion profiles could be well described based on gas-phase diffusion and the known structure of the snow sample at temperatures ≥ 253 K. At colder temperatures surface interactions start to dominate the diffusive transport. Parameterizing these interactions in terms of adsorption to the solid ice surface, i.e. using temperature dependent air-ice partitioning coefficients, better described the observed diffusion profiles than the use of air-liquid partitioning coefficients. No changes in the diffusive fluxes were observed by increasing the number of grain boundaries in the snow sample by a factor of 7, indicating that for these volatile organic trace gases, uptake into grain boundaries does not play a role on the timescale of diffusion through porous surface snow. In conclusion, we have shown that the diffusivity can be predicted when the structure of the snowpack and the partitioning of the trace gas to solid ice is known.

Tensile and fracture properties of type 316 stainless steel after creep

NASA Astrophysics Data System (ADS)

Gan, D.

1982-12-01

The effects of creep on the mechanical properties of type 316 stainless steel were studied. Tensile and Charpy specimens were machined from the oversize specimens crept at 750 °C and 103 MPa. The ambient fracture energy was found to deteriorate rapidly after creep. The ambient yield stress was increased moderately, but the tensile ductility was severely reduced. The effects of intergranular carbides alone on mechanical properties were studied with specimens thermal aged without load. These carbides were shown to cause a moderate reduction in fracture energy and tensile ductility but had little effect on yield stress. Extensive grain boundary separations were observed on the fracture surfaces. SEM studies showed that these grain boundaries were covered with micro voids initiated by the dense intergranular carbides. Frequently, large dimples on grain boundary joined up and initiated shear fracture into the grain. In the crept specimens additional microstructural changes in the form of intragranular carbides and subgrain boundaries were observed. Both are responsible for the increase in yield stress and the further reduction in tensile ductility and fracture energy. The intragranular carbides also modified the size and density of the dimples on the fracture surfaces.

Surface properties of atomically flat poly-crystalline SrTiO3

PubMed Central

Woo, Sungmin; Jeong, Hoidong; Lee, Sang A.; Seo, Hosung; Lacotte, Morgane; David, Adrian; Kim, Hyun You; Prellier, Wilfrid; Kim, Yunseok; Choi, Woo Seok

2015-01-01

Comparison between single- and the poly-crystalline structures provides essential information on the role of long-range translational symmetry and grain boundaries. In particular, by comparing single- and poly-crystalline transition metal oxides (TMOs), one can study intriguing physical phenomena such as electronic and ionic conduction at the grain boundaries, phonon propagation, and various domain properties. In order to make an accurate comparison, however, both single- and poly-crystalline samples should have the same quality, e.g., stoichiometry, crystallinity, thickness, etc. Here, by studying the surface properties of atomically flat poly-crystalline SrTiO3 (STO), we propose an approach to simultaneously fabricate both single- and poly-crystalline epitaxial TMO thin films on STO substrates. In order to grow TMOs epitaxially with atomic precision, an atomically flat, single-terminated surface of the substrate is a prerequisite. We first examined (100), (110), and (111) oriented single-crystalline STO surfaces, which required different annealing conditions to achieve atomically flat surfaces, depending on the surface energy. A poly-crystalline STO surface was then prepared at the optimum condition for which all the domains with different crystallographic orientations could be successfully flattened. Based on our atomically flat poly-crystalline STO substrates, we envision expansion of the studies regarding the TMO domains and grain boundaries. PMID:25744275

Discovering the Role of Grain Boundary Complexions in Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harmer, Martin P.

Grain boundaries are inherently an area of disorder in polycrystalline materials which define the transport and various other material properties. The relationship between the interfacial chemistry, structure and the material properties is not well understood. Among the various taxonomies for grain boundaries, Grain Boundary Complexion is a relatively new conceptual scheme that relates the structure and kinetic properties of grain boundaries. In this classification scheme, grain boundaries are considered to be distinct three dimensional (the thickness being considerably smaller as compared to the other two dimensions but nonetheless discernible) equilibrium thermodynamic phases abutted between two crystalline phases. The stability andmore » structure of these interfacial phases are dictated by various thermodynamic variables such as temperature, stress (pressure), interfacial chemistry (chemical potential) and most importantly by the energies of the adjoining crystal surfaces. These phases are only stable within the constraint of the adjoining grains. Although these interfacial phases are not stable in bulk form, they can transform from one complexion to another as a function of various thermodynamic variables analogous to the behavior of bulk phases. Examples of different complexions have been reported in various publications. However, a systematic investigation exploring the existence of grain boundary complexions in material systems other than alumina remains to be done. Although the role of interfacial chemistry on grain boundary complexions in alumina has been addressed, a clear understanding of the underlying thermodynamics governing complexion formation is lacking. Finally, the effects of grain boundary complexions in bulk material properties are widely unknown. Factors above urge a thorough exploration of grain boundary complexions in a range of different materials systems The purpose of the current program is to verify the existence of grain boundary complexion in a range of materials systems, and to characterize their structures, range of stability and selected physical properties. First, an Au-based bilayer interfacial phase was discovered at a bicrystal boundary in the Si-Au system. This bilayer transitioned abruptly to an intrinsic (“clean”) grain boundary phase, suggesting first-order phase behavior. This study represents the discovery of grain boundary complexions in a completely new system, i.e., a semiconductor-metal system, giving further support to the expectation that grain boundary complexions are a general phenomenon not limited to any particular class of materials. The TiO 2-CuO system exhibited four grain boundary interfacial phases: a monolayer, disordered bilayer, disordered trilayer, and non-wetting nanoscale amorphous drop (which likely resulted from dewetting of a nanoscale IGF). SiO 2 contamination was discovered in the TiO 2-CuO samples, and we hypothesize that this impurity may have caused an “order-disorder” transition to occur. In other words, we expect that pure TiO 2-CuO may have a higher tendency to exhibit ordered bilayer and trilayer complexions, which may also exhibit a well-defined order-disorder transition temperature. In this effort we have also identified unique complexion transitions in yttria and strontium titanate.« less

Domain pinning near a single-grain boundary in tetragonal and rhombohedral lead zirconate titanate films

DOE PAGES

Marincel, Dan M.; Zhang, H. R.; Briston, J.; ...

2015-04-27

The interaction of grain boundaries with ferroelectric domain walls strongly influences the extrinsic contribution to piezoelectric activity in Pb(Zr,Ti)O 3 (PZT), ubiquitous in modern transducers and actuators. However, the fundamental understanding of these phenomena has been limited by complex mechanisms originating from the interplay of atomic-level domain wall pinning, collective domain wall dynamics, and emergent mesoscopic behavior. This contribution utilizes engineered grain boundaries created by depositing epitaxial PZT films with various Zr:Ti ratio onto 24º SrTiO 3 tilt bicrystals. The nonlinear piezoelectric response and surface domain structure across the boundary are investigated using piezoresponse force microscopy whilst cross section domainmore » structure is studied using transmission electron microscopy. The grain boundary reduces domain wall motion over a width of 800±70 nm for PZT 45:55 and 450±30 nm for PZT 52:48. Phase field modeling provides an understanding of the elastic and electric fields associated with the grain boundary and local domain configurations. In conclusion, this study demonstrates that complex mesoscopic behaviors can be explored to complement atomic-level pictures of the material system.« less

Resistivity scaling and electron relaxation times in metallic nanowires

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moors, Kristof, E-mail: kristof@itf.fys.kuleuven.be; Imec, Kapeldreef 75, B-3001 Leuven; Sorée, Bart

2014-08-14

We study the resistivity scaling in nanometer-sized metallic wires due to surface roughness and grain-boundaries, currently the main cause of electron scattering in nanoscaled interconnects. The resistivity has been obtained with the Boltzmann transport equation, adopting the relaxation time approximation of the distribution function and the effective mass approximation for the conducting electrons. The relaxation times are calculated exactly, using Fermi's golden rule, resulting in a correct relaxation time for every sub-band state contributing to the transport. In general, the relaxation time strongly depends on the sub-band state, something that remained unclear with the methods of previous work. The resistivitymore » scaling is obtained for different roughness and grain-boundary properties, showing large differences in scaling behavior and relaxation times. Our model clearly indicates that the resistivity is dominated by grain-boundary scattering, easily surpassing the surface roughness contribution by a factor of 10.« less

Micromagnetic simulation of anisotropic grain boundary diffusion for sintered Nd-Fe-B magnets

NASA Astrophysics Data System (ADS)

Li, W.; Zhou, Q.; Zhao, L. Z.; Wang, Q. X.; Zhong, X. C.; Liu, Z. W.

2018-04-01

A systematic investigation on the anisotropic grain boundary diffusion in sintered Nd-Fe-B magnets is carried out by micromagnetic simulation. The results indicate that the critical reason for the anisotropic diffusion effect is not the difference in the amount of Dy diffused along different directions but the macroscopic demagnetizing field. The diffusion parallel to the easy axis from both pole surfaces of the magnet can increase the nucleation fields in the two major regions with large macroscopic demagnetizing fields, where the reverse domains can nucleate easily. As a consequence, the grain boundary diffusion along the directions parallel to the easy axis from two pole surfaces is more effective to improve the coercivity of the magnets than that along other directions. It is also found that, to enhance the coercivity, only a limited diffusion depth is required. The present result is in good agreement with the recent experimental findings.

Analysis of defect structure in silicon. Characterization of SEMIX material. Silicon sheet growth development for the large area silicon sheet task of the low-cost solar array project

NASA Technical Reports Server (NTRS)

Natesh, R.; Stringfellow, G. B.; Virkar, A. V.; Dunn, J.; Guyer, T.

1983-01-01

Statistically significant quantitative structural imperfection measurements were made on samples from ubiquitous crystalline process (UCP) Ingot 5848 - 13C. Important correlation was obtained between defect densities, cell efficiency, and diffusion length. Grain boundary substructure displayed a strong influence on the conversion efficiency of solar cells from Semix material. Quantitative microscopy measurements gave statistically significant information compared to other microanalytical techniques. A surface preparation technique to obtain proper contrast of structural defects suitable for quantimet quantitative image analyzer (QTM) analysis was perfected and is used routinely. The relationships between hole mobility and grain boundary density was determined. Mobility was measured using the van der Pauw technique, and grain boundary density was measured using quantitative microscopy technique. Mobility was found to decrease with increasing grain boundary density.

Microstructural Evolution at Micro/Meso-Scale in an Ultrafine-Grained Pure Aluminum Processed by Equal-Channel Angular Pressing with Subsequent Annealing Treatment.

PubMed

Xu, Jie; Li, Jianwei; Zhu, Xiaocheng; Fan, Guohua; Shan, Debin; Guo, Bin

2015-11-04

Micro-forming with ultrafine-grained (UFG) materials is a promising direction for the fabrication of micro-electro-mechanical systems (MEMS) components due to the improved formability, good surface quality, and excellent mechanical properties it provides. In this paper, micro-compression tests were performed using UFG pure aluminum processed by equal-channel angular pressing (ECAP) with subsequent annealing treatment. Microstructural evolution was investigated by electron back-scattered diffraction (EBSD) and transmission electron microscopy (TEM). The results show that microstructural evolutions during compression tests at the micro/meso-scale in UFG pure Al are absolutely different from the coarse-grained (CG) materials. A lot of low-angle grain boundaries (LAGBs) and recrystallized fine grains are formed inside of the original large grains in CG pure aluminum after micro-compression. By contrast, ultrafine grains are kept with few sub-grain boundaries inside the grains in UFG pure aluminum, which are similar to the original microstructure before micro-compression. The surface roughness and coordinated deformation ability can be signmicrostructure; micro/meso-forming; ultrafine grains; ECAP; aluminumificantly improved with UFG pure aluminum, which demonstrates that the UFG materials have a strong potential application in micro/meso-forming.

Structure Evolution and Distributions of Grain-Boundary Misorientainons in Submicrocrystalline Molybdenum Irradiated with a Pulsed Electron Beam

NASA Astrophysics Data System (ADS)

Stepanova, E. N.; Grabovetskaya, G. P.; Teresov, A. D.; Mishin, I. P.

2018-05-01

Using the methods of electron backscatter diffraction, electron microscopy and X-ray diffraction analysis, it is demonstrated that irradiation of the surface of a submicrocrystalline molybdenum specimen with a pulsed electron beam in a non-melt regime results in the formation of a gradient structure in its bulk. The irradiation temperature is shown to affect the density of defects, the value of stress, and the distributions of grain-boundary misorientations in the surface and bulk of the submicrocrystalline molybdenum specimens.

Effect of surface microstructure on electrochemical performance of garnet solid electrolytes.

PubMed

Cheng, Lei; Chen, Wei; Kunz, Martin; Persson, Kristin; Tamura, Nobumichi; Chen, Guoying; Doeff, Marca

2015-01-28

Cubic garnet phases based on Al-substituted Li7La3Zr2O12 (LLZO) have high ionic conductivities and exhibit good stability versus metallic lithium, making them of particular interest for use in next-generation rechargeable battery systems. However, high interfacial impedances have precluded their successful utilization in such devices until the present. Careful engineering of the surface microstructure, especially the grain boundaries, is critical to achieving low interfacial resistances and enabling long-term stable cycling with lithium metal. This study presents the fabrication of LLZO heterostructured solid electrolytes, which allowed direct correlation of surface microstructure with the electrochemical characteristics of the interface. Grain orientations and grain boundary distributions of samples with differing microstructures were mapped using high-resolution synchrotron polychromatic X-ray Laue microdiffraction. The electrochemical characteristics are strongly dependent upon surface microstructure, with small grained samples exhibiting much lower interfacial resistances and better cycling behavior than those with larger grain sizes. Low area specific resistances of 37 Ω cm(2) were achieved; low enough to ensure stable cycling with minimal polarization losses, thus removing a significant obstacle toward practical implementation of solid electrolytes in high energy density batteries.

Grain size evolution and convection regimes of the terrestrial planets

NASA Astrophysics Data System (ADS)

Rozel, A.; Golabek, G. J.; Boutonnet, E.

2011-12-01

A new model of grain size evolution has recently been proposed in Rozel et al. 2010. This new approach stipulates that the grain size dynamics is governed by two additive and simultaneous processes: grain growth and dynamic recrystallization. We use the usual normal grain growth laws for the growth part. For dynamic recrystallization, reducing the mean grain size increases the total area of grain boundaries. Grain boundaries carry some surface tension, so some energy is required to decrease the mean grain size. We consider that this energy is available during mechanical work. It is usually considered to produce some heat via viscous dissipation. A partitioning parameter f is then required to know what amount of energy is dissipated and what part is converted in surface tension. This study gives a new calibration of the partitioning parameter on major Earth materials involved in the dynamic of the terrestrial planets. Our calibration is in adequation with the published piezometric relations available in the literature (equilibrium grain size versus shear stress). We test this new model of grain size evolution in a set of numerical computations of the dynamics of the Earth using stagYY. We show that the grain size evolution has a major effect on the convection regimes of terrestrial planets.

System for characterizing semiconductor materials and photovoltaic device

DOEpatents

Sopori, B.L.

1996-12-03

Apparatus for detecting and mapping defects in the surfaces of polycrystalline material in a manner that distinguishes dislocation pits from grain boundaries includes a first laser of a first wavelength for illuminating a wide spot on the surface of the material, a second laser of a second relatively shorter wavelength for illuminating a relatively narrower spot on the surface of the material, a light integrating sphere with apertures for capturing light scattered by etched dislocation pits in an intermediate range away from specular reflection while allowing light scattered by etched grain boundaries in a near range from specular reflection to pass through, and optical detection devices for detecting and measuring intensities of the respective intermediate scattered light and near specular scattered light. A center blocking aperture or filter can be used to screen out specular reflected light, which would be reflected by nondefect portions of the polycrystalline material surface. An X-Y translation stage for mounting the polycrystalline material and signal processing and computer equipment accommodate raster mapping, recording, and displaying of respective dislocation and grain boundary defect densities. A special etch procedure is included, which prepares the polycrystalline material surface to produce distinguishable intermediate and near specular light scattering in patterns that have statistical relevance to the dislocation and grain boundary defect densities. A reflectance measurement of the piece of material is obtained by adding together the signals from the optical detection devices. In the case where the piece of material includes a photovoltaic device, the current induced in the device by the illuminating light can be measured with a current sensing amplifier after the light integrating sphere is moved away from the device. 22 figs.

System for characterizing semiconductor materials and photovoltaic device

DOEpatents

Sopori, Bhushan L.

1996-01-01

Apparatus for detecting and mapping defects in the surfaces of polycrystalline material in a manner that distinguishes dislocation pits from grain boundaries includes a first laser of a first wavelength for illuminating a wide spot on the surface of the material, a second laser of a second relatively shorter wavelength for illuminating a relatively narrower spot on the surface of the material, a light integrating sphere with apertures for capturing light scattered by etched dislocation pits in an intermediate range away from specular reflection while allowing light scattered by etched grain boundaries in a near range from specular reflection to pass through, and optical detection devices for detecting and measuring intensities of the respective intermediate scattered light and near specular scattered light. A center blocking aperture or filter can be used to screen out specular reflected light, which would be reflected by nondefect portions of the polycrystalline material surface. An X-Y translation stage for mounting the polycrystalline material and signal processing and computer equipment accommodate raster mapping, recording, and displaying of respective dislocation and grain boundary defect densities. A special etch procedure is included, which prepares the polycrystalline material surface to produce distinguishable intermediate and near specular light scattering in patterns that have statistical relevance to the dislocation and grain boundary defect densities. A reflectance measurement of the piece of material is obtained by adding together the signals from the optical detection devices. In the case where the piece of material includes a photovoltaic device, the current induced in the device by the illuminating light can be measured with a current sensing amplifier after the light integrating sphere is moved away from the device.

Non-wetting surface-driven high-aspect-ratio crystalline grain growth for efficient hybrid perovskite solar cells

DOE PAGES

Bi, Cheng; Wang, Qi; Shao, Yuchuan; ...

2015-07-20

Large-aspect-ratio grains are needed in polycrystalline thin-film solar cells for reduced charge recombination at grain boundaries; however, the grain size in organolead trihalide perovskite (OTP) films is generally limited by the film thickness. Here we report the growth of OTP grains with high average aspect ratio of 2.3–7.9 on a wide range of non-wetting hole transport layers (HTLs), which increase nucleus spacing by suppressing heterogeneous nucleation and facilitate grain boundary migration in grain growth by imposing less drag force. The reduced grain boundary area and improved crystallinity dramatically reduce the charge recombination in OTP thin films to the level inmore » OTP single crystals. Combining the high work function of several HTLs, a high stabilized device efficiency of 18.3% in low-temperature-processed planar-heterojunction OTP devices under 1 sun illumination is achieved. As a result, this simple method in enhancing OTP morphology paves the way for its application in other optoelectronic devices for enhanced performance.« less

Oxidation products of INCONEL alloys 600 and 690 in pressurized water reactor environments and their role in intergranular stress corrosion cracking

NASA Astrophysics Data System (ADS)

Ferguson, J. B.; Lopez, Hugo F.

2006-08-01

In this work, thermodynamic arguments for the stability of Ni and Cr compounds developed under pressurized water reactor environments ( P_{H_2 O} and P_{H_2 } ) were experimentally tested. A mechanism is proposed to explain crack initiation and propagation alloy 600 along the grain boundaries, where Cr2O3 has formed from the leaching of Cr from the matrix, leaving behind a porous Ni-rich region. The mechanism is based on the thermodynamic potential for the transformation of a protective NiO surface layer into an amorphous nonprotective Ni(OH)2 gel. This gel would also form along the grain boundaries and when hydrogenated steam reaches the porous Ni-rich regions. Crack initiation is then favored by tensile stressing of the grain boundary regions, which can easily rupture the gelatinous film. The leaching of matrix Cr to form nonprotective CrOOH gel at the crack tip followed by the exposure of fresh porous Ni to the environment could explain crack propagation in INCONEL alloy 600. The proposed crack initiation mechanism is not expected to occur in alloy 690 where a protective Cr2O3 film covers the entire metal surface. However, crack propagation along the grain boundaries in alloy 600 and precracked alloy 690 is expected to be active as hydroxide-forming reactions weaken the boundaries.

Spatial Heterogeneities and Onset of Passivation Breakdown at Lithium Anode Interfaces

DOE PAGES

Leung, Kevin; Jungjohann, Katherine L.

2017-09-08

Effective passivation of lithium metal surfaces, and prevention of battery-shorting lithium dendrite growth, are critical for implementing lithium metal anodes for batteries with increased power densities. Nanoscale surface heterogeneities can be “hot spots” where anode passivation breaks down. Motivated by the observation of lithium dendrites in pores and grain boundaries in all-solid batteries, we examine lithium metal surfaces covered with Li 2O and/or LiF thin films with grain boundaries in them. Electronic structure calculations show that at >0.25 V computed equilibrium overpotential Li 2O grain boundaries with sufficiently large pores can accommodate Li0 atoms which aid e– leakage and passivationmore » breakdown. Strain often accompanies Li insertion; applying an ~1.7% strain already lowers the computed overpotential to 0.1 V. Lithium metal nanostructures as thin as 12 Å are thermodynamically favored inside cracks in Li 2O films, becoming “incipient lithium filaments”. LiF films are more resistant to lithium metal growth. Finally, the models used herein should in turn inform passivating strategies in all-solid-state batteries.« less

Spatial Heterogeneities and Onset of Passivation Breakdown at Lithium Anode Interfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leung, Kevin; Jungjohann, Katherine L.

Effective passivation of lithium metal surfaces, and prevention of battery-shorting lithium dendrite growth, are critical for implementing lithium metal anodes for batteries with increased power densities. Nanoscale surface heterogeneities can be “hot spots” where anode passivation breaks down. Motivated by the observation of lithium dendrites in pores and grain boundaries in all-solid batteries, we examine lithium metal surfaces covered with Li 2O and/or LiF thin films with grain boundaries in them. Electronic structure calculations show that at >0.25 V computed equilibrium overpotential Li 2O grain boundaries with sufficiently large pores can accommodate Li0 atoms which aid e– leakage and passivationmore » breakdown. Strain often accompanies Li insertion; applying an ~1.7% strain already lowers the computed overpotential to 0.1 V. Lithium metal nanostructures as thin as 12 Å are thermodynamically favored inside cracks in Li 2O films, becoming “incipient lithium filaments”. LiF films are more resistant to lithium metal growth. Finally, the models used herein should in turn inform passivating strategies in all-solid-state batteries.« less

Carrier mobility enhancement of nano-crystalline semiconductor films: Incorporation of redox -relay species into the grain boundary interface

NASA Astrophysics Data System (ADS)

Desilva, L. A.; Bandara, T. M. W. J.; Hettiarachchi, B. H.; Kumara, G. R. A.; Perera, A. G. U.; Rajapaksa, R. M. G.; Tennakone, K.

Dye-sensitized and perovskite solar cells and other nanostructured heterojunction electronic devices require securing intimate electronic contact between nanostructured surfaces. Generally, the strategy is solution phase coating of a hole -collector over a nano-crystalline high-band gap n-type oxide semiconductor film painted with a thin layer of the light harvesting material. The nano-crystallites of the hole - collector fills the pores of the painted oxide surface. Most ills of these devices are associated with imperfect contact and high resistance of the hole conducting layer constituted of nano-crystallites. Denaturing of the delicate light harvesting material forbid sintering at elevated temperatures to reduce the grain boundary resistance. It is found that the interfacial and grain boundary resistance can be significantly reduced via incorporation of redox species into the interfaces to form ultra-thin layers. Suitable redox moieties, preferably bonded to the surface, act as electron transfer relays greatly reducing the film resistance offerring a promising method of enhancing the effective hole mobility of nano-crystalline hole-collectors and developing hole conductor paints for application in nanostructured devices.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bedekar, Vikram; Poplawsky, Jonathan D.; Guo, Wei

In grain finement and non-equilibrium there is carbon segregation within grain boundaries alters the mechanical performance of hard turning layers in carburized bearing steel. Moreover, an atom probe tomography (APT) study on the nanostructured hard turning layers reveals carbon migration to grain boundaries as a result of carbide decomposition during severe plastic deformation. In addition, samples exposed to different cutting speeds show that the carbon migration rate increases with the cutting speed. For these two effects lead to an ultrafine carbon network structure resulting in increased hardness and thermal stability in the severely deformed surface layer.

Static Grain Growth in Contact Metamorphic Calcite: A Cathodoluminescence Study.

NASA Astrophysics Data System (ADS)

Vogt, B.; Heilbronner, R.; Herwegh, M.; Ramseyer, K.

2009-04-01

In the Adamello contact aureole, monomineralic mesozoic limestones were investigated in terms of grain size evolution and compared to results on numerical modeling performed by Elle. The sampled area shows no deformation and therefore represents an appropriate natural laboratory for the study of static grain growth (Herwegh & Berger, 2003). For this purpose, samples were collected at different distances to the contact to the pluton, covering a temperature range between 270 to 630°C. In these marbles, the grain sizes increase with temperature from 5 µm to about 1 cm as one approaches the contact (Herwegh & Berger, 2003). In some samples, photomicrographs show domains of variable cathodoluminescence (CL) intensities, which are interpreted to represent growth zonations. Microstructures show grains that contain cores and in some samples even several growth stages. The cores are usually not centered and the zones not concentric. They may be in touch with grain boundaries. These zonation patterns are consistent within a given aggregate but differ among the samples even if they come from the same location. Relative CL intensities depend on the Mn/Fe ratio. We assume that changes in trace amounts of Mn/Fe must have occurred during the grain size evolution, preserving local geochemical trends and their variations with time. Changes in Mn/Fe ratios can either be explained by (a) locally derived fluids (e.g. hydration reactions of sheet silicate rich marbles in the vicinity) or (b) by the infiltration of the calcite aggregates by externally derived (magmatic?) fluids. At the present stage, we prefer a regional change in fluid composition (b) because the growth zonations only occur at distances of 750-1250 m from the pluton contact (350-450°C). Closer to the contact, neither zonations nor cores were found. At larger distances, CL intensities differ from grain to grain, revealing diagenetic CL patterns that were incompletely recrystallized by grain growth. The role of infiltration of magmatic fluids is also manifest in the vicinity of dikes, where intense zonation patterns are prominent in the marbles. The software Elle was developed to simulate microstructural evolution in rocks. The numerical model with the title "Grain boundary sweeping" was performed by M. Jessell and was found on http://www.materialsknowledge.org/elle. It displays the grain size evolution and the development of growth zonations during grain boundary migration of a 2D foam structure. This simulation was chosen because the driving force is the minimization of isotropic surface energies. It will be compared to the natural microstructures. At the last stage of the simulation the average grain and core sizes have increased. All, even the smallest grains, show growth zonations. Grains can be divided into two groups: (a) initially larger grains, increasing their grain size and maintaining their core size and (b) initially smaller grains with decreasing grain and decreasing core size. Group (a) grains show large areas swept by grain boundaries into the direction of small grains. Grain boundaries between large grains move more slowly. Their cores do not touch any grain boundaries. Cores of group (b) grains are in contact with the grain boundary network and are on the way to be consumed. In the numerical model and in the natural example similar features can be observed: The cores are not necessarily centered, the zonations are not necessarily concentric and some of the cores touch the grain boundary network. In the simulation, grain boundary migration velocity between large grains is smaller than between a large and a small grain. From this we would predict that - given enough time - a well sorted grain size distribution of increased grain size could be generated. But since many small grains occur we infer that this equilibrium has not been obtained. Analytical results of some natural samples that could be analyzed up to now indicate a relatively well sorted grain size distribution suggesting a more mature state of static grain growth. In comparison to the simulation, grain and core boundaries in the marbles are not always straight. For lobate grain boundaries the surface area has not been minimized in respect to the grain size. An explanation for this might be grain boundary pinning or a local dynamic overprint. Some cores and growth zones in the investigated calcites show a continuous change in luminescence. This is interpreted to be an effect of late diffusion within the grain and/or a continuous change of fluid composition and supply. The absence of zonation in samples close to the contact might be explained by fast grain growth due to high temperatures and/or fast fluid transport. Possibly, this is combined with an enhanced component of volume diffusion. Thus concentration variations of Mn/Fe are diminished and not visible in form of a growth zonation. Herwegh M, Berger A (2003) Differences in grain growth of calcite: a field-based modeling approach. Contr. Min. Pet. 145: 600-611

A study of the microstructure of a rapidly solidified nickel-base superalloy modified with boron. M.S. Thesis. Final Contractor Report

NASA Technical Reports Server (NTRS)

Speck, J. S.

1986-01-01

The microstructures of melt-spun superalloy ribbons with variable boron levels have been studied by transmission electron microscopy. The base alloy was of approximate composition Ni-11% Cr-5%Mo-5%Al-4%Ti with boron levels of 0.06, 0.12, and 0.60 percent (all by weight). Thirty micron thick ribbons display an equiaxed chill zone near the wheel contact side which develops into primary dendrite arms in the ribbon center. Secondary dendrite arms are observed near the ribbon free surface. In the higher boron bearing alloys, boride precipitates are observed along grain boundaries. A concerted effort has been made to elucidate true grain shapes by the use of bright field/dark field microscopy. In the low boron alloy, grain shapes are often convex, and grain faces are flat. Boundary faces frequently have large curvature, and grain shapes form concave polygons in the higher boron level alloys. It is proposed that just after solidification, in all of the alloys studied, grain shapes were initially concave and boundaries were wavy. Boundary straightening is presumed to occur on cooling in the low boron alloy. Boundary migration is precluded in the higher boron alloys by fast precipitation of borides at internal interfaces.

Strain induced grain boundary migration effects on grain growth of an austenitic stainless steel during static and metadynamic recrystallization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paggi, A., E-mail: alpaggi@tenaris.com; Angella, G.; Donnini, R.

Static and metadynamic recrystallization of an AISI 304L austenitic stainless steel was investigated at 1100 °C and 10{sup −} {sup 2} s{sup −} {sup 1} strain rate. The kinetics of recrystallization was determined through double hit compression tests. Two strain levels were selected for the first compression hit: ε{sub f} = 0.15 for static recrystallization (SRX) and 0.25 for metadynamic recrystallization (MDRX). Both the as-deformed and the recrystallized microstructures were investigated through optical microscopy and electron back-scattered diffraction (EBSD) technique. During deformation, strain induced grain boundary migration appeared to be significant, producing a square-like grain boundary structure aligned along themore » directions of the maximum shear stresses in compression. EBSD analysis revealed to be as a fundamental technique that the dislocation density was distributed heterogeneously in the deformed grains. Grain growth driven by surface energy reduction was also investigated, finding that it was too slow to explain the experimental data. Based on microstructural results, it was concluded that saturation of the nucleation sites occurred in the first stages of recrystallization, while grain growth driven by strain induced grain boundary migration (SIGBM) dominated the subsequent stages. - Highlights: • Recrystallization behavior of a stainless steel was investigated at 1100 °C. • EBSD revealed that the dislocation density distribution was heterogeneous during deformation. • Saturation of nucleation sites occurred in the first stages of recrystallization. • Strain induced grain boundary migration (SIGBM) effects were significant. • Grain growth driven by SIGBM dominated the subsequent stages.« less

Experiment-based modelling of grain boundary β-phase (Mg2Al3) evolution during sensitisation of aluminium alloy AA5083.

PubMed

Zhang, R; Steiner, M A; Agnew, S R; Kairy, S K; Davies, C H J; Birbilis, N

2017-06-07

An empirical model for the evolution of β-phase (Mg 2 Al 3 ) along grain boundaries in aluminium alloy AA5083 (Al-Mg-Mn) during isothermal exposures is proposed herein. Developing a quantitative understanding of grain boundary precipitation is important to interpreting intergranular corrosion and stress corrosion cracking in this alloy system. To date, complete ab initio models for grain boundary precipitation based upon fundamental principles of thermodynamics and kinetics are not available, despite the critical role that such precipitates play in dictating intergranular corrosion phenomena. Empirical models can therefore serve an important role in advancing the understanding of grain boundary precipitation kinetics, which is an approach applicable beyond the present context. High resolution scanning electron microscopy was to quantify the size and distribution of β-phase precipitates on Ga-embrittled intergranular fracture surfaces of AA5083. The results are compared with the degree of sensitisation (DoS) as judged by nitric acid mass loss testing (ASTM-G67-04), and discussed with models for sensitisation in 5xxx series Al-alloys. The work herein allows sensitisation to be quantified from an unambiguous microstructural perspective.

Characterization of erosion of metallic materials under cavitation attack in a mineral oil

NASA Technical Reports Server (NTRS)

Rao, B. C. S.; Buckley, D. H.

1985-01-01

Cavitation erosion and erosion rates of eight metallic materials representing three crystal structures were studied. The erosion experiments were conducted with a 20-kHz ultrasonic magnetostrictive oscillator in a viscous mineral oil. The erosion rates of the metals with an fcc matrix were 10 to 100 times higher than that of an hop-matrix titanium alloy. The erosion rates of iron and molybdenum, with bcc matrices, were higher than that of the titanium alloy but lower than those of those of the fcc materials. Studies with scanning electron microscopy indicated that the cavitation pits were initially formed at the grain boundaries and precipitates and that the pits formed at the junction of grain boundaries grew faster than the others. Transcrystalline craters formed by cavitation attack over the surface of grains and roughened the surfaces by multiple slip and twinning. Surface roughness measurements showed that the pits that formed over the grain boundaries deepened faster than pits. Computer analysis revealed that a geometric expression describes the nondimensional erosion curves during the time period 0.5 t (sub 0) t 2.5 t (sub 0), where t (sub 0) is the incubation period. The fcc metals had very short incubation periods; the titanium alloy had the longest incubation period.

Electrical, optical, and photoluminescence properties of ZnO films subjected to thermal annealing and treatment in hydrogen plasma

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abdullin, Kh. A.; Gabdullin, M. T.; Gritsenko, L. V.

The photoluminescence and optical absorption spectra and electrical properties of ZnO films grown by the metal–organic chemical vapor deposition and hydrothermal techniques, subjected to heat treatments and plasma treatment in a hydrogen atmosphere, are studied. It is shown that the adsorption of oxygen at grain boundaries upon annealing in an oxidizing atmosphere determines the electrical properties of the films. Vacuum annealing improves the electrical properties of the samples after degradation induced by annealing in air. Treatment in hydrogen plasma passivates surface states at the grain boundaries. The intrinsic photoluminescence intensity after plasma treatment is higher in the case of increasedmore » amounts of oxygen adsorbed at grain surfaces upon annealing in air. Surface states involving oxygen and hydrogen atoms are responsible for the high-intensity intrinsic photoluminescence band.« less

Effects of hydraulic roughness on surface textures of gravel-bed rivers

Treesearch

John M. Buffington; David R. Montgomery

1999-01-01

Field studies of forest gravel-bed rivers in northwestern Washington and southeastern Alaska demonstrate that bed-surface grain size is responsive to hydraulic roughness caused by bank irregularities, bars, and wood debris. We evaluate textural response by comparing reach-average median grain size (D50) to that predicted from the total bank-full boundary shear stress (...

Phase-field study of grain boundary tracking behavior in crack-seal microstructures

NASA Astrophysics Data System (ADS)

Ankit, Kumar; Nestler, Britta; Selzer, Michael; Reichardt, Mathias

2013-12-01

In order to address the growth of crystals in veins, a multiphase-field model is used to capture the dynamics of crystals precipitating from a super-saturated solution. To gain a detailed understanding of the polycrystal growth phenomena in veins, we investigate the influence of various boundary conditions on crystal growth. In particular, we analyze the formation of vein microstructures resulting from the free growth of crystals as well as crack-sealing processes. We define the crystal symmetry by considering the anisotropy in surface energy to simulate crystals with flat facets and sharp corners. The resulting growth competition of crystals with different orientations is studied to deduce a consistent orientation selection rule in the free-growth regime. Using crack-sealing simulations, we correlate the grain boundary tracking behavior depending on the relative rate of crack opening, opening trajectory, initial grain size, and wall roughness. Further, we illustrate how these parameters induce the microstructural transition between blocky (crystals growing anisotropically) to fibrous morphology (isotropic) and formation of grain boundaries. The phase-field simulations of crystals in the free-growth regime (in 2D and 3D) indicate that the growth or consumption of a crystal is dependent on the orientation difference with neighboring crystals. The crack-sealing simulation results (in 2D and 3D) reveal that crystals grow isotropically and grain boundaries track the opening trajectory if the wall roughness is high, opening increments are small, and crystals touch the wall before the next crack increment starts. Further, we find that within the complete crack-seal regime, anisotropy in surface energy results in the formation of curved/oscillating grain boundaries (instead of straight) when the crack-opening velocity is increased and wall roughness is not sufficiently high. Additionally, the overall capability of phase-field method to simulate large-scale polycrystal growth in veins (in 3D) is demonstrated enumerating the main advantages of adopting the novel approach.

Subsurface Grain Morphology Reconstruction by Differential Aperture X-ray Microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eisenlohr, Philip; Shanthraj, Pratheek; Vande Kieft, Brendan R.

A multistep, non-destructive grain morphology reconstruction methodology that is applicable to near-surface volumes is developed and tested on synthetic grain structures. This approach probes the subsurface crystal orientation using differential aperture X-ray microscopy (DAXM) on a sparse grid across the microstructure volume of interest. Resulting orientation data is clustered according to proximity in physical and orientation space and used as seed points for an initial Voronoi tessellation to (crudely) approximate the grain morphology. Curvature-driven grain boundary relaxation, simulated by means of the Voronoi Implicit Interface Method (VIIM), progressively improves the reconstruction accuracy. The similarity between bulk and readily accessible surfacemore » reconstruction error provides an objective termination criterion for boundary relaxation.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo, Rui; Gao, Liming, E-mail: liming.gao@sjtu.edu.cn; Li, Ming, E-mail: mingli90@sjtu.edu.cn

As the continuous shrinkage of the interconnect line width in microelectronics devices, there is a growing concern about the electromigration (EM) failure of bonding wire. In addition, an innovative Ag–8Au–3Pd alloy wire has shown promise as an economical substitute for gold wire interconnects due to the cost pressure of gold in the last decade. In present study of the Ag–8Au–3Pd alloy wire, the surface diffusion occupied the dominant position during EM failure, and the activation energy was found to be 0.61 eV. In order to reveal the failure mechanism, the cross-sections of the Ag–8Au–3Pd alloy wire during EM were preparedmore » by focused ion beam (FIB) micro-machining for electron backscatter diffraction (EBSD) analysis. The microstructure evolution of the Ag–8Au–3Pd alloy wire was characterized by the grain size and grain boundary. As a result, the EM failure originates in the atom transportation, which causes grain size increasing and atom diffusion on the wire surface. - Highlights: • The activation energy of Ag–8Au–3Pd alloy wire was obtained as 0.61 eV. • During EM, the silver atoms diffused from negative to the positive terminal on the wire surface. • The microstructure (grain size and grain boundary) was characterized by FIB-EBSD. • During EM, the atom transportation was found to cause grain size growth and atom diffusion on the wire surface.« less

Synthesis and characterization of hollow mesoporous BaFe{sub 12}O{sub 19} spheres

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Xia; Department of Chemical and Biological Engineering, The University of Alabama, Tuscaloosa, AL 35487; Park, Jihoon

2015-02-15

A facile method is reported to synthesize hollow mesoporous BaFe{sub 12}O{sub 19} spheres using a template-free chemical etching process. Hollow BaFe{sub 12}O{sub 19} spheres were synthesized by conventional spray pyrolysis. The mesoporous structure is achieved by alkaline ethylene glycol etching at 185 °C, with the porosity controlled by the heating time. The hollow porous structure is confirmed by SEM, TEM, and FIB-FESEM characterization. The crystal structure and magnetic properties are not significantly affected after the chemical etching process. The formation mechanism of the porous structure is explained by grain boundary etching. - Graphical abstract: Hollow spherical BaFe{sub 12}O{sub 19} particlesmore » are polycrystalline with both grains and grain boundaries. Grain boundaries have less ordered structure and lower stability. When the particles are exposed to high temperature alkaline ethylene glycol, the grain boundaries are etched, leaving small grooves between grains. These grooves allow ethylene glycol to diffuse inside to further etch the grains. As the grain size decreases, gaps appear on the particle surfaces, and a porous structure is finally formed. - Highlights: • Two-step synthesis method for hollow mesoporous BaFe{sub 12}O{sub 19} spheres is proposed. • Porosity of the product can be regulated by controlling the second step of chemical etching. • The crystal structure and magnetic properties are examined to be little affected during the chemical etching. • The mesoporous structure formation mechanism is explained by grain boundary etching.« less

Large grain CBMM Nb ingot slices: An ideal test bed for exploring the microstructure-electromagnetic property relationships relevant to SRF

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sung, Zu-Hawn, E-mail: ZSung@uss.com; Now at US-Steel, Pittsburgh, US; Lee, Peter J., E-mail: lee@asc.magnet.fsu.edu

2015-12-04

High purity (RRR > 200), large grain (> 5-10 cm) niobium ingot slices have been successfully used to fabricate radio frequency (RF) cavities for particle accelerators. They offer significantly reduced fabrication cost by eliminating processing steps and furthermore they provide the opportunity to study the influence of individual grain boundaries in SRF Nb. Here we summarize our measurements of grain boundary (GB) effects on the superconducting properties of large grain high purity niobium sheet manufactured by CBMM. We show by magneto-optical (MO) imaging that GBs allow premature flux penetration, but only when they are oriented close to the direction of themore » magnetic field. However, even low angle GBs produced by minor deformations commensurate with half-cell forming produce localized flux penetration. The transport properties of grain boundaries were investigated by direct transport across them and evidence for preferential vortex flow along the GBs of SRF Nb was observed for the first time. Using transmission electron microscopy (TEM) and micro crystallographic analysis with electron backscattered diffraction (EBSD), we were able to quantitatively characterize surface substructures that can lead to localized thermal breakdown of superconductivity. Important to these studies was the development of sample preparation techniques that made the cutout single, bi-crystal and tri-crystal Nb coupons as representative as possible of the surface properties of cavities manufactured by standard techniques.« less

Computational and Experimental Studies of Microstructure-Scale Porosity in Metallic Fuels for Improved Gas Swelling Behavior

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mllett, Paul; McDeavitt, Sean; Deo, Chaitanya

This proposal will investigate the stability of bimodal pore size distributions in metallic uranium and uranium-zirconium alloys during sintering and re-sintering annealing treatments. The project will utilize both computational and experimental approaches. The computational approach includes both Molecular Dynamics simulations to determine the self-diffusion coefficients in pure U and U-Zr alloys in single crystals, grain boundaries, and free surfaces, as well as calculations of grain boundary and free surface interfacial energies. Phase-field simulations using MOOSE will be conducted to study pore and grain structure evolution in microstructures with bimodal pore size distributions. Experiments will also be performed to validate themore » simulations, and measure the time-dependent densification of bimodal porous compacts.« less

Investigation of Material Problems for High Temperature, High Power Space Energy-Conversion Systems.

DTIC Science & Technology

1986-07-01

Microplastic Deformation in Molybdenum with Grain-Boundary Segregations of Nickel, Phys. Met. Metall. 54, 180, 1982. 76. C. Lea, B. Muddle and D...8217-- *. ~a.-. ~ ~ ~ .. . ~ . ~ . .*.. -- ~ .. 25 93. T. Noda, T. Kainuma and M. Okada: Oxygen Desorption from Grain Boundaries of Molybdenum During Vacuu...behavior of this work function climb was explained by the desorption of atoms adsorbed or, the surface. The test result of the present W-Re samples showed

Impedance and electric modulus approaches to investigate four origins of giant dielectric constant in CaCu3Ti4O12 ceramics

NASA Astrophysics Data System (ADS)

Yuan, Wen-Xiang

2012-03-01

The frequency dependence of electric modulus of polycrystalline CaCu3Ti4O12 (CCTO) ceramics has been investigated. The experimental data have also been analyzed in the complex plane of impedance and electric modulus, and a suitable equivalent circuit has been proposed to explain the dielectric response. Four dielectric responses are first distinguished in the impedance and modulus spectroscopies. The results are well interpreted in terms of a triple insulating barrier capacitor model. Using this model, these four dielectric relaxations are attributed to the domain, domain-boundary, grain-boundary, and surface layer effects with three Maxwell-Wagner relaxations. Moreover, the values of the resistance and capacitance of bulk CCTO phase, domain-boundary, grain-boundary and surface layer contributions have been calculated directly from the peak characteristics of spectroscopic plots.

Size effects and charge transport in metals: Quantum theory of the resistivity of nanometric metallic structures arising from electron scattering by grain boundaries and by rough surfaces

NASA Astrophysics Data System (ADS)

Munoz, Raul C.; Arenas, Claudio

2017-03-01

We discuss recent progress regarding size effects and their incidence upon the coefficients describing charge transport (resistivity, magnetoresistance, and Hall effect) induced by electron scattering from disordered grain boundaries and from rough surfaces on metallic nanostructures; we review recent measurements of the magneto transport coefficients that elucidate the electron scattering mechanisms at work. We review as well theoretical developments regarding quantum transport theories that allow calculating the increase in resistivity induced by electron-rough surface scattering (in the absence of grain boundaries) from first principles—from the parameters that describe the surface roughness that can be measured with a Scanning Tunnelling Microscope (STM). We evaluate the predicting power of the quantum version of the Fuchs-Sondheimer theory and of the model proposed by Calecki, abandoning the method of parameter fitting used for decades, but comparing instead theoretical predictions with resistivity measured in thin films where surface roughness has also been measured with a STM, and where electron-grain boundary scattering can be neglected. We also review the theory of Mayadas and Shatzkes (MS) [Phys. Rev. B 1, 1382 (1970)] used for decades, and discuss its severe conceptual difficulties that arise out of the fact that: (i) MS employed plane waves to describe the electronic states within the metal sample having periodic grain boundaries, rather than the Bloch states known since the thirties to be the solutions of the Schrödinger equation describing electrons propagating through a Krönig-Penney [Proc. R. Soc. London Ser. A 130, 499 (1931)] periodic potential; (ii) MS ignored the fact that the wave functions describing electrons propagating through a 1-D disordered potential are expected to decay exponentially with increasing distance, a fact known since the work of Anderson [Phys. Rev. 109, 1492 (1958)] in 1958 for which he was awarded the Nobel Prize in 1977; (iii) The current in the sample should be proportional to TN, the probability that an electron traverses N consecutive (disordered) grains found along a mean free path; MS assumed that TN = 1. We review unpublished details of a quantum transport theory based upon a model of diffusive transport and Kubo's linear response formalism recently published [Arenas et al., Appl. Surf. Sci. 329, 184 (2015)], which permits estimating the increase in resistivity of a metallic specimen (over the bulk resistivity) under the combined effects of electron scattering by phonons, impurities, disordered grain boundaries, and rough surfaces limiting the sample. We evaluate the predicting power of both the MS theory and of the new quantum model on samples where the temperature dependence of the resistivity has been measured between 4 K and 300 K, and where surface roughness and grain size distribution has been measured on each sample via independent experiments. We find that the quantum theory does exhibit a predicting power, whereas the predicting power of the MS model as well as the significance and reliability of its fitting parameters seems questionable. We explore the power of the new theory by comparing, for the first time, the resistivity predicted and measured on nanometric Cu wires of (approximately) rectangular cross section employed in building integrated circuits, based upon a quantum description of electron motion.

Micro-mechanisms of Surface Defects Induced on Aluminum Alloys during Plastic Deformation at Elevated Temperatures

NASA Astrophysics Data System (ADS)

Gali, Olufisayo A.

Near-surface deformed layers developed on aluminum alloys significantly influence the corrosion and tribological behavior as well as reduce the surface quality of the rolled aluminum. The evolution of the near-surface microstructures induced on magnesium containing aluminum alloys during thermomechanical processing has been investigated with the aim generating an understanding of the influence of individual forming parameters on its evolution and examine the microstructure of the roll coating induced on the mating steel roll through material transfer during rolling. The micro-mechanisms related to the various features of near-surface microstructure developed during tribological conditions of the simulated hot rolling process were identified. Thermomechanical processing experiments were performed with the aid of hot rolling (operating temperature: 550 to 460 °C, 4, 10 and 20 rolling pass schedules) and hot forming (operating temperature: 350 to 545 °C, strain rate: 4 x 10-2 s-1) tribo-simulators. The surface, near-surface features and material transfer induced during the elevated temperature plastic deformation were examined and characterized employing optical interferometry, SEM/EDS, FIB and TEM. Near-surface features characterized on the rolled aluminum alloys included; cracks, fractured intermetallic particles, aluminum nano-particles, oxide decorated grain boundaries, rolled-in oxides, shingles and blisters. These features were related to various individual rolling parameters which included, the work roll roughness, which induced the formation of shingles, rolling marks and were responsible for the redistribution of surface oxide and the enhancements of the depth of the near-surface damage. The enhanced stresses and strains experienced during rolling were related to the formation and propagation of cracks, the nanocrystalline structure of the near-surface layers and aluminum nano-particles. The mechanism of the evolution of the near-surface microstructure were determined to include grain boundary sliding which induced the cracks at the surface and subsurface of the alloy, magnesium diffusion to free surfaces, crack propagation from shear stresses and the shear strains inducing the nanocrystalline grain structure, the formation of shingles by the shear deformation of micro-wedges induced by the work roll grooves, and the deformation of this oxide covered micro-wedges inducing the rolled-in oxides. Magnesium diffusion to free surfaces was identified as inducing crack healing due to the formation of MgO within cracks and was responsible for the oxide decorated grain boundaries. An examination of the roll coating revealed a complex layered microstructure that was induced through tribo-chemical and mechanical entrapment mechanisms. The microstructure of the roll coating suggested that the work roll material and the rolled aluminum alloy were essential in determining its composition and structure. Subsequent hot forming processes revealed the rich oxide-layer of the near-surface microstructure was beneficial for reducing the coefficient of friction during tribological contact with the steel die. Damage to the microstructure include cracks induced from grain boundary sliding of near-surface grains and the formation of oxide fibres within cracks of the near-surface deformed layers.

Microstructural-Scale Model for Surfaces Spreading of Intergranular Corrosion in Sensitized Stainless Steels and Aluminum-Magnesium (AA5XXX) Alloys

NASA Astrophysics Data System (ADS)

Jain, Swati

Components from AA5XXX (Al-Mg alloys with more than 3 wt% Mg) alloys are X attractive due to availability of low cost, high strength to weight ratio and good weldability. Therefore, these alloys have potential applications in Naval ships. However, these alloys become susceptible to IGC (intergranular corrosion) due to beta-phase precipitation due to improper heat treatment or inadvertent thermal exposure. Stainless steels may also become susceptible due to carbide precipitation and chromium depletion on grain boundaries. IGC susceptibility depends on the interplay between the metallurgical conditions, electrochemical conditions, and chemical conditions. Specific combinations cause IGC while others do not. The objective of this study is to investigate the conditions which bring about surface spreading of IGC in these alloy classes. To accomplish this goal, a microstructure scale model was developed with experimental inputs to understand the 2-D IGC spreading in stainless steels and AA5XXX alloys. The conditions strongly affecting IGC spreading were elucidated. Upon natural and artificial aging, the stainless steels become susceptible to intergranular corrosion because of chromium depletion in the grain boundaries. After aging Al-Mg (AA5XXX) alloys show susceptibility due to the precipitation of the beta-phase (Al3Mg7) in the grain boundaries. Chromium depleted grain boundaries in stainless steels are anodically more active as compared to the interior of the grains. (3-phase rich grain boundaries have lower OCP (open circuit potential) and pitting potentials as compared to the Al-Mg solid solutions. A new approach to modeling the IGC surface spreading in polycrystalline materials that is presented. This model is the first to couple several factors into one granular scale model that illustrates the way in which they interact and IGC occurs. It sheds new information on conditions which cause IGC spreading in two alloy classes and describes a new theory for the critical potential associated with IGC. The outcomes from this contribute to ways to advance the goal of corrosion resistant computational design of alloys, guiding mitigation strategies for suppressing IGC in existing alloys, and to damage prognosis aimed at predicting damage and structural integrity.

Atomic migration of carbon in hard turned layers of carburized bearing steel

DOE PAGES

Bedekar, Vikram; Poplawsky, Jonathan D.; Guo, Wei; ...

2016-01-01

In grain finement and non-equilibrium there is carbon segregation within grain boundaries alters the mechanical performance of hard turning layers in carburized bearing steel. Moreover, an atom probe tomography (APT) study on the nanostructured hard turning layers reveals carbon migration to grain boundaries as a result of carbide decomposition during severe plastic deformation. In addition, samples exposed to different cutting speeds show that the carbon migration rate increases with the cutting speed. For these two effects lead to an ultrafine carbon network structure resulting in increased hardness and thermal stability in the severely deformed surface layer.

Prevention of weld-decay in austenitic stainless steel by using surface mechanical attrition treatment

NASA Astrophysics Data System (ADS)

Laleh, Majid; Kargar, Farzad; Rouhaghdam, Alireza Sabour

2012-11-01

Surface mechanical attrition treatment (SMAT) was applied to the samples of a type AISI 304 stainless steel in order to induce grain refinement as well as formation of twins. Transmission electron microscopy and X-ray diffraction analysis results showed that the average grain size at the surface of the SMATed sample was about 10 nm. The untreated and SMATed samples were then welded using a one-pass gas tungsten arc procedure. The heat-affected zone (HAZ) of the samples was examined by optical microscopy and corrosion tests. Results of the double loop electrochemical potentiokinetic reactivation tests showed that the degree of sensitization in the HAZ for the SMATed sample was very low as compared to that of the untreated one. The pre-SMATed sample was resistant to intergranular corrosion. This is mainly due to the formation of high density of twins which are not prone to carbide precipitation because of their regular and coherent atomic structure and extreme low grain boundary energy as compared with those of other grain boundaries.

Spectrum-per-Pixel Cathodoluminescence Imaging of CdTe Thin-Film Bevels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moseley, John; Al-Jassim, Mowafak M.; Burst, James

2016-11-21

We conduct T=6 K cathodoluminescence (CL) spectrum imaging with a nano-scale electron beam on beveled surfaces of CdTe thin-films at different critical stages of standard CdTe device fabrication. The through-thickness total CL intensity profiles are consistent with a reduction in grain boundary recombination due to the CdCl2 treatment. Color-coded maps of the low-temperature luminescence transition energies reveal that CdTe thin films have remarkably non-uniform opto-electronic properties, which depend strongly on sample processing history. The grain-to-grain S content in the interdiffused CdTe/CdS region is estimated from a sample size of thirty-five grains, and the S content in adjacent grains varies significantlymore » in CdCl2-treated samples. A low-temperature luminescence model is developed to interpret spectral behavior at grain boundaries and grain interiors.« less

On the interaction of solutes with grain boundaries

DOE PAGES

Dingreville, Remi Philippe Michel; Berbenni, Stephane

2015-11-01

Solute segregation to grain boundaries is considered by modeling solute atoms as misfitting inclusions within a disclination structural unit model describing the grain boundary structure and its intrinsic stress field. The solute distribution around grain boundaries is described through Fermi–Dirac statistics of site occupancy. The susceptibility of hydrogen segregation to symmetric tilt grain boundaries is discussed in terms of the misorientation angle, the defect type characteristics at the grain boundary, temperature, and the prescribed bulk hydrogen fraction of occupied sites. Through this formalism, it is found that hydrogen trapping on grain boundaries clearly correlates with the grain boundary structure (i.e.more » type of structural unit composing the grain boundary), and the associated grain boundary misorientation. Specifically, for symmetric tilt grain boundaries about the [001] axis, grain boundaries composed of both B and C structural units show a lower segregation susceptibility than other grain boundaries. A direct correlation between the segregation susceptibility and the intrinsic net defect density is provided through the Frank–Bilby formalism. Moreover, the present formulation could prove to be a simple and useful model to identify classes of grain boundaries relevant to grain boundary engineering.« less

On the interaction of solutes with grain boundaries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dingreville, Remi Philippe Michel; Berbenni, Stephane

Solute segregation to grain boundaries is considered by modeling solute atoms as misfitting inclusions within a disclination structural unit model describing the grain boundary structure and its intrinsic stress field. The solute distribution around grain boundaries is described through Fermi–Dirac statistics of site occupancy. The susceptibility of hydrogen segregation to symmetric tilt grain boundaries is discussed in terms of the misorientation angle, the defect type characteristics at the grain boundary, temperature, and the prescribed bulk hydrogen fraction of occupied sites. Through this formalism, it is found that hydrogen trapping on grain boundaries clearly correlates with the grain boundary structure (i.e.more » type of structural unit composing the grain boundary), and the associated grain boundary misorientation. Specifically, for symmetric tilt grain boundaries about the [001] axis, grain boundaries composed of both B and C structural units show a lower segregation susceptibility than other grain boundaries. A direct correlation between the segregation susceptibility and the intrinsic net defect density is provided through the Frank–Bilby formalism. Moreover, the present formulation could prove to be a simple and useful model to identify classes of grain boundaries relevant to grain boundary engineering.« less

Grain-boundary-dependent CO2 electroreduction activity.

PubMed

Feng, Xiaofeng; Jiang, Kaili; Fan, Shoushan; Kanan, Matthew W

2015-04-15

Uncovering new structure-activity relationships for metal nanoparticle (NP) electrocatalysts is crucial for advancing many energy conversion technologies. Grain boundaries (GBs) could be used to stabilize unique active surfaces, but a quantitative correlation between GBs and catalytic activity has not been established. Here we use vapor deposition to prepare Au NPs on carbon nanotubes (Au/CNT). As deposited, the Au NPs have a relatively high density of GBs that are readily imaged by transmission electron microscopy (TEM); thermal annealing lowers the density in a controlled manner. We show that the surface-area-normalized activity for CO2 reduction is linearly correlated with GB surface density on Au/CNT, demonstrating that GB engineering is a powerful approach to improving the catalytic activity of metal NPs.

Thermodynamic understanding of Sn whisker growth on the Cu surface in Cu(top)-Sn(bottom) bilayer system upon room temperature aging

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Lin; Jian, Wei; Lin, Bing

2015-06-07

Sn whiskers are observed by scanning electron microscope on the Cu surface in Cu(top)-Sn(bottom) bilayer system upon room temperature aging. Only Cu{sub 6}Sn{sub 5} phase appears in the X-ray diffraction patterns and no Sn element is detected in the Cu sublayer by scanning transmission electron microscopy. Based on the interfacial thermodynamics, the intermetallic Cu{sub 6}Sn{sub 5} compound phase may form directly at the Sn grain boundary. Driven by the stress gradient during the formation of Cu{sub 6}Sn{sub 5} compound at Sn grain boundaries, Sn atoms segregate onto the Cu surface and accumulate to form Sn whisker.

Periodic grain-boundary formation in a poly-Si thin film crystallized by linearly polarized Nd:YAG pulse laser with an oblique incident angle

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaki, Hirokazu; Horita, Susumu

2005-01-01

We investigated the periodic grain-boundary formation in the polycrystalline silicon film crystallized by a linearly polarized Nd:YAG (where YAG is yttrium aluminum garnet) pulse laser with an oblique incident angle {theta}{sub i}=25 deg. , compared with the normal incident angle {theta}{sub i}=0. The alignment of the grain boundary was uncontrollable and fluctuated in the case of the oblique incident and large irradiation pulse number while that in the case of the normal incident was performed stably. It was found that the main cause for its low controllability was the nonphase matching between the periodic surface corrugation of the crystallized siliconmore » film and the periodic temperature profile induced by the laser irradiation. Also, it was found that, in the case of {theta}{sub i}=25 deg. , the dominant periodic width of the grain boundary depended on the pulse number N. That is, it was around {lambda}/(1+sin {theta}{sub i}) for small N{approx_equal}10 and {lambda}/(1-sin {theta}{sub i}) for large N{approx_equal}100 at the laser wavelength of {lambda}=532 nm. In order to explain this dependence, we proposed a model to take into account the periodic corrugation height proportional to the molten volume of the silicon film, the impediment in interference between the incident beam and diffracted beam on the irradiated surface due to the corrugation height, and the reduction of the liquid surface roughness during melting-crystallization process due to liquid-silicon viscosity.« less

Oxidation and low cycle fatigue life prediction

NASA Technical Reports Server (NTRS)

Oshida, Y.; Liu, H. W.

1984-01-01

When a metallic material is exposed to a high temperature in an ambient atmosphere, oxidation takes place on the metallic surface. The formed oxides (both surface and grain boundary oxides) are mechanically brittle so that if the stress is high enough the oxides will be cracked. The grain boundary oxide formation in TAZ-8A nickel-base superalloy was studied. The effect of oxide crack nucleus on low cycle fatigue life will be analyzed. The TAZ-8A was subjected to high temperature oxidation tests in air under the stress-free condition. The oxidation temperatures were 600, 800, and 1000 C. The oxidation time varies from 10 to 1000 hours.

C-Cr segregation at grain boundary before the carbide nucleation in Alloy 690

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li Hui, E-mail: huili@shu.edu.cn; Laboratory for Microstructures, Shanghai University, Shanghai, 200444; Xia Shuang

2012-04-15

The grain boundary segregation in Alloy 690 was investigated by atom probe tomography. B, C and Si segregated at the grain boundary. The high concentration regions for each segregation element form a set of straight arrays that are parallel to each other in the grain boundary plane. The concentration fluctuation has a periodicity of about 7 nm in the grain boundary plane. Before the Cr{sub 23}C{sub 6} nucleation at grain boundaries, the C-Cr co-segregate on one side of the grain boundaries while not the exact grain boundary core regions have been detected. The reasons why grain boundary carbides have coherentmore » orientation relationship only with one side of nearby grain which grain boundary is located at high index crystal plane were discussed. - Highlights: Black-Right-Pointing-Pointer Grain boundary segregation in Alloy 690 was investigated by atom probe tomography. Black-Right-Pointing-Pointer B, C and Si segregate at the grain boundary. Black-Right-Pointing-Pointer Concentration of segregated atoms periodicity fluctuated in the grain boundary plane. Black-Right-Pointing-Pointer C and Cr co-segregate on one side of the grain boundary before carbide nucleation.« less

Study the Formation of H2, HD and D2 under Various Interstellar Conditions

NASA Astrophysics Data System (ADS)

Sahu, Dipen; Chakrabarti, Sandip Kumar; Das, Ankan

2016-07-01

Hydrogen is the most abundant molecule in the Interstellar medium (ISM). Formation of gas phase hydrogen molecule is inefficient; perhaps grain surface acts as a necessary ingredients for the formation of H_2 molecule. H atoms accrete on the grain surface, recombine there and desorb in the gas phase. Similarly, deuterium accretion on grain surfaces can produce simple dueterated molecules (HD and D_2) on the ISM. Unlike gas phase reactions, rate equations can not yield accurate result for grain surface reactions due to inherent randomness of surface species. We use Monte-Carlo method to follow this surface chemistry which effectively take care of this randomness. We use square grids and impose periodic boundary condition on them to mimic the spherical nature of grains. Various types of rough surfaces are considered to study the impact on effective production rates. We found that these simple but most important molecules are produced in low temperature (physisorption sites) as well as in high temperature (chemisorption sites) regions.

Friction angle measurements on a naturally formed gravel streambed: Implications for critical boundary shear stress

Treesearch

John M. Buffington; William E. Dietrich; James W. Kirchner

1992-01-01

We report the first measurements of friction angles for a naturally formed gravel streambed. For a given test grain size placed on a bed surface, friction angles varied from 10º to over 100º; friction angle distributions can be expressed as a function of test grain size, median bed grain size, and bed sorting parameter. Friction angles decrease with increasing grain...

Surface evolution in bare bamboo-type metal lines under diffusion and electric field effects

NASA Astrophysics Data System (ADS)

Averbuch, Amir; Israeli, Moshe; Nathan, Menachem; Ravve, Igor

2003-07-01

Irregularities such as voids and cracks often occur in bamboo-type metal lines of microelectronic interconnects. They increase the resistance of the circuits, and may even lead to a fatal failure. In this work, we analyze numerically the electromigration of an unpassivated bamboo-type line with pre-existing irregularities in its top surface (also called a grain-void interface). The bamboo line is subjected to surface diffusion forces and external electric fields. Under these forces, initial defects may either heal or become worse. The grain-void interface is considered to be one-dimensional, and the physical formulation of an electromigration and diffusion model results in two coupled, fourth order, one-dimensional time-dependent PDEs, with the boundary conditions imposed at the electrode points and at the triple point, which belongs to two neighboring grains and the void. These equations are discretized by finite differences on a regular grid in space, and by a Runge-Kutta integration scheme in time, and solved simultaneously with a static Laplace equation describing the voltage distribution throughout each grain, when the substrate conductivity is neglected. Since the voltage distribution is required only along an interface line, the two-dimensional discretization of the grain interior is not needed, and the static problem is solved by the boundary element method at each time step. The motion of the interface line is studied for different ratios between diffusion and electric field forces, and for different initial configurations of the grain-void interface. We study plain and tilted contour lines, considering positive and negative tilts with respect to the external electric field, a stepped contour with field lines entering or exiting the 'step', and a number of modifications of the classical Mullins problem of thermal grooving. We also consider a two-grain Mullins problem with a normal and tilted boundary between the grains, examining positive and negative tilts.

Atomistic modeling of grain boundary behavior under shear conditions in magnesium and magnesium-based binary alloys

NASA Astrophysics Data System (ADS)

Nahhas, M. K.; Groh, S.

2018-02-01

In this study, the structure, the energetic, and the strength of a { 10 1 bar 1 } < 11 2 bar 0 > symmetric tilt grain boundary in magnesium and magnesium binary alloys were analyzed in the framework of (semi-)empirical potentials. Following a systematic investigation of the transferability and accuracy of the interatomic potentials, atomistic calculations of the grain boundary energy, the grain boundary sliding energy, and the grain boundary strength were performed in pure magnesium and in binary MgX alloys (X = Al, Ca, Gd, Li, Sn, Y, Ag, Nd, and Pb). The data gained in this study were analyzed to identify the most critical material parameters controlling the strength of the grain boundary, and their consequence on atomic shuffling motions occurring at the grain boundary. From the methodology perspective, the role of in-plane and out-of plane relaxation on the grain boundary sliding energy curves was investigated. In pure magnesium, the results showed that in-plane relaxation is critical in activating b2{ 10 1 bar 1 } twinning dislocation resulting in grain boundary migration. In the alloy systems, however, grain boundary migration was disabled as a consequence of the pinning of the grain boundary by segregated elements. Finally, while the grain boundary energy, the shape of the grain boundary sliding energy curves, and the grain boundary sliding energy are critical parameters controlling the grain boundary strength in pure magnesium, only the grain boundary energy and the segregation energy of the alloying elements at the grain boundary were identified as critical material parameters in the alloys system.

Growth kinetics of white graphene (h-BN) on a planarised Ni foil surface

PubMed Central

Cho, Hyunjin; Park, Sungchan; Won, Dong-Il; Kang, Sang Ook; Pyo, Seong-Soo; Kim, Dong-Ik; Kim, Soo Min; Kim, Hwan Chul; Kim, Myung Jong

2015-01-01

The morphology of the surface and the grain orientation of metal catalysts have been considered to be two important factors for the growth of white graphene (h-BN) by chemical vapour deposition (CVD). We report a correlation between the growth rate of h-BN and the orientation of the nickel grains. The surface of the nickel (Ni) foil was first polished by electrochemical polishing (ECP) and subsequently annealed in hydrogen at atmospheric pressure to suppress the effect of the surface morphology. Atmospheric annealing with hydrogen reduced the nucleation sites of h-BN, which induced a large crystal size mainly grown from the grain boundary with few other nucleation sites in the Ni foil. A higher growth rate was observed from the Ni grains that had the {110} or {100} orientation due to their higher surface energy. PMID:26156068

Large grain CBMM Nb ingot slices: An ideal test bed for exploring the microstructure-electromagnetic property relationships relevant to SRF

DOE PAGES

Sung, Zu -Hawn; Lee, Peter J.; Polyanskii, Anatolii; ...

2015-12-04

High purity (RRR > 200), large grain (> 5-10 cm) niobium ingot slices have been successfully used to fabricate radio frequency (RF) cavities for particle accelerators. In addition, they offer significantly reduced fabrication cost by eliminating processing steps and furthermore they provide the opportunity to study the influence of individual grain boundaries in SRF Nb. Here we summarize our measurements of grain boundary (GB) effects on the superconducting properties of large grain high purity niobium sheet manufactured by CBMM. We show by magneto-optical (MO) imaging that GBs allow premature flux penetration, but only when they are oriented close to themore » direction of the magnetic field. However, even low angle GBs produced by minor deformations commensurate with half-cell forming produce localized flux penetration. The transport properties of grain boundaries were investigated by direct transport across them and evidence for preferential vortex flow along the GBs of SRF Nb was observed for the first time. Using transmission electron microscopy (TEM) and micro crystallographic analysis with electron backscattered diffraction (EBSD), we were able to quantitatively characterize surface substructures that can lead to localized thermal breakdown of superconductivity. Important to these studies was the development of sample preparation techniques that made the cut-out single, bi-crystal and tri-crystal Nb coupons as representative as possible of the surface properties of cavities manufactured by standard techniques.« less

Influence of SiC grain boundary character on fission product transport in irradiated TRISO fuel

NASA Astrophysics Data System (ADS)

Lillo, T. M.; van Rooyen, I. J.

2016-05-01

In this study, the fission product precipitates at silicon carbide grain boundaries from an irradiated TRISO particle were identified and correlated with the associated grain boundary characteristics. Precession electron diffraction in the transmission electron microscope provided the crystallographic information needed to identify grain boundary misorientation and boundary type (i.e., low angle, random high angle or coincident site lattice (CSL)-related). The silicon carbide layer was found to be composed mainly of twin boundaries and small fractions of random high angle and low angle grain boundaries. Most fission products were found at random, high-angle grain boundaries, with small fractions at low-angle and CSL-related grain boundaries. Palladium (Pd) was found at all types of grain boundaries while Pd-uranium and Pd-silver precipitates were only associated with CSL-related and random, high-angle grain boundaries. Precipitates containing only Ag were found only at random, high-angle grain boundaries, but not at low angle or CSL-related grain boundaries.

Atomic scale study of grain boundary segregation before carbide nucleation in Ni-Cr-Fe Alloys

NASA Astrophysics Data System (ADS)

Li, Hui; Xia, Shuang; Liu, Wenqing; Liu, Tingguang; Zhou, Bangxin

2013-08-01

Three dimensional chemical information concerning grain boundary segregation before carbide nucleation was characterized by atom probe tomography in two Ni-Cr-Fe alloys which were aged at 500 °C for 0.5 h after homogenizing treatment. B, C and Si atoms segregation at grain boundary in Alloy 690 was observed. B, C, N and P atoms segregation at grain boundary in 304 austenitic stainless steel was observed. C atoms co-segregation with Cr atoms at the grain boundaries both in Alloy 690 and 304 austenitic stainless steel was found, and its effect on the carbide nucleation was discussed. The amount of each segregated element at grain boundaries in the two Ni-Cr-Fe alloys were analyzed quantitatively. Comparison of the grain boundary segregation features of the two Ni-Cr-Fe alloys were carried out based on the experimental results. The impurity and solute atoms segregate inhomogeneously in the same grain boundary both in 304 SS and Alloy 690. The grain boundary segregation tendencies (Sav) are B (11.8 ± 1.4) > P (5.4 ± 1.4) > N (4.7 ± 0.3) > C (3.7 ± 0.4) in 304 SS, and B (6.9 ± 0.9) > C (6.7 ± 0.4) > Si (1.5 ± 0.2) in Alloy 690. Cr atoms may co-segregate with C atoms at grain boundaries before carbide nucleation at the grain boundaries both in 304 SS and Alloy 690. Ni atoms generally deplete at grain boundary both in 304 SS and Alloy 690. The literature shows that the Ni atoms may co-segregate with P atoms at grain boundaries [28], but the P atoms segregation do not leads to Ni segregation in the current study. In the current study, Fe atoms may segregate or deplete at grain boundary in Alloy 690. But Fe atoms generally deplete at grain boundary in 304 SS. B atoms have the strongest grain boundary segregation tendency both in 304 SS and Alloy 690. The grain boundary segregation tendency and Gibbs free energy of B in 304 SS is higher than in Alloy 690. C atoms are easy to segregate at grain boundaries both in 304 SS and Alloy 690. The grain boundary segregation tendency and Gibbs free energy of C in Alloy 690 is higher than in 304 SS, due to the higher bulk C concentration and the site competition of P atoms which segregate at grain boundary [29,30]. It is imply that the segregation tendency is influenced by the bulk concentration of the segregates. Si atoms slightly segregate at grain boundaries in Alloy 690, but do not segregate at grain boundaries in 304 SS. N and P atoms segregate at grain boundary in 304 SS, and their segregation Gibbs free energy are similar. N atoms may be exhausted by the TiN precipitated in the matrix and can not be observed in the grain boundary of Alloy 690 [19]. Mn atoms deplete at grain boundary in 304 SS. This phenomenon is similar to that of proton irradiation induced segregation in 304 SS [32]. B, C, N, P segregation Gibbs energies are similar both in 304 SS and Alloy 690. B and C atoms segregate at grain boundary both in Alloy 690 and 304 SS, P and N segregate at grain boundary in 304 SS. Si atoms segregate at grain boundary in Alloy 690, but do not segregate at grain boundary in 304 SS. Cr enriches at grain boundary both in Alloy 690 and 304 SS, although carbide does not nucleate. Ni and Fe may segregate, deplete or homogeneously distribute at grain boundary in Alloy 690, but they deplete at grain boundary in 304 SS. C and Cr atoms co-segregate at grain boundaries before carbide nucleation in Alloy 690 and 304 SS. Combination with other results in literatures, the evolution of Cr concentration at grain boundary should be enrichment at grain boundary before carbide nucleation, depletion at grain boundary after carbide precipitation, and healing after obvious growth of carbide. After aging treatment at 500 °C for 0.5 h, the total reduction of grain boundary free energy due to segregation is 27.489 kJ/mol for Alloy 690 and 45.207 kJ/mol for 304.

Low-temperature direct copper-to-copper bonding enabled by creep on (111) surfaces of nanotwinned Cu

PubMed Central

Liu, Chien-Min; Lin, Han-Wen; Huang, Yi-Sa; Chu, Yi-Cheng; Chen, Chih; Lyu, Dian-Rong; Chen, Kuan-Neng; Tu, King-Ning

2015-01-01

Direct Cu-to-Cu bonding was achieved at temperatures of 150–250 °C using a compressive stress of 100 psi (0.69 MPa) held for 10–60 min at 10−3 torr. The key controlling parameter for direct bonding is rapid surface diffusion on (111) surface of Cu. Instead of using (111) oriented single crystal of Cu, oriented (111) texture of extremely high degree, exceeding 90%, was fabricated using the oriented nano-twin Cu. The bonded interface between two (111) surfaces forms a twist-type grain boundary. If the grain boundary has a low angle, it has a hexagonal network of screw dislocations. Such network image was obtained by plan-view transmission electron microscopy. A simple kinetic model of surface creep is presented; and the calculated and measured time of bonding is in reasonable agreement. PMID:25962757

Microstructural study of the polymorphic transformation in pentacene thin films.

PubMed

Murakami, Yosuke; Tomiya, Shigetaka; Koshitani, Naoki; Kudo, Yoshihiro; Satori, Kotaro; Itabashi, Masao; Kobayashi, Norihito; Nomoto, Kazumasa

2009-10-02

We have observed, by high-resolution cross-sectional transmission electron microscopy, the first direct evidence of polymorphic transformation in pentacene thin films deposited on silicon oxide substrates. Polymorphic transformation from the thin-film phase to the bulk phase occurred preferentially near polycrystalline grain boundaries, which exhibit concave surfaces. This process is thought to be driven by compressive stress caused by the grain boundaries. In addition to this stress, lattice mismatch between the two phases also results in structural defect formation.

Influence of SiC grain boundary character on fission product transport in irradiated TRISO fuel

DOE PAGES

Lillo, T. M.; Rooyen, I. J.

2016-02-26

The relationship between grain boundary character and fission product migration is identified as an important knowledge gap in order to advance the understanding of fission product release from TRISO fuel particles. Precession electron diffraction (PED), a TEM-based technique, was used in this study to quickly and efficiently provide the crystallographic information needed to identify grain boundary misorientation, grain boundary type (low or high angle) and whether the boundary is coincident site lattice (CSL) – related, in irradiated SiC. Analysis of PED data showed the grain structure of the SiC layer in an irradiated TRISO fuel particle from the AGR-1 experimentmore » to be composed mainly of twin boundaries with a small fraction of low angle grain boundaries (<10%). In general, fission products favor precipitation on random, high angle grain boundaries but can precipitate out on low angle and CSL-related grain boundaries to a limited degree. Pd is capable of precipitating out on all types of grain boundaries but most prominently on random, high angle grain boundaries. Pd-U and Pd-Ag precipitates were found on CSL-related as well as random high angle grain boundaries but not on low angle grain boundaries. In contrast, precipitates containing only Ag were found only on random, high angle grain boundaries but not on either low angle or CSL-related grain boundaries.« less

Influence of SiC grain boundary character on fission product transport in irradiated TRISO fuel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lillo, T. M.; Rooyen, I. J.

The relationship between grain boundary character and fission product migration is identified as an important knowledge gap in order to advance the understanding of fission product release from TRISO fuel particles. Precession electron diffraction (PED), a TEM-based technique, was used in this study to quickly and efficiently provide the crystallographic information needed to identify grain boundary misorientation, grain boundary type (low or high angle) and whether the boundary is coincident site lattice (CSL) – related, in irradiated SiC. Analysis of PED data showed the grain structure of the SiC layer in an irradiated TRISO fuel particle from the AGR-1 experimentmore » to be composed mainly of twin boundaries with a small fraction of low angle grain boundaries (<10%). In general, fission products favor precipitation on random, high angle grain boundaries but can precipitate out on low angle and CSL-related grain boundaries to a limited degree. Pd is capable of precipitating out on all types of grain boundaries but most prominently on random, high angle grain boundaries. Pd-U and Pd-Ag precipitates were found on CSL-related as well as random high angle grain boundaries but not on low angle grain boundaries. In contrast, precipitates containing only Ag were found only on random, high angle grain boundaries but not on either low angle or CSL-related grain boundaries.« less

The use of the ion probe mass spectrometer in the measurement of hydrogen concentration gradients in Monel K 500

NASA Technical Reports Server (NTRS)

Truhan, J. J., Jr.; Hehemann, R. F.

1974-01-01

The ion probe mass spectrometer was used to measure hydrogen concentration gradients in cathodically charged Monel K 500. Initial work with the ion probe involved the calibration of the instrument and the establishment of a suitable experimental procedure for this application. Samples of Monel K 500 were cathodically charged in a weak sulfuric acid solution. By varying the current density, different levels of hydrogen were introduced into the samples. Hydrogen concentration gradients were taken by ion sputtering on the surface of these samples and monitoring the behavior of the hydrogen mass peak as a function of time. An attempt was made to determine the relative amounts of hydrogen in the bulk and grain boundaries by analyzing a fresh fracture surface with a higher proportion of grain boundary area. It was found that substantially more hydrogen was detected in the grain boundaries than in the bulk, confirming the predictions of previous workers. A sputter rate determination was made in order to establish the rate of erosion.

An experimental assessment of the size effects on the strength and ductility of freestanding copper films under macroscopically homogenous deformation

NASA Astrophysics Data System (ADS)

Chauhan, Shakti Singh

Metallic interconnects and circuitry has been experiencing excessive deformation beyond their elastic limits in many applications, ranging from micro-electromechanical systems (MEMS) to flexible electronics. These broad applications are creating needs to understand the extent of strength and ductility of freestanding metallic films at scales approaching the micron and sub micron range. This work aims to elucidate the effects of microstructural constraint as well as geometric dimensional constraint on the strength and ductility of freestanding Cu films under uniaxial tension. Two types of films are tested (i) high purity rolled films of 12.5-100microm thickness and average grain sizes of 11-47microm and (ii) electroplated films of 2-50 microm thickness and average grain sizes of 1.8-5microm. Several experimental tools including residual electrical resistivity measurements, surface strain measurements and surface roughness measurements are employed to highlight the underlying deformation mechanisms leading to the observed size effects. With respect to the strength of the specimens, we find that the nature and magnitude of thickness effects is very sensitive to the average grain size. In all cases, coupled thickness and grain size effects were observed. This study shows that this observed coupling, unique to the case of freestanding specimen, arises because the observed size effects are an outcome of the size dependence of two fundamental microstructural parameters i.e. volume fraction of surface grains and grain boundary area per unit specimen volume. For films having thickness and grain sizes greater than 5microm, thickness dependent weakening is observed for a constant grain size. Reducing thickness results in an increase in the volume fraction of grains exposed to the free surface as well as a reduction in the grain boundary area per unit specimen volume. The former effect leads to a reduction in the effective microstructural constraint on the intragranular dislocation activity in individual grains. This free surface related effect is the origin of a weakening contribution to the overall specimen strength with reducing thickness. For specimens with grain sizes ˜ O (10-50microm), this effect was found to be dominating i.e. reducing thickness resulted in reducing strength. A phenomenological model employing the flow strength of surface and bulk grains is proposed to model the observed trends. For films having thickness and grain sizes smaller than 5microm, size dependent strengthening is observed for a constant grain size. At this scale, grain boundary dislocations dominate. As a consequence, thickness effects arise because grain boundary dislocation source density per unit specimen volume reduces with reducing specimen thickness. This statistical reduction in dislocation source density leads to increasing specimen strength via source starvation strengthening. Our results show that such increasing specimen strength with reducing thickness, which has only been observed previously for nanocrystalline thin films, first appears at average grain size of ˜5microm or xx smaller. The measurements showed a characteristic length scale of about 5microm, which defines the size dependent strengthening or weakening of the film. With respect to the thickness effects on ductility, it was found that both thickness and average grain size affect ductility. While prominent thickness effects persist at larger grain sizes, for specimens with grain size approaching 1microm, the loss of strain hardening ability at such fine microstructures dominates and a limiting ductility of ˜2% is seen irrespective of the thickness. The observed thickness effects on ductility were investigated via surface roughness measurements that allow the characterization of initiation and evolution of deformation heterogeneities. It was found that thickness has a strong influence on the characteristic heterogeneity of deformation. At small specimen thicknesses, the deformation was found to be highly localized i.e. widely spaced regions showing substantial thickness reduction, hence increasing the vulnerability to the onset of plastic instabilities. At larger thicknesses, however, the increasing microstructural constraint delocalizes the strain and thereby precludes the early onset of instability, leading to enhanced ductility.

The relationship between structure and magnetic properties in ultra-fine grained/nanostructured FePd alloys

NASA Astrophysics Data System (ADS)

Okumura, Hideyuki

In this study, the magnetic behavior including coercivity and the magnetic phase transition (ferromagnetic ↔ paramagnetic) and related phenomena were qualitatively and quantitatively investigated in ultra-fine grained/nanostructured FePd permanent magnet alloys, in relation to the microstructure and defect structure, and the results were compared with bulk FePd. Most of the alloy specimens investigated were in the form of epoxybonded magnets or isostatically-pressed pellets, formed from powders which were produced with high energy ball milling. Some results of thin films and ribbons produced with sputtering and melt-spinning, respectively, are also included in this thesis. Characterization of the materials was performed by using X-ray diffraction techniques with texture measurement, transmission electron microscopy with Lorentz microscopy, scanning electron microscopy with EDS analysis, optical microscopy and vibrating sample magnetometry. X-ray line broadening analysis was utilized for the quantitative characterization of the nanoscale microstructure, and it was found that the Cauchy-Gaussian profile assumption best describes the broadening data. Enhanced coercivities ˜10 times those of the bulk FePd obtained using conventional heat treatments were explained as the result of statistical (stochastic) unpinning of interaction domain walls out of the potential well at the grain boundary, and there is also an additional effect ascribed to an increase of the magnetocrystalline anisotropy, which is mainly due to the metastable c/a ratio of the nanostructured ordered phase and possibly to stress anisotropy. At the same time, there is also a decrease of the coercivity for smaller grain sizes because of the "magnetically soft" grain boundary phase. A semi-quantitative theoretical model is proposed, which includes the effect of exchange coupling between the ordered grains. The so-called Kronmuller analysis based on the wall pinning model was self-consistent, supporting the notion that wall pinning by grain boundary is the dominant mechanism controlling the coercivity in the nanostructured aggregates in which the magnetic structure is comprised of interaction domains. Furthermore, conventionally structure-insensitive, intrinsic properties such as the saturation magnetization and Curie temperature were found to become structure-sensitive in these materials. The results were semi-quantitatively explained by consideration of the extraordinary microstructure and defect structure involving the high and complex strain fields, metastable tetragonalities, nonequilibrium grain boundaries, extremely high surface-to-volume ratios and perturbed coordination spheres. The possible change in the atomic bond character particularly around grain boundaries is also briefly discussed. It seems that there is a significant fluctuation in exchange couplings at the grain boundary volume, causing the variation of the saturation magnetization, while for the variation of the Curie temperature the powder surface instead of the grain boundary is more important. A modified localized moment model and thus Hund's rules seem applicable to the FePd alloy systems, and the spin density fluctuations seem small in the FePd alloys.

Effects of microstructural variation on Charpy impact properties in heavy-section Mn-Mo-Ni low alloy steel for reactor pressure vessel

NASA Astrophysics Data System (ADS)

Hong, Seokmin; Song, Jaemin; Kim, Min-Chul; Choi, Kwon-Jae; Lee, Bong-Sang

2016-03-01

The effects of microstructural changes in heavy-section Mn-Mo-Ni low alloy steel on Charpy impact properties were investigated using a 210 mm thick reactor pressure vessel. Specimens were sampled from 5 different positions at intervals of 1/4 thickness from the inner surface to the outer surface. A detailed microstructural analysis of impact-fractured specimens showed that coarse carbides along the lath boundaries acted as fracture initiation sites, and cleavage cracks deviated at prior-austenite grain boundaries and bainite lath boundaries. Upper shelf energy was higher and energy transition temperature was lower at the surface positon, where fine bainitic microstructure with homogeneously distributed fine carbides were present. Toward the center, coarse upper bainite and precipitation of coarse inter-lath carbides were observed, which deteriorated impact properties. At the 1/4T position, the Charpy impact properties were worse than those at other positions owing to the combination of elongated-coarse inter-lath carbides and large effective grain size.

Irradiation-induced grain growth and defect evolution in nanocrystalline zirconia with doped grain boundaries

DOE PAGES

Dey, Sanchita; Mardinly, John; Wang, Yongqiang; ...

2016-05-27

Grain boundaries are effective sinks for radiation-induced defects, ultimately impacting the radiation tolerance of nanocrystalline materials (dense materials with nanosized grains) against net defect accumulation. However, irradiation-induced grain growth leads to grain boundary area decrease, shortening potential benefits of nanostructures. A possible approach to mitigate this is the introduction of dopants to target a decrease in grain boundary mobility or a reduction in grain boundary energy to eliminate driving forces for grain growth (using similar strategies as to control thermal growth). Here, in this study, we tested this concept in nanocrystalline zirconia doped with lanthanum. Although the dopant is observedmore » to segregate to the grain boundaries, causing grain boundary energy decrease and promoting dragging forces for thermally activated boundary movement, irradiation induced grain growth could not be avoided under heavy ion irradiation, suggesting a different growth mechanism as compared to thermal growth. Furthermore, it is apparent that reducing the grain boundary energy reduced the effectiveness of the grain boundary as sinks, and the number of defects in the doped material is higher than in undoped (La-free) YSZ.« less

A kinetic model for stress generation in thin films grown from energetic vapor fluxes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chason, E.; Karlson, M.; Colin, J. J.

We have developed a kinetic model for residual stress generation in thin films grown from energetic vapor fluxes, encountered, e.g., during sputter deposition. The new analytical model considers sub-surface point defects created by atomic peening, along with processes treated in already existing stress models for non-energetic deposition, i.e., thermally activated diffusion processes at the surface and the grain boundary. According to the new model, ballistically induced sub-surface defects can get incorporated as excess atoms at the grain boundary, remain trapped in the bulk, or annihilate at the free surface, resulting in a complex dependence of the steady-state stress on themore » grain size, the growth rate, as well as the energetics of the incoming particle flux. We compare calculations from the model with in situ stress measurements performed on a series of Mo films sputter-deposited at different conditions and having different grain sizes. The model is able to reproduce the observed increase of compressive stress with increasing growth rate, behavior that is the opposite of what is typically seen under non-energetic growth conditions. On a grander scale, this study is a step towards obtaining a comprehensive understanding of stress generation and evolution in vapor deposited polycrystalline thin films.« less

Improve sensitization and corrosion resistance of an Al-Mg alloy by optimization of grain boundaries

NASA Astrophysics Data System (ADS)

Yan, Jianfeng; Heckman, Nathan M.; Velasco, Leonardo; Hodge, Andrea M.

2016-05-01

The sensitization and subsequent intergranular corrosion of Al-5.3 wt.% Mg alloy has been shown to be an important factor in stress corrosion cracking of Al-Mg alloys. Understanding sensitization requires the review of grain boundary character on the precipitation process which can assist in developing and designing alloys with improved corrosion resistance. This study shows that the degree of precipitation in Al-Mg alloy is dependent on grain boundary misorientation angle, adjacent grain boundary planes and grain boundary types. The results show that the misorientation angle is the most important factor influencing precipitation in grain boundaries of the Al-Mg alloy. Low angle grain boundaries (≤15°) have better immunity to precipitation and grain boundary acid attack. High angle grain boundaries (>15°) are vulnerable to grain boundary acid attack. Grain boundaries with adjacent plane orientations near to {100} have potential for immunity to precipitation and grain boundary acid attack. This work shows that low Σ (Σ ≤ 29) coincident site lattice (CSL) grain boundaries have thinner β precipitates. Modified nitric acid mass loss test and polarization test demonstrated that the global corrosion resistance of sputtered Al-Mg alloy is enhanced. This may be attributed to the increased fractions of low Σ (Σ ≤ 29) CSL grain boundaries after sputtering.

Erosion of phosphor bronze under cavitation attack in a mineral oil

NASA Technical Reports Server (NTRS)

Rao, B. C. S.; Buckley, D. H.

1986-01-01

Experimental investigations on erosion of a copper alloy, phosphor bronze, under cavitation attack in a viscous mineral oil are presented. The details of pit formation and erosion were studied using scanning electron microscopy. The mean depth of penetration, the variations in surface roughness, and the changes in erosion pit size were studied. Cavitation pits formed initially over the grain boundaries while the surface grains were plastically deformed. Erosion of surface grains occurred largely by ductile fracture involving microcracking and removal in layers. The ratio h/a of the depth h to half width a of cavitation pits increased with test duration from 0.047 to 0.55.

Pressure-induced transition in the grain boundary of diamond

NASA Astrophysics Data System (ADS)

Chen, J.; Tang, L.; Ma, C.; Fan, D.; Yang, B.; Chu, Q.; Yang, W.

2017-12-01

Equation of state of diamond powder with different average grain sizes was investigated using in situ synchrotron x-ray diffraction and a diamond anvil cell (DAC). Comparison of compression curves was made for two samples with average grain size of 50nm and 100nm. The two specimens were pre-pressed into pellets and loaded in the sample pressure chamber of the DAC separately to minimized differences of possible systematic errors for the two samples. Neon gas was used as pressure medium and ruby spheres as pressure calibrant. Experiments were conducted at room temperature and high pressures up to 50 GPa. Fitting the compression data in the full pressure range into the third order Birch-Murnaghan equation of state yields bulk modulus (K) and its pressure derivative (K') of 392 GPa and 5.3 for 50nm sample and 398GPa and 4.5 for 100nm sample respectively. Using a simplified core-shell grain model, this result indicates that the grain boundary has an effective bulk modulus of 54 GPa. This value is similar to that observed for carbon nanotube[1] validating the recent theoretical diamond surface modeling[2]. Differential analysis of the compression cures demonstrates clear relative compressibility change at the pressure about 20 GPa. When fit the compression data below and above this pressure separately, the effect of grain size on bulk modulus reverses in the pressure range above 20 GPa. This observation indicates a possible transition of grain boundary structure, likely from sp2 hybridization at the surface[2] towards sp3like orbital structure which behaves alike the inner crystal. [1] Jie Tang, Lu-Chang Qin, Taizo Sasaki, Masako Yudasaka, Akiyuki Matsushita, and Sumio Iijima, Compressibility and Polygonization of Single-Walled Carbon Nanotubes under Hydrostatic Pressure, Physical Review Letters, 85(9), 1187-1198, 2000. [2] Shaohua Lu, Yanchao Wang, Hanyu Liu, Mao-sheng Miao, and Yanming Ma, Self-assembled ultrathin nanotubes on diamond (100) surface, Nature Communications, DOI: 10.1038/ncomms4666, 2014

Trapping charges at grain boundaries and degradation of CH3NH3Pb(I1-x Br x )3 perovskite solar cells.

PubMed

Nguyen, Bich Phuong; Kim, Gee Yeong; Jo, William; Kim, Byeong Jo; Jung, Hyun Suk

2017-08-04

The electrical properties of CH 3 NH 3 Pb(I 1-x Br x ) 3 (x = 0.13) perovskite materials were investigated under ambient conditions. The local work function and the local current were measured using Kelvin probe force microscopy and conductive atomic force microscopy, respectively. The degradation of the perovskite layers depends on their grain size. As the material degrades, an additional peak in the surface potential appears simultaneously with a sudden increase and subsequent relaxation of the local current. The potential bending at the grain boundaries and the intragrains is the most likely reason for the change of the local current surface of the perovskite layers. The improved understanding of the degradation mechanism garnered from this study helps pave the way toward an improved photo-conversion efficiency in perovskite solar cells.

Trapping charges at grain boundaries and degradation of CH3NH3Pb(I1-x Br x )3 perovskite solar cells

NASA Astrophysics Data System (ADS)

Phuong Nguyen, Bich; Kim, Gee Yeong; Jo, William; Kim, Byeong Jo; Jung, Hyun Suk

2017-08-01

The electrical properties of CH3NH3Pb(I1-x Br x )3 (x = 0.13) perovskite materials were investigated under ambient conditions. The local work function and the local current were measured using Kelvin probe force microscopy and conductive atomic force microscopy, respectively. The degradation of the perovskite layers depends on their grain size. As the material degrades, an additional peak in the surface potential appears simultaneously with a sudden increase and subsequent relaxation of the local current. The potential bending at the grain boundaries and the intragrains is the most likely reason for the change of the local current surface of the perovskite layers. The improved understanding of the degradation mechanism garnered from this study helps pave the way toward an improved photo-conversion efficiency in perovskite solar cells.

Methylammonium lead iodide grain boundaries exhibit depth-dependent electrical properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

MacDonald, Gordon A.; Yang, Mengjin; Berweger, Samuel

In this paper, the nanoscale through-film and lateral photo-response and conductivity of large-grained methylammonium lead iodide (MAPbI 3) thin films are studied. In perovskite solar cells (PSC), these films result in efficiencies >17%. The grain boundaries (GBs) show high resistance at the top surface of the film, and act as an impediment to photocurrent collection. However, lower resistance pathways between grains exist below the top surface of the film, indicating that there exists a depth-dependent resistance of GBs (R GB(z)). Furthermore, lateral conductivity measurements indicate that R GB(z) exhibits GB-to-GB heterogeneity. These results indicate that increased photocurrent collection along GBsmore » is not a prerequisite for high-efficiency PSCs. Rather, better control of depth-dependent GB electrical properties, and an improvement in the homogeneity of the GB-to-GB electrical properties, must be managed to enable further improvements in PSC efficiency. Finally, these results refute the implicit assumption seen in the literature that the electrical properties of GBs, as measured at the top surface of the perovskite film, necessarily reflect the electrical properties of GBs within the thickness of the film.« less

Nanoscale imaging of photocurrent and efficiency in CdTe solar cells

DOE PAGES

Leite, Marina S.; National Inst. of Standards and Technology; Abashin, Maxim; ...

2014-10-15

The local collection characteristics of grain interiors and grain boundaries in thin film CdTe polycrystalline solar cells are investigated using scanning photocurrent microscopy. The carriers are locally generated by light injected through a small aperture (50-300 nm) of a near-field scanning optical microscope in an illumination mode. Possible influence of rough surface topography on light coupling is examined and eliminated by sculpting smooth wedges on the granular CdTe surface. By varying the wavelength of light, nanoscale spatial variations in external quantum efficiency are mapped. We find that the grain boundaries (GBs) are better current collectors than the grain interiors (GIs).more » The increased collection efficiency is caused by two distinct effects associated with the material composition of GBs. First, GBs are charged, and the corresponding built-in field facilitates the separation and the extraction of the photogenerated carriers. Second, the GB regions generate more photocurrent at long wavelength corresponding to the band edge, which can be caused by a smaller local band gap. As a result, resolving carrier collection with nanoscale resolution in solar cell materials is crucial for optimizing the polycrystalline device performance through appropriate thermal processing and passivation of defect and surfaces.« less

Methylammonium lead iodide grain boundaries exhibit depth-dependent electrical properties

DOE PAGES

MacDonald, Gordon A.; Yang, Mengjin; Berweger, Samuel; ...

2016-09-23

In this paper, the nanoscale through-film and lateral photo-response and conductivity of large-grained methylammonium lead iodide (MAPbI 3) thin films are studied. In perovskite solar cells (PSC), these films result in efficiencies >17%. The grain boundaries (GBs) show high resistance at the top surface of the film, and act as an impediment to photocurrent collection. However, lower resistance pathways between grains exist below the top surface of the film, indicating that there exists a depth-dependent resistance of GBs (R GB(z)). Furthermore, lateral conductivity measurements indicate that R GB(z) exhibits GB-to-GB heterogeneity. These results indicate that increased photocurrent collection along GBsmore » is not a prerequisite for high-efficiency PSCs. Rather, better control of depth-dependent GB electrical properties, and an improvement in the homogeneity of the GB-to-GB electrical properties, must be managed to enable further improvements in PSC efficiency. Finally, these results refute the implicit assumption seen in the literature that the electrical properties of GBs, as measured at the top surface of the perovskite film, necessarily reflect the electrical properties of GBs within the thickness of the film.« less

Meso-scale anisotropic hydrogen segregation near grain-boundaries in polycrystalline nickel characterized by EBSD/SIMS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oudriss, A.; Le Guernic, Solenne; Wang, Zhaoying

2016-02-15

To study anisotropic hydrogen segregation and diffusion in nickel polycrystalline, Secondary Ion Mass Spectrometry (SIMS) and Electron Back Scattered Diffraction (EBSD) are integrated to investigate hydrogen distribution around grain boundaries. Hydrogen distribution in pre-charged samples were correlated with grain boundary character by integrating high-resolution grain microstructure from EBSD inverse pole figure map and low-resolution hydrogen concentration profile map from SIMS. This multimodal imaging instrumentation shows that grain boundaries in nickel can be categorized into two families based on behavior of hydrogen distribution crossing grain boundary: the first one includes random grain boundaries with fast hydrogen diffusivity, showing a sharp gapmore » for hydrogen concentration profile cross the grain boundaries. The second family are special Σ3n grain boundaries with low hydrogen diffusivity, showing a smooth gradient of hydrogen concentration cross the grain boundary. Heterogeneous hydrogen distributions due to grain boundary family revealed by SIMS/EBSD on mesoscale further validate the recent hydrogen permeation data and anisotropic ab-initio calculations in nanoscale. The results highlight the fact that grain boundaries character impacts hydrogen distribution significantly.« less

Atomic level characterization in corrosion studies

NASA Astrophysics Data System (ADS)

Marcus, Philippe; Maurice, Vincent

2017-06-01

Atomic level characterization brings fundamental insight into the mechanisms of self-protection against corrosion of metals and alloys by oxide passive films and into how localized corrosion is initiated on passivated metal surfaces. This is illustrated in this overview with selected data obtained at the subnanometre, i.e. atomic or molecular, scale and also at the nanometre scale on single-crystal copper, nickel, chromium and stainless steel surfaces passivated in well-controlled conditions and analysed in situ and/or ex situ by scanning tunnelling microscopy/spectroscopy and atomic force microscopy. A selected example of corrosion modelling by ab initio density functional theory is also presented. The discussed aspects include the surface reconstruction induced by hydroxide adsorption and formation of two-dimensional (hydr)oxide precursors, the atomic structure, orientation and surface hydroxylation of three-dimensional ultrathin oxide passive films, the effect of grain boundaries in polycrystalline passive films acting as preferential sites of passivity breakdown, the differences in local electronic properties measured at grain boundaries of passive films and the role of step edges at the exposed surface of oxide grains on the dissolution of the passive film. This article is part of the themed issue 'The challenges of hydrogen and metals'.

A Compendium of Scale Surface Microstructures: Ni(pt)al Coatings Oxidized at 1150 C for 2000 1-h Cycles

NASA Technical Reports Server (NTRS)

Smialek, James L.; Garg, Anita

2010-01-01

The surface structure of scales formed on Ni(Pt)Al coatings was characterized by SEM/EDS/BSE in plan view. Two nominally identical {100} samples of aluminide coated CMSX4 single crystal were oxidized at 1150 C for 2000 1-h cycles and were found to produce somewhat disparate behavior. One sample, with less propensity for coating grain boundary ridge deformation, presented primarily alpha-Al2O3 scale structures, with minimal weight loss and spallation. The original scale structure, still retained over most of the sample, consisted of the classic theta-alpha transformation-induced ridge network structure, with approx. 25 nm crystallographic steps and terraces indicative of surface rearrangement to low energy alumina planes. The scale grain boundary ridges were often decorated with a fine, uniform distribution of (Hf,Ti)O2 particles. Another sample, producing steady state weight losses, exhibited much interfacial spallation and a complex assortment of different structures. Broad areas of interfacial spalling, crystallographically-faceted (Ni,Co)(Al,Cr)2O4 spinel, with an alpha-Al2O3 base scale, were the dominant features. Other regions exhibited nodular spinel grains, with fine or (Ta,Ti)-rich (rutile) particles decorating or interspersed with the spinel. While these features were consistent with a coating that presented more deformation at extruded grain boundaries, the root cause of the different behavior between the duplicate samples could not be conclusively identified.

Effects of oxide distributed in grain boundaries on microstructure stability of nanocrystalline metals

NASA Astrophysics Data System (ADS)

Zhou, Kai; Li, Hui; Biao Pang, Jin; Wang, Zhu

2013-06-01

Nanocrystalline copper and zinc prepared by high-pressure compaction method have been studied by positron lifetime spectroscopy associated with X-ray diffraction. For nanocrystalline Cu, mean grain sizes of the samples decrease after being annealed at 900 °C and increase during aging at 180 °C, revealing that the atoms exchange between the two regions. The positron lifetime results indicate that the vacancy clusters formed in the annealing process are unstable and decomposed at the aging time below 6 hours. In addition, the partially oxidized surfaces of the nanoparticles hinder the grain growth during the ageing at 180 °C, and the vacancy clusters inside the disorder regions which are related to Cu2O need longer aging time to decompose. In the case of nanocrystalline Zn, the open volume defect (not larger than divacancy) is dominant according to the high relative intensity for the short positron lifetime (τ1). The oxide (ZnO) inside the grain boundaries has been found having an effect to hinder the decrease of average positron lifetime (τav) during the annealing, which probably indicates that the oxide stabilizes the microstructure of the grain boundaries. For both nanocrystalline copper and zinc, the oxides in grain boundaries enhance the thermal stability of the microstucture, in spite of their different crystal structures. This effect is very important for the nanocrystalline materials using as radiation resistant materials.

Effects of film growth kinetics on grain coarsening and grain shape.

PubMed

Reis, F D A Aarão

2017-04-01

We study models of grain nucleation and coarsening during the deposition of a thin film using numerical simulations and scaling approaches. The incorporation of new particles in the film is determined by lattice growth models in three different universality classes, with no effect of the grain structure. The first model of grain coarsening is similar to that proposed by Saito and Omura [Phys. Rev. E 84, 021601 (2011)PLEEE81539-375510.1103/PhysRevE.84.021601], in which nucleation occurs only at the substrate, and the grain boundary evolution at the film surface is determined by a probabilistic competition of neighboring grains. The surface grain density has a power-law decay, with an exponent related to the dynamical exponent of the underlying growth kinetics, and the average radius of gyration scales with the film thickness with the same exponent. This model is extended by allowing nucleation of new grains during the deposition, with constant but small rates. The surface grain density crosses over from the initial power law decay to a saturation; at the crossover, the time, grain mass, and surface grain density are estimated as a function of the nucleation rate. The distributions of grain mass, height, and radius of gyration show remarkable power law decays, similar to other systems with coarsening and particle injection, with exponents also related to the dynamical exponent. The scaling of the radius of gyration with the height h relative to the base of the grain show clearly different exponents in growth dominated by surface tension and growth dominated by surface diffusion; thus it may be interesting for investigating the effects of kinetic roughening on grain morphology. In growth dominated by surface diffusion, the increase of grain size with temperature is observed.

Phase-field model with plastic flow for grain growth in nanocrystalline material

NASA Astrophysics Data System (ADS)

Steinbach, Ingo; Song, Xiaoyan; Hartmaier, Alexander

2010-01-01

A phase-field model is presented which considers the accumulation of structural defects in grain boundaries by an isotropic eigenstrain associated with the grain boundaries. It is demonstrated that the elastic energy caused by dilatation of the grain boundary with respect to the bulk crystal contributes largely to the grain boundary energy. The sign of this contribution can be both positive and negative dependent on the local stress state in the grain boundary. Self-diffusion of atoms is taken into account to relax the stress caused by the dilatation of the grain boundary. Application of the model to discontinuous grain growth in pure nanocrystalline cobalt material is presented. Linear grain growth is found in the nanocrystalline state, which is explained by the interpretation of grain boundary motion as a diffusive process defining an upper limit of the grain boundary velocity independent of the grain boundary curvature but dependent on temperature. The transition to regular grain growth at a critical temperature, as observed experimentally, is explained by the drop of theoretical grain boundary velocity due to its mean curvature during coarsening of the nanograin structure below the maximum velocity.

The Effects of Grain Size and Texture on Dynamic Abnormal Grain Growth in Mo

NASA Astrophysics Data System (ADS)

Noell, Philip J.; Taleff, Eric M.

2016-10-01

This is the first report of abnormal grain morphologies specific to a Mo sheet material produced from a commercial-purity arc-melted ingot. Abnormal grains initiated and grew during plastic deformation of this material at temperatures of 1793 K and 1813 K (1520 °C and 1540 °C). This abnormal grain growth during high-temperature plastic deformation is termed dynamic abnormal grain growth, DAGG. DAGG in this material readily consumes nearly all grains near the sheet center while leaving many grains near the sheet surface unconsumed. Crystallographic texture, grain size, and other microstructural features are characterized. After recrystallization, a significant through-thickness variation in crystallographic texture exists in this material but does not appear to directly influence DAGG propagation. Instead, dynamic normal grain growth, which may be influenced by texture, preferentially occurs near the sheet surface prior to DAGG. The large grains thus produced near the sheet surface inhibit the subsequent growth of the abnormal grains produced by DAGG, which preferentially consume the finer grains near the sheet center. This produces abnormal grains that span the sheet center but leave unconsumed polycrystalline microstructure near the sheet surface. Abnormal grains are preferentially oriented with the < 110rangle approximately along the tensile axis. These results provide additional new evidence that boundary curvature is the primary driving force for DAGG in Mo.

Structural and electrical properties of conducting diamond nanowires.

PubMed

Sankaran, Kamatchi Jothiramalingam; Lin, Yen-Fu; Jian, Wen-Bin; Chen, Huang-Chin; Panda, Kalpataru; Sundaravel, Balakrishnan; Dong, Chung-Li; Tai, Nyan-Hwa; Lin, I-Nan

2013-02-01

Conducting diamond nanowires (DNWs) films have been synthesized by N₂-based microwave plasma enhanced chemical vapor deposition. The incorporation of nitrogen into DNWs films is examined by C 1s X-ray photoemission spectroscopy and morphology of DNWs is discerned using field-emission scanning electron microscopy and transmission electron microscopy (TEM). The electron diffraction pattern, the visible-Raman spectroscopy, and the near-edge X-ray absorption fine structure spectroscopy display the coexistence of sp³ diamond and sp² graphitic phases in DNWs films. In addition, the microstructure investigation, carried out by high-resolution TEM with Fourier transformed pattern, indicates diamond grains and graphitic grain boundaries on surface of DNWs. The same result is confirmed by scanning tunneling microscopy and scanning tunneling spectroscopy (STS). Furthermore, the STS spectra of current-voltage curves discover a high tunneling current at the position near the graphitic grain boundaries. These highly conducting regimes of grain boundaries form effective electron paths and its transport mechanism is explained by the three-dimensional (3D) Mott's variable range hopping in a wide temperature from 300 to 20 K. Interestingly, this specific feature of high conducting grain boundaries of DNWs demonstrates a high efficiency in field emission and pave a way to the next generation of high-definition flat panel displays or plasma devices.

Formation of intra-island grain boundaries in pentacene monolayers.

PubMed

Zhang, Jian; Wu, Yu; Duhm, Steffen; Rabe, Jürgen P; Rudolf, Petra; Koch, Norbert

2011-12-21

To assess the formation of intra-island grain boundaries during the early stages of pentacene film growth, we studied sub-monolayers of pentacene on pristine silicon oxide and silicon oxide with high pinning centre density (induced by UV/O(3) treatment). We investigated the influence of the kinetic energy of the impinging molecules on the sub-monolayer growth by comparing organic molecular beam deposition (OMBD) and supersonic molecular beam deposition (SuMBD). For pentacene films fabricated by OMBD, higher pentacene island-density and higher polycrystalline island density were observed on UV/O(3)-treated silicon oxide as compared to pristine silicon oxide. Pentacene films deposited by SuMBD exhibited about one order of magnitude lower island- and polycrystalline island densities compared to OMBD, on both types of substrates. Our results suggest that polycrystalline growth of single islands on amorphous silicon oxide is facilitated by structural/chemical surface pinning centres, which act as nucleation centres for multiple grain formation in a single island. Furthermore, the overall lower intra-island grain boundary density in pentacene films fabricated by SuMBD reduces the number of charge carrier trapping sites specific to grain boundaries and should thus help achieving higher charge carrier mobilities, which are advantageous for their use in organic thin-film transistors.

Formation of Graphene Grain Boundaries on Cu(100) Surface and a Route Towards Their Elimination in Chemical Vapor Deposition Growth

NASA Astrophysics Data System (ADS)

Yuan, Qinghong; Song, Guangyao; Sun, Deyan; Ding, Feng

2014-10-01

Grain boundaries (GBs) in graphene prepared by chemical vapor deposition (CVD) greatly degrade the electrical and mechanical properties of graphene and thus hinder the applications of graphene in electronic devices. The seamless stitching of graphene flakes can avoid GBs, wherein the identical orientation of graphene domain is required. In this letter, the graphene orientation on one of the most used catalyst surface -- Cu(100) surface, is explored by density functional theory (DFT) calculations. Our calculation demonstrates that a zigzag edged hexagonal graphene domain on a Cu(100) surface has two equivalent energetically preferred orientations, which are 30 degree away from each other. Therefore, the fusion of graphene domains on Cu(100) surface during CVD growth will inevitably lead to densely distributed GBs in the synthesized graphene. Aiming to solve this problem, a simple route, that applies external strain to break the symmetry of the Cu(100) surface, was proposed and proved efficient.

The Role of Grain Boundary Energy on Grain Boundary Complexion Transitions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bojarski, Stephanie A.; Rohrer, Gregory S.

Grain boundary complexions are distinct equilibrium structures and compositions of a grain boundary and complexion transformations are transition from a metastable to an equilibrium complexion at a specific thermodynamic and geometric conditions. Previous work indicates that, in the case of doped alumina, a complexion transition that increased the mobility of transformed boundaries and resulted in abnormal grain growth also caused a decrease in the mean relative grain boundary energy as well as an increase in the anisotropy of the grain boundary character distribution (GBCD). The current work will investigate the hypothesis that the rates of complexion transitions that result inmore » abnormal grain growth (AGG) depend on grain boundary character and energy. Furthermore, the current work expands upon this understanding and tests the hypothesis that it is possible to control when and where a complexion transition occurs by controlling the local grain boundary energy distribution.« less

SILICON CARBIDE GRAIN BOUNDARY DISTRIBUTIONS, IRRADIATION CONDITIONS, AND SILVER RETENTION IN IRRADIATED AGR-1 TRISO FUEL PARTICLES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lillo, T. M.; Rooyen, I. J.; Aguiar, J. A.

Precession electron diffraction in the transmission electron microscope was used to map grain orientation and ultimately determine grain boundary misorientation angle distributions, relative fractions of grain boundary types (random high angle, low angle or coincident site lattice (CSL)-related boundaries) and the distributions of CSL-related grain boundaries in the SiC layer of irradiated TRISO-coated fuel particles. Two particles from the AGR-1 experiment exhibiting high Ag-110m retention (>80%) were compared to a particle exhibiting low Ag-110m retention (<19%). Irradiated particles with high Ag-110m retention exhibited a lower fraction of random, high angle grain boundaries compared to the low Ag-110m retention particle. Anmore » inverse relationship between the random, high angle grain boundary fraction and Ag-110m retention is found and is consistent with grain boundary percolation theory. Also, comparison of the grain boundary distributions with previously reported unirradiated grain boundary distributions, based on SEM-based EBSD for similarly fabricated particles, showed only small differences, i.e. a greater low angle grain boundary fraction in unirradiated SiC. It was, thus, concluded that SiC layers with grain boundary distributions susceptible to Ag-110m release were present prior to irradiation. Finally, irradiation parameters were found to have little effect on the association of fission product precipitates with specific grain boundary types.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Hak-Sung, E-mail: hslee@kims.re.kr; Park, Chanbum; Oh, Chang-Seok

Highlights: • We model the sample grain boundary of LiCoO2, one of important Li cathode materials. • Rigid body translation was found the asymmetric GB is more stable than symmetric GB. • The vacancy formation energy of Li and O was estimated with first principles calculations. • This model boundary can help to find a new dopant to improve Li diffusions. - Abstract: An atomic structure of LiCoO{sub 2} model grain boundary, Σ2 [1120](1102), is introduced and grain boundary energies with rigid body translations are investigated systematically to find the most stable interface structures. It is found that the coordinatedmore » structures of Co and O in the vicinity of grain boundary are strongly related to grain boundary energy. Examining nonstoichiometry at grain boundary, the defect energetics of Li and O site at grain boundary are estimated. In addition, the effect of grain boundary on Li diffusion is investigated to calculate Li diffusion across grain boundary.« less

Microscopic Distributions of Defect Luminescence From Subgrain Boundaries in Multicrystalline Silicon Wafers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, Hieu T.; Jensen, Mallory A.; Li, Li

We investigate the microscopic distributions of sub-band-gap luminescence emission (the so-called D-lines D1/D2/D3/D4) and the band-to-band luminescence intensity, near recombination-active sub-grain boundaries in multicrystalline silicon wafers for solar cells. We find that the sub-band-gap luminescence from decorating defects/impurities (D1/D2) and from intrinsic dislocations (D3/D4) have distinctly different spatial distributions, and are asymmetric across the sub-grain boundaries. The presence of D1/D2 is correlated with a strong reduction in the band-to-band luminescence, indicating a higher recombination activity. In contrast, D3/D4 emissions are not strongly correlated with the band-to-band intensity. Based on spatially-resolved, synchrotron-based micro-X-ray fluorescence measurements of metal impurities, we confirm thatmore » high densities of metal impurities are present at locations with strong D1/D2 emission but low D3/D4 emission. Finally, we show that the observed asymmetry of the sub-band-gap luminescence across the sub-grain boundaries is due to their inclination below the wafer surface. Based on the luminescence asymmetries, the sub-grain boundaries are shown to share a common inclination locally, rather than be orientated randomly.« less

Nanometer-Scale Force Detected Nuclear Magnetic Resonance Imaging

DTIC Science & Technology

2013-01-01

different crystallographic orientation. Single crystal thin films should thus minimize the stray electric fields by reducing the number of grain ...from epitaxial Ag films, rather than polycrystalline Ag films. It is thought that grain boundaries in polycrystalline metal films give rise to stray...electric fields near the surface of the film. The electric fields are produced as a consequence of the work func- tion difference between grains of

BaFe2As2/Fe Bilayers with [001]-tilt Grain Boundary on MgO and SrTiO3 Bicrystal Substrates

NASA Astrophysics Data System (ADS)

Iida, K.; Haindl, S.; Kurth, F.; Hänisch, J.; Schulz, L.; Holzapfel, B.

Co-doped BaFe2As2 (Ba-122) can be realized on both MgO and SrTiO3 bicrystal substrates with [001]-tilt grain boundary by employing Fe buffer layers. However, an additional spinel (i.e. MgAl2O4) buffer between Fe and SrTiO3 is necessary since an epitaxial, smooth surface of Fe layer can not be grown on bare SrTiO3. Both types of bicrystal films show good crystalline quality.

Friction stir welded AM50 and AZ31 Mg alloys: Microstructural evolution and improved corrosion resistance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Templeman, Yael

One of the major drawbacks of Mg alloys is poor weldability, caused by porosity formation during conventional fusion welding processes. Friction Stir Welding (FSW) is promising technique in this context since it is a solid state technique. Contradicting results were published in the literature regarding the FSWed Mg alloys joint's properties. Current research was performed in order to investigate the microstructure and corrosion properties of FSWed Mg alloys, studying representatives of two commercial families: wrought AZ31-H24 and die cast AM50. It was found that in both alloys recrystallization occurred during the FSW. In AM50 the mechanism of the recrystallization wasmore » continuous, manifested by dislocation rearrangement into sub grain boundaries. In AZ31 discontinuous recrystallization had occurred through grain boundaries migration - twins rotated with respect to the matrix, turning into low angle grain boundaries. Corrosion resistance has improved during the FSW in both alloys to different extents. In the AM50 alloy, the nugget exhibited significantly higher surface potential than the base metal mainly due to the higher Al concentration in the matrix of the nugget, resulting from the dissolution of Al-enrichment and β-Mg{sub 17}Al{sub 12} phase. In the AZ31 alloy, no change in Al concentration had occurred, and the surface potential measured in the nugget was only slightly higher than in the base metal. These results underline the appropriateness of the FSW for Mg alloys since during the conventional welding deterioration of the corrosion resistance occurs. - Highlights: • Following FSW, AZ31-H24 experienced discontinuous recrystallization. • In AZ31 grain boundaries migration occurred, thus twins rotated. • In die cast AM50 continuous recrystallization occurred during the FSW. • In AM50 - dislocations rearranged into sub grain boundaries. • Corrosion resistance has improved during the FSW in both alloys to different extent.« less

Oxidation products of Inconel alloys 600 and 690 in hydrogenated steam environments and their role in stress corrosion cracking

NASA Astrophysics Data System (ADS)

Ferguson, J. Bryce

Inconel Alloys 600 and 690 are used extensively in components of Nuclear Pressurized Water Reactors (PWR) in the primary water loop which consists of H2 supersaturated steam. Alloy 600 has been found to crack intergranularly when exposed to primary water conditions. Alloy 690 was designed as a replacement and is generally regarded as immune to cracking. There is no consensus as to the mechanism which is responsible for cracking or the lack thereof in these alloys. In this work thermodynamic arguments for the stability of Ni and Cr compounds developed under pressurized water reactor environments ( PH2O and PH2 ) were experimentally tested. A mechanism is proposed to explain crack initiation and propagation alloy 600 along the grain boundaries where Cr2O3 has formed from the leaching of Cr from the matrix leaving behind a porous Ni-rich region. The mechanism is based on the thermodynamic potential for the transformation of a protective NiO surface layer into an amorphous non-protective Ni(OH)2 gel. This gel would also form along the grain boundaries and when hydrogenated steam reaches the porous Ni-rich regions. Crack initiation is then favored by tensile stressing of the grain boundary regions which can easily rupture the gelatinous film. The leaching of matrix Cr to form non-protective CrOOH gel at the crack tip followed by the exposure of fresh porous Ni to the environment also explains crack propagation in inconel alloy 600. The proposed crack initiation mechanism is not expected to occur in alloy 690 where a protective Cr2O 3 film covers the entire metal surface. However, crack propagation along the grain boundaries in alloy 600 and pre-cracked alloy 690 is expected to be active as hydroxide-forming reactions weaken the material at the grain boundaries.

Evolution of grain boundary character distributions in alloy 825 tubes during high temperature annealing: Is grain boundary engineering achieved through recrystallization or grain growth?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bai, Qin; Zhao, Qing

Grain boundary engineering (GBE) of nickel-based alloy 825 tubes was carried out with different cold drawing deformations by using a draw-bench on a factory production line and subsequent annealing at various temperatures. The microstructure evolution of alloy 825 during thermal-mechanical processing (TMP) was characterized by means of the electron backscatter diffraction (EBSD) technique to study the TMP effects on the grain boundary network and the evolution of grain boundary character distributions during high temperature annealing. The results showed that the proportion of ∑ 3{sup n} coincidence site lattice (CSL) boundaries of alloy 825 tubes could be increased to > 75%more » by the TMP of 5% cold drawing and subsequent annealing at 1050 °C for 10 min. The microstructures of the partially recrystallized samples and the fully recrystallized samples suggested that the proportion of low ∑ CSL grain boundaries depended on the annealing time. The frequency of low ∑ CSL grain boundaries increases rapidly with increasing annealing time associating with the formation of large-size highly-twinned grains-cluster microstructure during recrystallization. However, upon further increasing annealing time, the frequency of low ∑ CSL grain boundaries decreased markedly during grain growth. So it is concluded that grain boundary engineering is achieved through recrystallization rather than grain growth. - Highlights: •The grain boundary engineering (GBE) is applicable to 825 tubes. •GBE is achieved through recrystallization rather than grain growth. •The low ∑ CSL grain boundaries in 825 tubes can be increased to > 75%.« less

Boundaries of intergrowths between mineral individuals: A zone of secondary mineral formation in aggregates

NASA Astrophysics Data System (ADS)

Brodskaya, R. L.; Bil'Skaya, I. V.; Lyakhnitskaya, V. D.; Markovsky, B. A.; Sidorov, E. G.

2007-12-01

Intergrowth boundaries between mineral individuals in dunite of the Gal’moenan massif in Koryakia was studied in terms of crystal morphology, crystal optics, and ontogenesis. The results obtained allowed us to trace the staged formation of olivine and chromite and four generations of these minerals. Micro-and nanotopography of boundary surfaces between intergrown mineral individuals of different generations was examined with optic, electron, and atomic force microscopes. The boundaries between mineral individuals of different generations are distinguished by their microsculpture for both olivine and chromite grains. Both minerals demonstrate a compositional trend toward refinement from older to younger generations. The decrease in the iron mole fraction in olivine and chromite is accompanied by the crystallization of magnetite along weakened zones in olivine of the first generation and as outer rims around the chromite grains of the second generation observable under optic and electronic microscopes. The subsequent refinement of chromite results in the release of PGE from its lattice, as established by atomic power microscopy. The newly formed PGM are localized at the boundaries between mineral individuals and, thus, mark a special stage in the ontogenetic evolution of mineral aggregates. Further recrystallization is expressed in the spatial redistribution of grain boundaries and the formation of monomineralic intergrowth boundaries, i.e., the glomerogranular structure of rock and substructures of PGM, chromite, and olivine grains as intermediate types of organization of the granular assemblies in the form of reticulate, chain, and cellular structures and substructures of aggregates.

Deformation twinning in irradiated ferritic/martensitic steels

NASA Astrophysics Data System (ADS)

Wang, K.; Dai, Y.; Spätig, P.

2018-04-01

Two different ferritic/martensitic steels were tensile tested to gain insight into the mechanisms of embrittlement induced by the combined effects of displacement damage and helium after proton/neutron irradiation in SINQ, the Swiss spallation neutron source. The irradiation conditions were in the range: 15.8-19.8 dpa (displacement per atom) with 1370-1750 appm He at 245-300 °C. All the samples fractured in brittle mode with intergranular or cleavage fracture surfaces when tested at room temperature (RT) or 300 °C. After tensile test, transmission electron microscopy (TEM) was employed to investigate the deformation microstructures. TEM-lamella samples were extracted directly below the intergranular fracture surfaces or cleavage surfaces by using the focused ion beam technique. Deformation twinning was observed in irradiated specimens at high irradiation dose. Only twins with {112} plane were observed in all of the samples. The average thickness of twins is about 40 nm. Twins initiated at the fracture surface, became gradually thinner with distance away from the fracture surface and finally stopped in the matrix. Novel features such as twin-precipitate interactions, twin-grain boundary and/or twin-lath boundary interactions were observed. Twinning bands were seen to be arrested by grain boundaries or large precipitates, but could penetrate martensitic lath boundaries. Unlike the case of defect free channels, small defect-clusters, dislocation loops and dense small helium bubbles were observed inside twins.

Three dimensional microstructural characterization of nanoscale precipitates in AA7075-T651 by focused ion beam (FIB) tomography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singh, Sudhanshu S.; Loza, Jose J.

2016-08-15

The size and distribution of precipitates in Al 7075 alloys affects both the mechanical and corrosion behavior (including stress corrosion cracking and fatigue corrosion) of the alloy. Three dimensional (3D) quantitative microstructural analysis of Al 7075 in the peak aged condition (T651) allows for a better understanding of these behaviors. In this study, Focused ion beam (FIB) tomography was used to characterize the microstructure in three dimensions. Analysis of grains and precipitates was performed in terms of volume, size, and morphology. It was found that the precipitates at the grain boundaries are larger in size, higher in aspect ratios andmore » maximum Feret diameter compared to the precipitates inside the grains, due to earlier nucleation of the precipitates at the grain boundaries. Our data on the precipitates at the interface between grains and Mg{sub 2}Si inclusion show that the surfaces of inclusion (impurity) particles can serve as a location for heterogeneous nucleation of precipitates. - Highlights: •Focused ion beam (FIB) tomography was used to characterize the microstructure of Al 7075 in three dimensions. •Analysis of grains and precipitates was performed in terms of volume, size, and morphology. •Precipitates at the grain boundaries have larger size and aspect ratio compared to the precipitates inside the grains.« less

Grain boundary imaging, gallium diffusion and the fracture behavior of Al-Zn Alloy - An in situ study

NASA Astrophysics Data System (ADS)

Tsai, W. L.; Hwu, Y.; Chen, C. H.; Chang, L. W.; Je, J. H.; Lin, H. M.; Margaritondo, G.

2003-01-01

Phase contrast radiology using unmonochromatic synchrotron X-ray successfully imaged the grain boundaries of Al and AlZn alloy without contrast agent. Combining the high penetration of X-ray and the possibility of 3D reconstruction by tomorgraphy or stereography method, this approach can be very used for nondestructive characterization of polycrystalline materials. By examine the images with 3D perspective, we were able locate the observed void-like defects which lies exclusively on the grain boundary and identify their origin from last stage of the rolling process. We studied the Ga Liquid metal diffusion in the AlZn alloy, under different temperature and stress conditions. High resolution images, ˜2 μm, of Ga liquid metal diffusion in AlZn were obtained in real time and diffusion paths alone grain boundaries and surfaces were clearly identified. Embrittled AlZn responses to the tensile stress and fractures in a drastic different manner than the pure AlZn. These results, although very much expected from the known weakening effect of the liquid metal embrittlement demonstrated, however, that this particular radiology method is fully capable of dynamic study in the micrometer scale.

Localizing sources of acoustic emission during the martensitic transformation

NASA Astrophysics Data System (ADS)

Niemann, R.; Kopeček, J.; Heczko, O.; Romberg, J.; Schultz, L.; Fähler, S.; Vives, E.; Mañosa, L.; Planes, A.

2014-06-01

Acoustic avalanches are a general feature of solids under stress, e.g., evoked by external compression or arising from internal processes like martensitic phase transformations. From integral measurements, it is usually concluded that nucleation, phase boundary pinning, or interface incompatibilities during this first-order phase transition all may generate acoustic emission. This paper studies the local sources of acoustic emission to enlight the microscopic mechanisms. From two-dimensional spatially resolved acoustic emission measurement and simultaneous optical observation of the surface, we can identify microstructural events at the phase boundary that lead to acoustic emission. A resolution in the 100-μm range was reached for the location of acoustic emission sources on a coarse-grained Ni-Mn-Ga polycrystal. Both, the acoustic activity and the size distribution of the microstructural transformation events, exhibit power-law behavior. The origin of the acoustic emission are elastically incompatible areas, such as differently oriented martensitic plates that meet each other, lamellae growing up to grain boundaries, and grain boundaries in proximity to transforming grains. Using this result, we propose a model to explain the decrease of the critical exponent under a mechanical stress or magnetic field.

The Role of Grain Orientation and Grain Boundary Characteristics in the Mechanical Twinning Formation in a High Manganese Twinning-Induced Plasticity Steel

NASA Astrophysics Data System (ADS)

Shterner, Vadim; Timokhina, Ilana B.; Rollett, Anthony D.; Beladi, Hossein

2018-04-01

In the current study, the dependence of mechanical twinning on grain orientation and grain boundary characteristics was investigated using quasi in-situ tensile testing. The grains of three main orientations (i.e., <111>, <110>, and <100> parallel to the tensile axis (TA)) and certain characteristics of grain boundaries (i.e., the misorientation angle and the inclination angle between the grain boundary plane normal and the TA) were examined. Among the different orientations, <111> and <100> were the most and the least favored orientations for the formation of mechanical twins, respectively. The <110> orientation was intermediate for twinning. The annealing twin boundaries appeared to be the most favorable grain boundaries for the nucleation of mechanical twinning. No dependence was found for the inclination angle of annealing twin boundaries, but the orientation of grains on either side of the annealing twin boundary exhibited a pronounced effect on the propensity for mechanical twinning. Annealing twin boundaries adjacent to high Taylor factor grains exhibited a pronounced tendency for twinning regardless of their inclination angle. In general, grain orientation has a significant influence on twinning on a specific grain boundary.

Mechanisms by which oxygen acts as a surfactant in giant magnetoresistance film growth

NASA Astrophysics Data System (ADS)

Larson, D. J.; Petford-Long, A. K.; Cerezo, A.; Bozeman, S. P.; Morrone, A.; Ma, Y. Q.; Georgalakis, A.; Clifton, P. H.

2003-04-01

The mechanisms by which oxygen acts as a surfactant in giant magnetoresistance multilayers have been elucidated for the first time. Three-dimensional atom probe analysis of Cu/CoFe multilayers reveals the elemental distributions at the atomic level. Interfacial intermixing and oxygen impurity levels have been quantified for the first time. Both with and without oxygen the intermixing is greater at the CoFe-on-Cu interface than at the Cu-on-CoFe one and for both interfaces, oxygen reduced the intermixing. The oxygen largely floats to the growing surface and is incorporated at grain boundaries. The oxygen also reduces conformal roughness and grain boundary grooving, indicating a reduction in long-range surface diffusion.

Damage Tolerance and Mechanics of Interfaces in Nanostructured Metals

NASA Astrophysics Data System (ADS)

Foley, Daniel J.

The concept of interface driven properties in crystalline metals has been one of the most intensely discussed topics in materials science for decades. Since the 1980s researchers have been exploring the concept of grain boundary engineering as route for tuning properties such as fracture toughness and irradiation resistance. This is especially true in ultra-fine grained and nanocrystalline materials where grain boundary mediated properties become dominant. More recently, materials composed of hierarchical nanostructures, such as amorphous-crystalline nanolaminates, have attracted considerable attention due to their favorable properties, ease of manufacture and highly tunable microstructure. While both grain boundary engineering and hierarchical nanostructures have shown promise there are still questions remaining regarding the role of specific attributes of the microstructure (such as grain boundaries, grain/layer size and inter/intralayer morphology) in determining material properties. This thesis attempts to address these questions by using atomistic simulations to perform deformation and damage loading studies on a series of nanolaminate and bicrystalline structures. During the course of this thesis the roles of layer thickness, interlayer structure and interlayer chemistry on the mechanical properties of Ni-NiX amorphous-crystalline nanolaminates were explored using atomistic simulations. This thesis found that layer thickness/thickness ratio and amorphous layer chemistry play a crucial role in yield strength and Young's modulus. Analysis of the deformation mechanisms at the atomic scale revealed that structures containing single crystalline, crystalline layers undergo plastic deformation when shear transformation zones form in the amorphous layer and impinge on the amorphous-crystalline interface, leading to dislocation emission. However, structures containing nanocrystalline, crystalline layers (both equiaxed and columnar nanocrystalline) undergo plastic deformation through a combination of grain boundary sliding and grain boundary mediated dislocation nucleation. Since grain boundaries were found to play a critical role as sources and sinks for dislocations in amorphous-crystalline nanolaminates a follow-up study on the effect of grain boundary character on damage accumulation/accommodation in copper symmetric tilt grain boundaries was performed. This study found that grain boundaries will become saturated with damage, a state where grain boundary energy and grain boundary free volume oscillate about a plateau during continuous defect loading (vacancy, interstitial and frenkel pair loading were all considered). Further, grain boundary character (specifically equilibrium grain boundary energy) was strongly correlated to the damage accommodation behavior of grain boundaries in copper. Finally, a study that attempted to link grain boundary damage saturation behavior to variations in grain boundary mechanical properties was performed. This study found no direct relationships between grain boundary damage saturation behavior and variations in grain boundary properties. The results of this thesis provide researchers with several strategies for tuning the properties of amorphous-crystalline nanolaminates. These strategies include manipulated bulk attributes such as layer thickness and morphology as well as manipulation of microscale attributes such as grain boundary engineering. Finally, this thesis provides valuable insight into the damage loading/accommodation behavior of FCC symmetric tilt grain boundaries.

Density Functional Theory plus Hubbard U Study of the Segregation of Pt to the CeO2- x Grain Boundary.

PubMed

Zhou, Guoli; Li, Pan; Ma, Qingmin; Tian, Zhixue; Liu, Ying

2018-03-14

Grain boundaries (GBs) can be used as traps for solute atoms and defects, and the interaction between segregants and GBs is crucial for understanding the properties of nanocrystalline materials. In this study, we have systematically investigated the Pt segregation and Pt-oxygen vacancies interaction at the ∑3 (111) GB in ceria (CeO 2 ). The Pt atom has a stronger tendency to segregate to the ∑3 (111) GB than to the (111) and (110) free surfaces, but the tendency is weaker than to (112) and (100). Lattice distortion plays a dominant role in Pt segregation. At the Pt-segregated-GB (Pt@GB), oxygen vacancies prefer to form spontaneously near Pt in the GB region. However, at the pristine GB, oxygen vacancies can only form under O-poor conditions. Thus, Pt segregation to the GB promotes the formation of oxygen vacancies, and their strong interactions enhance the interfacial cohesion. We propose that GBs fabricated close to the surfaces of nanocrystalline ceria can trap Pt from inside the grains or other types of surface, resulting in the suppression of the accumulation of Pt on the surface under redox reactions, especially under O-poor conditions.

Simulation and measurement of nanometer-scale resistivity of copper films for interconnect applications

NASA Astrophysics Data System (ADS)

Yarimbiyik, Arif Emre

2007-12-01

A highly versatile simulation program is developed and used to examine how the resistivity of thin metal films and lines increases as their dimensions approach and become smaller than the mean fee path of electrons in metals such as copper (size effect). The simulation program: (1) provides a more accurate calculation of surface scattering effects than that obtained from the usual formulation of Fuchs' theory, (2) calculates grain-boundary effects that are consistent with the theory of Mayadas and Shatzkes, (3) includes the effects of surface and grain-boundary scattering either separately or together, and (4) simulates the effect on resistivity if a surface of a film or line has a different value for the scattering parameter. The increase in resistivity with decreasing thickness of thin, evaporated copper films (approximately 10 nm to 150 nm thick) was determined from sheet resistance and film thickness measurements. Good agreement between the experimental results with those of the simulation program was obtained when the measured mean grain sizes were used by the simulation program. The mean of the grain sizes tend to decrease with decreasing film thickness and thereby increase the impact of grain-boundary scattering on the effective resistivity of the film. Estimates of the mean grain size for each film were determined from using, in combination, the electron backscatter diffraction (EBSD) and the X-ray diffraction (XRD) methods. With values for the measured change in sheet resistance with temperature of these films, it is shown that measurements of the electrical film thickness, using Matthiessen's rule, agreed to within 3 nm of the physical measurements (profilometer) of these films. Hence, Matthiessen's rule can continue to be used to measure the thickness of a copper film and, by inference, the cross-sectional area of a copper line for dimensions well below the mean free path of electrons in copper at room temperature (39 nm).

Grain boundary diffusion in olivine (Invited)

NASA Astrophysics Data System (ADS)

Marquardt, K.; Dohmen, R.

2013-12-01

Olivine is the main constituent of Earth's upper mantle. The individual mineral grains are separated by grain boundaries that have very distinct properties compared to those of single crystals and strongly affect large-scale physical and chemical properties of rocks, e.g. viscosity, electrical conductivity and diffusivity. Knowledge on the grain boundary physical and chemical properties, their population and distribution in polycrystalline materials [1] is a prerequisite to understand and model bulk (rock) properties, including their role as pathways for element transport [2] and the potential of grain boundaries as storage sites for incompatible elements [3]. Studies on selected and well characterized single grain boundaries are needed for a detailed understanding of the influence of varying grain boundaries. For instance, the dependence of diffusion on the grain boundary structure (defined by the lattice misfit) and width in silicates is unknown [2, 4], but limited experimental studies in material sciences indicate major effects of grain boundary orientation on diffusion rates. We characterized the effect of grain boundary orientation and temperature on element diffusion in forsterite grain boundaries by transmission electron microscopy (TEM).The site specific TEM-foils were cut using the focused ion beam technique (FIB). To study diffusion we prepared amorphous thin-films of Ni2SiO4 composition perpendicular to the grain boundary using pulsed laser deposition. Annealing (800-1450°C) leads to crystallization of the thin-film and Ni-Mg inter-diffuse into the crystal volume and along the grain boundary. The inter-diffusion profiles were measured using energy dispersive x-ray spectrometry in the TEM, standardized using the Cliff-Lorimer equation and EMPA measurements. We obtain volume diffusion coefficients that are comparable to Ni-Mg inter-diffusion rates in forsterite determined in previous studies at comparable temperatures, with similar activation energies. Grain boundary diffusion perpendicular to the dislocation lines of the small angle grain boundaries proved to be about an order of magnitude faster than volume diffusion, whereas diffusion in high angle grain boundaries is several orders of magnitude faster. We will discuss the variation of element diffusion rates with grain boundary orientation and the temperature- and/or time-induced transition from one diffusion regime to the next regime. This is done using time series experiments and two-dimensional grain boundary diffusion simulations. Finally, we will debate the differences between our data and other data sets that result from different experimental setups, conditions and analyses.

The Effect of Humidity and Particle Characteristics on Friction and Stick-slip Instability in Granular Fault Gouge

NASA Astrophysics Data System (ADS)

Anthony, J. L.; Marone, C. J.

2003-12-01

Previous studies have shown that particle characteristics such as shape, dimension, and roughness affect friction in granular shear zones. Other work shows that humidity plays a key role in frictional healing and rate/state dependence within granular gouge. In order to improve our understanding of grain-scale deformation mechanisms within fault gouge, we performed laboratory experiments using a double-direct-shear testing apparatus. This assembly includes three rigid forcing blocks with two gouge layers sandwiched between rough or smooth surfaces. Roughened surfaces were triangular grooves 0.8 mm deep and 1 mm wavelength. These promote distributed shear throughout the layer undergoing cataclastic deformation. Smooth surfaces were mirror-finished hardened steel and were used to promote and isolate grain boundary sliding. The center block is forced at controlled displacement rate between the two side blocks to create frictional shear. We studied gouge layers 3-7 mm thick, consisting of either quartz rods sheared in 1-D and 2-D configurations and smooth glass beads mixed with varying amounts of rough sand particles. We report on particle diameters that range from 0.050-0.210 mm, and quartz rods 1 mm in diameter and 100 mm long. The experiments are run at room temperature, controlled relative humidity ranging from 5 to 100%, and shear displacement rates from 0.1 to 300 microns per second. Experiments are carried out under a normal stress of 5 MPa, a non-fracture loading regime where sliding friction for smooth spherical particles is measurably lower than for rough angular particles. We compare results from shear between smooth boundaries, where we hypothesize that grain boundary sliding is the mechanism influencing granular friction, to rough sample experiments where shear undergoes a transition from distributed, pervasive shear to progressively localized as a function of increasing strain. For shear within rough surfaces, stick-slip instability occurs in gouge that consists of less than 30% angular grains and begins once the coefficient of friction (shear stress divided by normal stress) reaches a value of 0.35-0.40. Peak friction during stick-slip cycles is 0.40-0.45. Each stick-slip event involves a small amount of quasi-static displacement prior to failure, which we refer to as pre-seismic slip. For unstable sliding regimes, we measure the amount of pre-seismic slip and the magnitude of dynamic stress drop. These parameters vary systematically with sliding velocity, particle characteristics, and bounding roughness. For shear within smooth surfaces, friction is very low (0.15-0.16 for spherical particles) and sliding is stable, without stick-slip instability. As more angular grains are mixed with spherical beads the coefficient of friction increases. This holds true for both the rough and smooth sample experiments. We expand on previous work done by Frye and Marone 2002 (JGR) to study the effect of humidity on 1-D, 2-D, and 3-D gouge layer configurations. Our data show that humidity has a significant effect on frictional strength and stability and that this effect is observed for both smooth surfaces, where grain boundary sliding is the dominant deformation mechanisms, and for shear within rough surfaces where gouge deformation occurs by rolling, dilation, compaction, and grain boundary sliding.

Molecular microelectrostatic view on electronic states near pentacene grain boundaries

NASA Astrophysics Data System (ADS)

Verlaak, Stijn; Heremans, Paul

2007-03-01

Grain boundaries are the most inevitable and pronounced structural defects in pentacene films. To study the effect of those structural defects on the electronic state distribution, the energy levels of a hole on molecules at and near the defect have been calculated using a submolecular self-consistent-polarization-field approach in combination with atomic charge-quadrupole interaction energy calculations. This method has been benchmarked prior to application on four idealized grain boundaries: a grain boundary void, a void with molecules squeezed in between two grains, a boundary between two grains with different crystallographic orientations, and a grain boundary void in which a permanent dipole (e.g., a water molecule) has nested. While idealized, those views highlight different aspects of real grain boundaries. Implications on macroscopic charge transport models are discussed, as well as some relation between growth conditions and the formation of the grain boundary.

Mechanisms of devitrification of grain boundary glassy phases in Si3N4 materials

NASA Technical Reports Server (NTRS)

Hench, L. L.

1982-01-01

Changes in the grain boundary (g.b.) phases of Si3N4 are analyzed, the effects of composition and thermal history on devitrification of the g.b. phases are determined, devitrification of the g.b. phases of Si3N are related to mechanical behavior and oxidation sensitivity of the material. The phase relationships that occur within the grain boundaries of Si3N4 containing various densification aids are reviewed. Comparisons of the effects of MgO, Y2O3, CeO2, and Y2O3 + AL2O3 are made in terms of the phase equilibria of the Si3N4 + SiO2 + additive compositional system. Two new equilibrium phase diagrams for the Si3N4-SiO2 and Y2O3 and Si3N4-SiO2-Ce2O3 systems are preented. The effects of Y2O3 vs CeO2 densification aids on the fracture surfaces of Si3N4 are compared. Auger electron spectroscopy shows that both oxides are concentrated within the fracture surface. Scanning electron microscopy shows evidence that Si3N4 with CeO2 formed an intergranular structure of fine grained oxynitride reaction products, as predicted by phase quilibria, whereas the Y2O3 containing sample shows evidence of an intergranular glassy phase.

Atomistic simulations of dislocation pileup: Grain boundaries interaction

DOE PAGES

Wang, Jian

2015-05-27

Here, using molecular dynamics (MD) simulations, we studied the dislocation pileup–grain boundary (GB) interactions. Two Σ11 asymmetrical tilt grain boundaries in Al are studied to explore the influence of orientation relationship and interface structure on dislocation activities at grain boundaries. To mimic the reality of a dislocation pileup in a coarse-grained polycrystalline, we optimized the dislocation population in MD simulations and developed a predict-correct method to create a dislocation pileup in MD simulations. MD simulations explored several kinetic processes of dislocations–GB reactions: grain boundary sliding, grain boundary migration, slip transmission, dislocation reflection, reconstruction of grain boundary, and the correlation ofmore » these kinetic processes with the available slip systems across the GB and atomic structures of the GB.« less

Electron beam physical vapor deposition of YSZ electrolyte coatings for SOFCs

NASA Astrophysics Data System (ADS)

He, Xiaodong; Meng, Bin; Sun, Yue; Liu, Bochao; Li, Mingwei

2008-09-01

YSZ electrolyte coatings were prepared by electron beam physical vapor deposition (EB-PVD) at a high deposition rate of up to 1 μm/min. The YSZ coating consisted of a single cubic phase and no phase transformation occurred after annealing treatment at 1000 °C. A typical columnar structure was observed in this coating by SEM and feather-like characteristics appeared in every columnar grain. In columnar grain boundaries there were many micron-sized gaps and pores. In TEM image, many white lines were found, originating from the alignment of nanopores existing within feather-like columnar grains. The element distribution along the cross-section of the coating was homogeneous except Zr with a slight gradient. The coating exhibited a characteristic anisotropic behavior in electrical conductivity. In the direction perpendicular to coating surface the electrical conductivity was remarkably higher than that in the direction parallel to coating surface. This mainly attributed to the typical columnar structure for EB-PVD coating and the existence of many grain boundaries along the direction parallel to coating surface. For as-deposited coating, the gas permeability coefficient of 9.78 × 10 -5 cm 4 N -1 s -1 was obtained and this value was close to the critical value of YSZ electrolyte layer required for solid oxide fuel cell (SOFC) operation.

The contribution of grain boundary and defects to the resistivity in the ferromagnetic state of polycrystalline manganites

NASA Astrophysics Data System (ADS)

Sagdeo, P. R.; Anwar, Shahid; Lalla, N. P.; Patil, S. I.

2006-11-01

In the present study we report the precise resistivity measurements for the polycrystalline bulk sample as well as highly oriented thin-films of La 0.8Ca 0.2MnO 3. The poly crystalline sample was prepared by standard solid-state reaction route and the oriented thin film was prepared by pulsed laser deposition (PLD). The phase purity of these samples was confirmed by X-ray diffraction and the back-scattered electron imaging using scanning electron microscopy (SEM). The oxygen stoichiometry analysis was done by iodimetry titration. The resistivities of these samples were carried out with four-probe resistivity measurement setup. The observed temperature dependence of resistivity data for both the samples was fitted using the polaron model. We have found that polaronic model fits well with the experimental data of both polycrystalline and single crystal samples. A new phenomenological model is proposed and used to estimate contribution to the resistivity due to grain boundary in the ferromagnetic state of polycrystalline manganites and it has been shown that the scattering of electrons from the grain boundary (grain surface) is a function of temperature and controlled by the effective grain resistance at that temperature.

Dielectric and magnetic studies of BaTi0.5Fe0.5O3 ceramic materials, synthesized by solid state sintering.

PubMed

Samuvel, K; Ramachandran, K

2015-02-05

A comparative study of the surface morphology, dielectric and magnetic properties of the BaTi0.5Fe0.5O3 (BTFO) ceramics materials. This has been carried out by synthesizing the samples in different routes. BTFO samples have shown single phased 12R type hexagonal structure with R3m, P4mm space group. Interfacial effects on the dielectric properties of the samples have been understood by Cole-Cole plots in complex impedance and modulus formalism. It has been identified that huge dielectric constant (10(3)-10(6)) at lower frequencies is largely contributed by the heterogeneous electronic microstructure at the interfaces of grains. Modulus formalism has identified the effects of both grain and grain boundary microstructure on the dielectric properties, particularly in chemical routed samples. The order of grain boundary resistivity suggests the semiconductor/insulator class of the material. The grain boundary resistivity of the mechanical alloyed samples is remarkably lower than the solid state and chemical routed samples. Few samples have of the samples have exhibited signature of ferromagnetism at the room temperature. Copyright © 2014 Elsevier B.V. All rights reserved.

Subsurface imaging of grain microstructure using picosecond ultrasonics

DOE PAGES

Khafizov, M.; Pakarinen, J.; He, L.; ...

2016-04-21

We report on imaging subsurface grain microstructure using picosecond ultrasonics. This approach relies on elastic anisotropy of crystalline materials where ultrasonic velocity depends on propagation direction relative to the crystal axes. Picosecond duration ultrasonic pulses are generated and detected using ultrashort light pulses. In materials that are transparent or semitransparent to the probe wavelength, the probe monitors GHz Brillouin oscillations. The frequency of these oscillations is related to the ultrasonic velocity and the optical index of refraction. Ultrasonic waves propagating across a grain boundary experience a change in velocity due to a change in crystallographic orientation relative to the ultrasonicmore » propagation direction. This change in velocity is manifested as a change in the Brillouin oscillation frequency. Using the ultrasonic propagation velocity, the depth of the interface can be determined from the location in time of the transition in oscillation frequency. An image of the grain boundary is obtained by scanning the beam along the surface. We demonstrate this volumetric imaging capability using a polycrystalline UO 2 sample. As a result, cross section liftout analysis of the grain boundaries using electron microscopy were used to verify our imaging results.« less

Migration of grain boundaries and triple junctions in high-purity aluminum during annealing after slight cold rolling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yin, Wenhong; School of Mechanical Engineering, Shandong University of Technology, Zibo 255049; Wang, Weiguo, E-mail: wang_weiguo@vip.163.com

Grain orientations and grain boundary migrations near triple junctions in a high purity aluminum were analyzed by electron back scattered diffraction. The results indicate that there are good correlations between the Schmid factors or Taylor factors and the misorientation values of point to original point in grains near the triple junctions in a slightly deformed sample. Grains with higher Schmid factors or lower Taylor factors typically correspond to higher misorientation values near the triple junctions. In a subsequent annealing at 400 °C, both grain boundaries and triple junctions migrate, but the former leave ghost lines. During such migration, a grainmore » boundary grows from the grain with lower Schmid factor (higher Taylor factor) into the grain with higher Schmid factor (lower Taylor factor). Usually, the amount of migration of a grain boundary is considerably greater than that of a triple junction, and the grain boundary becomes more curved after migration. These observations indicate that the triple junctions have drag effects on grain boundary migration. - Highlights: • Polycrystalline aluminum with fine grains about 30 μm were used. • Off-line in situ EBSD was used to identify TJs before and after annealing. • Grains with higher SFs have higher misorientation values near TJs after deformation. • Grain boundaries grow from hard grains into soft grains during annealing. • Triple junctions have drag effects on grain boundaries migration.« less

Effects of Intergranular Gas Bubbles on Thermal Conductivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

K. Chockalingam; Paul C. Millett; M. R. Tonks

2012-11-01

Model microstructures obtained from phase-field simulations are used to study the effective heat transfer across bicrys- tals with stationary grain boundary bubble populations. We find that the grain boundary coverage, irrespective of the intergranular bubble radii, is the most relevant parameter to the thermal resistance, which we use to derive effec- tive Kapitza resistances that are dependent on the grain boundary coverage and Kaptiza resistance of the intact grain boundary. We propose a model to predict thermal conductivity as a function of porosity, grain-size, Kaptiza resistance of the intact grain boundary, and grain boundary bubble coverage.

Chemical signature of a migrating grain boundaries in polycrystalline olivine

NASA Astrophysics Data System (ADS)

Boneh, Y.; Marquardt, K.; Skemer, P. A.

2017-12-01

Olivine is the most abundant phase and influences strongly the physical and chemical properties of the upper mantle. The structure and chemistry of olivine grain-boundaries is important to understand, as these interfaces provide a reservoir for incompatible elements and partial melt, and serve as a fast pathway for chemical diffusion. This project investigates the chemical characteristics of grain boundaries in an olivine-rich aggregate. The sample is composed of Fo50 olivine crystals with minor amounts of enstatite. It was previously deformed (Hansen et al., 2016) and then annealed (Boneh et al., 2017) to investigate the microstructural changes during recrystallization. This transient microstructure has a bimodal grain size distribution and includes grains that experienced abnormal grain-growth, (porphyroblasts) and highly strained grains with no significant recrystallization or growth (matrix). Using high-resolution transmission electron microscopy (HR-TEM) with energy dispersive X-ray (EDX) at the Bayerisches Geoinstitut (BGI), we characterized boundaries between pairs of porphyroblasts, pairs of matrix grains, and mixed boundaries between porphyroblast and matrix grains. It was found that the boundary between porphyroblasts is enriched in Al and Ca and depleted in Mg, in comparison to grain interiors. However, matrix-matrix boundaries show less chemical segregation of these elements. The relatively high level of chemical segregation to porphyroblast grain boundaries offers different possible interpretations: 1) During grain boundary migration incompatible elements are swept up by the migrating grain boundary. 2) Large angle grain boundaries provide a large density of energetically favorable storage sites for incompatible elements. 3) Diffusion along low angle grain boundaries is too slow to allow for fast chemical equilibration between the different grain boundaries. 4) Dislocations cores serve as an important transport media for impurities (i.e., Cottrell atmosphere). We will further discuss these different interpretations, their feasibility, and implications for the geochemistry of the mantle.

Electrical properties of polycrystalline olivine: evidence for grain boundary transport

NASA Astrophysics Data System (ADS)

Ten Grotenhuis, S. M.; Drury, M. R.; Peach, C. J.; Spiers, C. J.

2003-12-01

The physical and chemical properties of grain boundaries are known to play an important role in determining the electrical properties of polycrystalline oxides. Grain boundaries can either enhance conductivity if the transport of charge carriers along the grain boundaries is faster than through the lattice, or grain boundaries can reduce conductivity if the grain boundaries block the transport of charge carriers. The purpose of the experiments presented here is to deduce the mechanisms responsible for electrical conductivity in fine-grained forsterite, the Mg-end member of olivine, in order to get a better understanding of the contribution of grain boundary transport, of the properties of the grain boundaries, and to determine any relation between grain size and conductivity. A relationship between grain size and conductivity at high temperature could potentially be used to interpret zones of anomalous conductivity in the upper mantle. The materials studied consist of fine-grained forsterite (Mg2SiO4) with a minor amount (5%) of enstatite (MgSiO3) added. The electrical conductivity of three melt-free synthetic polycrystalline samples, with grain sizes between 1.1 and 4.7 mm, was measured at temperatures up to 1470° C. The complex impedance plots display one clear arc, indicating a single dominant conduction mechanism. Bulk conductivity is inversely proportional to the grain size of the different samples. This relation suggests that grain boundary diffusion of the charge carriers is controlling the electrical conductivity of the samples. The activation energy for diffusion of the charge carriers lies between 315 and 323 kJ/mol. This resembles previous data on grain boundary diffusion of Mg in forsterite and grain boundary diffusion creep. A geometrical model of less conducting cubic grains and more conducting grain boundaries agrees well with the experimental data. This model is applied to a natural mantle shear zone to predict the conductivity contrast between fine-grained shear zones and less deformed regions in the lithosphere. Upper mantle shear zones are predicted to have 1.5 to 2 orders of magnitude higher conductivity than less deformed regions in the lithosphere. This may mean that fine-grained shear zones can be detected using magnetotelluric methods.

Effects of grain size and humidity on fretting wear in fine-grained alumina, Al{sub 2}O{sub 3}/TiC, and zirconia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Krell, A.; Klaffke, D.

Friction and wear of sintered alumina with grain sizes between 0.4 and 3 {micro}m were measured in comparison with Al{sub 2}O{sub 3}/TiC composites and with tetragonal ZrO{sub 2} (3 mol% Y{sub 2}O{sub 3}). The dependence on the grain boundary toughness and residual microstresses is investigated, and a hierarchical order of influencing parameters is observed. In air, reduced alumina grain sizes improve the micromechanical stability of the grain boundaries and the hardness, and reduced wear is governed by microplastic deformation, with few pullout events. Humidity and water slightly reduce the friction of all of the investigated ceramics. In water, this effectmore » reduces the wear of coarser alumina microstructures. The wear of aluminas and of the Al{sub 2}O{sub 3}/TiC composite is similar; it is lower than observed in zirconia, where extended surface cracking occurs at grain sizes as small as 0.3 {micro}m.« less

Effect of nanostructured titanium on anodization growth of self-organized TiO2 nanotubes

NASA Astrophysics Data System (ADS)

Zhang, Lan; Han, Yong

2010-02-01

To understand the effect of substrate microstructure on the formation of TiO2 nanotubes, anodic oxidizations of commercially pure titanium subjected to surface mechanical attrition treatment (SMATed-Ti) and unSMATed-Ti in a glycol solution containing NH4F and small amounts of water were investigated. The SMATed-Ti exhibit a nanocrystallized surface layer containing a high density of grain boundaries compared with unSMATed-Ti. The anodization results show that the formed TiO2 nanotube layer on the SMATed-Ti is much thicker than that on the unSMATed-Ti. It is indicated that nanocrystallized Ti is propitious to the growth of TiO2 nanotubes; grain boundaries and dislocations play the leading role in accelerating the reaction rate and ion diffusion coefficient during anodization. In addition, nanocrystallization of Ti does not change surface morphologies and phase components of the TiO2 nanotubes.

Three dimensional grain boundary modeling in polycrystalline plasticity

NASA Astrophysics Data System (ADS)

Yalçinkaya, Tuncay; Özdemir, Izzet; Fırat, Ali Osman

2018-05-01

At grain scale, polycrystalline materials develop heterogeneous plastic deformation fields, localizations and stress concentrations due to variation of grain orientations, geometries and defects. Development of inter-granular stresses due to misorientation are crucial for a range of grain boundary (GB) related failure mechanisms, such as stress corrosion cracking (SCC) and fatigue cracking. Local crystal plasticity finite element modelling of polycrystalline metals at micron scale results in stress jumps at the grain boundaries. Moreover, the concepts such as the transmission of dislocations between grains and strength of the grain boundaries are not included in the modelling. The higher order strain gradient crystal plasticity modelling approaches offer the possibility of defining grain boundary conditions. However, these conditions are mostly not dependent on misorientation of grains and can define only extreme cases. For a proper definition of grain boundary behavior in plasticity, a model for grain boundary behavior should be incorporated into the plasticity framework. In this context, a particular grain boundary model ([l]) is incorporated into a strain gradient crystal plasticity framework ([2]). In a 3-D setting, both bulk and grain boundary models are implemented as user-defined elements in Abaqus. The strain gradient crystal plasticity model works in the bulk elements and considers displacements and plastic slips as degree of freedoms. Interface elements model the plastic slip behavior, yet they do not possess any kind of mechanical cohesive behavior. The physical aspects of grain boundaries and the performance of the model are addressed through numerical examples.

The effect of hydrocarbons on the microstructural evolution in rock salt: a case study on hydrocarbon bearing Ara salt from the South Oman Salt Basin

NASA Astrophysics Data System (ADS)

Schmatz, Joyce; Urai, Janos L.; Wübbeler, Franziska M. M.; Sadler, Marc

2014-05-01

It has been shown that dilatant deformation promotes the incorporation of hydrocarbons into typically low permeable rock salt (Schoenherr et al., 2007). However, there is not much knowledge on subsequent mechanisms related to recrystallization processes, which cause morphological and chemical changes of the carbonic inclusions. This work aims to contribute to an increased understanding of fluid inclusion dynamics related to grain boundary migration recrystallization and hence to facilitate the interpretation of complex microstructures in recrystallized, multiphase salt rocks. In this case study we investigate hydrocarbon-impregnated salt from the Cambrian Ara Group in the South Oman Salt Basin. The samples were cored from cm-m thick anhydrite-salt sequences overlying hydrocarbon bearing carbonate stringers in 3300 m depth. The anhydrite layers consist mainly of fine-grained anhydrite, which contains calcite, dolomite, and olivine inclusions. Solid bitumen and lighter hydrocarbon phases are observed in between the anhydrite grains and along cracks. Anhydrite layers host salt veins, which contain fragments of anhydrite. These fragments do not differ in composition or structure from the host material and the related vein microstructures indicate crack-seal mechanisms. Halite in the salt layers is almost entirely recrystallized with solid inclusions consisting of anhydrite, calcite, dolomite and olivine with hydrocarbon-coatings present inside grains and along grain boundaries. Solid inclusions cause pinning indicated by a decreased recrystallized grain size and by the presence of grains with preserved substructures representing earlier deformation phases. We observe two types of carbonic inclusions: I) solid bitumen coatings along grain boundaries and microcracks, interpreted to be incorporated into the salt in an overpressure state that allowed dilatancy of the salt, and II) less degraded, liquid hydrocarbons along grain boundaries in the vicinity of the anhydrite, interpreted to be incorporated into the salt in a subsequent deformation phase. Type II inclusions usually form arrays of isolated inclusions (liquid hydrocarbons, vapor, and aqueous phases in minor proportions) along grain boundaries of the recrystallized grains, presumably formed in a surface-energy controlled shrinking process from thin fluid films. Here, the contact with mobile grain boundaries promoted necking down and decomposition of multiphase inclusions. We present a model, which describes the dynamic behavior of liquid hydrocarbons in mobile grain boundaries after their enclosure into the salt layers. The model is based on numerous microanalytical methods, such as optical microscopy, fluorescence microscopy, cryo-SEM, and EDX. Schoenherr, J., et al. (2007), Limits to the sealing capacity of rock salt: A case study of the infra-Cambrian Ara Salt from the South Oman salt basin, AAPG Bulletin, 91(11), 1541-1557

Nanoscale Properties of Rocks and Subduction Zone Rheology: Inferences for the Mechanisms of Deep Earthquakes

NASA Astrophysics Data System (ADS)

Riedel, M. R.

2007-12-01

Grain boundaries are the key for the understanding of mineral reaction kinetics. More generally, nanometer scale processes involved in breaking and establishing bonds at reaction sites determine how and at which rate bulk rock properties change in response to external tectonic forcing and possibly feed back into various geodynamic processes. A particular problem is the effects of grain-boundary energy on the kinetics of the olivine-spinel phase transformation in subducting slabs. Slab rheology is affected in many ways by this (metastable) mineral phase change. Sluggish kinetics due to metastable hindrance is likely to cause particular difficulties, because of possible strong non-linear feedback loops between strain-rate and change of creep properties during transformation. In order to get these nanoscale properties included into thermo-mechanical models, reliable kinetic data is required. The measurement of grain-boundary energies is, however, a rather difficult problem. Conventional methods of grain boundary surface tension measurement include (a) equilibrium angles at triple junction (b) rotating ball method (c) thermal groove method, and others (Gottstein & Shvindlerman, 1999). Here I suggest a new method that allows for the derivation of grain-boundary energies for an isochemical phase transformation based on experimental (in-situ) kinetic data in combination with a corresponding dynamic scaling law (Riedel and Karato, 1997). The application of this method to the olivine-spinel phase transformation in subducting slabs provides a solution to the extrapolation problem of measured kinetic data: Any kinetic phase boundary measured at the laboratory time scale can be "scaled" to the correct critical isotherm at subduction zones, under experimentelly "forbidden" conditions (Liou et al., 2000). Consequences for the metastability hypothesis that relates deep seismicity with olivine metastability are derived and discussed. References: Gottstein G, Shvindlerman LS (1999) Grain Boundary Migration in Metals, CRC Press, 385 pp., New York. Riedel MR, Karato S (1997) Grain-Size Evolution in Subducted Oceanic Lithosphere Associated with the Olivine- Spinel Transformation and Its Effects on Rheology. EPSL 148: 27-43. Liou JG, Hacker BR, Zhang RY (2000) Into the forbidden zone. Science 287, 1215-1216.

Multiscale Characterization of Microstructure in Near-Surface Regions of a 16MnCr5 Gear Wheel After Cyclic Loading

NASA Astrophysics Data System (ADS)

Medghalchi, Setareh; Jamebozorgi, Vahid; Bala Krishnan, Arjun; Vincent, Smobin; Salomon, Steffen; Basir Parsa, Alireza; Pfetzing, Janine; Kostka, Aleksander; Li, Yujiao; Eggeler, Gunther; Li, Tong

2018-05-01

The dependence of the microstructure on the degree of deformation in near-surface regions of a 16MnCr5 gear wheel after 2.1 × 106 loading cycles has been investigated by x-ray diffraction analysis, transmission electron microscopy, and atom probe tomography. Retained austenite and large martensite plates, along with elongated lamella-like cementite, were present in a less deformed region. Comparatively, the heavily deformed region consisted of a nanocrystalline structure with carbon segregation up to 2 at.% at grain boundaries. Spheroid-shaped cementite, formed at the grain boundaries and triple junctions of the nanosized grains, was enriched with Cr and Mn but depleted with Si. Such partitioning of Cr, Mn, and Si was not observed in the elongated cementite formed in the less deformed zone. This implies that rolling contact loading induced severe plastic deformation as well as a pronounced annealing effect in the active contact region of the toothed gear during cyclic loading.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khafizov, M.; Pakarinen, J.; He, L.

We report on imaging subsurface grain microstructure using picosecond ultrasonics. This approach relies on elastic anisotropy of crystalline materials where ultrasonic velocity depends on propagation direction relative to the crystal axes. Picosecond duration ultrasonic pulses are generated and detected using ultrashort light pulses. In materials that are transparent or semitransparent to the probe wavelength, the probe monitors GHz Brillouin oscillations. The frequency of these oscillations is related to the ultrasonic velocity and the optical index of refraction. Ultrasonic waves propagating across a grain boundary experience a change in velocity due to a change in crystallographic orientation relative to the ultrasonicmore » propagation direction. This change in velocity is manifested as a change in the Brillouin oscillation frequency. Using the ultrasonic propagation velocity, the depth of the interface can be determined from the location in time of the transition in oscillation frequency. An image of the grain boundary is obtained by scanning the beam along the surface. We demonstrate this volumetric imaging capability using a polycrystalline UO 2 sample. As a result, cross section liftout analysis of the grain boundaries using electron microscopy were used to verify our imaging results.« less

Grain boundary engineering: fatigue fracture

NASA Astrophysics Data System (ADS)

Das, Arpan

2017-04-01

Grain boundary engineering has revealed significant enhancement of material properties by modifying the populations and connectivity of different types of grain boundaries within the polycrystals. The character and connectivity of grain boundaries in polycrystalline microstructures control the corrosion and mechanical behaviour of materials. A comprehensive review of the previous researches has been carried out to understand this philosophy. Present research thoroughly explores the effect of total strain amplitude on phase transformation, fatigue fracture features, grain size, annealing twinning, different grain connectivity and grain boundary network after strain controlled low cycle fatigue deformation of austenitic stainless steel under ambient temperature. Electron backscatter diffraction technique has been used extensively to investigate the grain boundary characteristics and morphologies. The nominal variation of strain amplitude through cyclic plastic deformation is quantitatively demonstrated completely in connection with the grain boundary microstructure and fractographic features to reveal the mechanism of fatigue fracture of polycrystalline austenite. The extent of boundary modifications has been found to be a function of the number of applied loading cycles and strain amplitudes. It is also investigated that cyclic plasticity induced martensitic transformation strongly influences grain boundary characteristics and modifications of the material's microstructure/microtexture as a function of strain amplitudes. The experimental results presented here suggest a path to grain boundary engineering during fatigue fracture of austenite polycrystals.

Diffusion of nitrogen oxides and oxygenated volatile organic compounds through snow

NASA Astrophysics Data System (ADS)

Bartels-Rausch, T.; Ammann, M.; Schneebeli, M.; Riche, F.; Wren, S. N.

2013-12-01

Release of trace gases from surface snow on Earth drives atmospheric chemistry, especially in the Polar Regions. The exchange of atmospheric trace gases between snow or firn and atmosphere can also determine how these species are incorporated into glacial ice, which serves as archive. At low wind conditions, such fluxes between the porous surface snow and the overlaying atmosphere are driven by diffusion through the interstitial air. Here we present results from two laboratory studies where we looked at how the structure of the snowpack, the interaction of the trace gases with the snow surface, and the grain boundaries influence the diffusion of NO, NO2, HONO, methanol, and acetone on time scales up to 1 h. The diffusion through a snow sample was the direct observable of the experiments. Results for different snow types are presented, the structures of which were analysed by means of X-ray computed micro-tomography. Grain boundary content was quantified in one sample using a stereological method. The observed diffusion profiles were very well reproduced in simulations based on gas-phase diffusion and the known structure of the snow sample at temperatures above 253 K. At colder temperatures surface interactions start to dominate the diffusion. Parameterizing these in terms of adsorption to the solid ice surface gave much better agreement to the observations than the use of air - liquid partitioning coefficients. This is a central result as field and modelling studies have indicated that the partitioning to liquid water might describe the diffusion through snow much better even at cold temperatures. This will be discussed using our recent results from surface sensitive spectroscopy experiments. No changes in the diffusion was observed by increasing the number of grain boundaries in the snow sample by a factor of 7.

Cellular response of preosteoblasts to nanograined/ultrafine-grained structures.

PubMed

Misra, R D K; Thein-Han, W W; Pesacreta, T C; Hasenstein, K H; Somani, M C; Karjalainen, L P

2009-06-01

Metallic materials with submicron- to nanometer-sized grains provide surfaces that are different from conventional polycrystalline materials because of the large proportion of grain boundaries with high free energy. In the study described here, the combination of cellular and molecular biology, materials science and engineering advances our understanding of cell-substrate interactions, especially the cellular activity between preosteoblasts and nanostructured metallic surfaces. Experiments on the effect of nano-/ultrafine grains have shown that cell attachment, proliferation, viability, morphology and spread are favorably modulated and significantly different from conventional coarse-grained structures. Additionally, immunofluorescence studies demonstrated stronger vinculin signals associated with actin stress fibers in the outer regions of the cells and cellular extensions on nanograined/ultrafine-grained substrate. These observations suggest enhanced cell-substrate interaction and activity. The differences in the cellular response on nanograined/ultrafine-grained and coarse-grained substrates are attributed to grain size and degree of hydrophilicity. The outcomes of the study are expected to reduce challenges to engineer bulk nanostructured materials with specific physical and surface properties for medical devices with improved cellular attachment and response. The data lay the foundation for a new branch of nanostructured materials for biomedical applications.

Grain size effect on the electrical and magneto-transport properties of nanosized Pr0.67Sr0.33MnO3

NASA Astrophysics Data System (ADS)

Ng, S. W.; Lim, K. P.; Halim, S. A.; Jumiah, H.

2018-06-01

In this study, nanosized of Pr0.67Sr0.33MnO3 prepared via sol-gel method followed by heat treatment at 600-1000 °C in intervals of 100 °C were synthesized. The structure, surface morphology, electrical, magneto-transport and magnetic properties of the samples were investigated. Rietveld refinements of X-ray diffraction patterns confirm that single phase orthorhombic crystal structure with the space group of Pnma (62) is formed at 600 °C. A strong dependence of surface morphology, electrical and magneto-transport properties on grain size have been observed in this manganites system. Both grain size and crystallite size are increases with the sintering temperature due to the congregation effect. Upon increasing grain size, the paramagnetic-ferromagnetic transition temperature increases from 278 K to 295 K. The resistivity drops and the metal-insulator transition temperature shifted from 184 K to 248 K with increases of grain size due to the grain growth and reduction of grain boundary. Below metal-insulator transition temperature, the samples fit well to the combination of resistivity due to grain or domain boundaries, electron-electron scattering process and electron-phonon interaction. The resistivity data above the metal-insulator transition temperature is well described using small polaron hopping and variable range hopping models. It is found that the negative magnetoresistance also increases with larger grain size where the highest %MR of - 26% can be observed for sample sintered at 1000 °C (245 nm).

Grain boundary crystallography in polycrystalline yttria-stabilised cubic zirconia

NASA Astrophysics Data System (ADS)

Kini, Maya K.

2018-07-01

Properties of grain boundaries such as grain boundary energy, mobility and diffusion are reported to depend strongly on their crystallography. While studies on ceramic bicrystals with low Σ misorientations have shown highly ordered structures and low energies, studies on dense polycrystalline ceramics often show the significance of grain boundary planes. In the present study, grain boundary plane distributions were studied for yttria-stabilised cubic zirconia with varying grain sizes using Electron Back Scattered Diffraction technique combined with a stereological approach. Despite nearly isotropic grain boundary plane distributions, a highly anisotropic grain boundary character distribution is observed for specific misorientations. Certain low-energy symmetric tilts such as Σ3 and Σ11 are found to occur with high frequencies across the grain size range studied, leading to an inverse correlation between GB energy and frequency of occurrence, consistent with other ceramics studied in literature.

Re-exchange of Fe and Cu at the interface in sintered Nd-Fe-B magnets: A method to eliminate Fe precipitation at grain boundaries

NASA Astrophysics Data System (ADS)

Yang, YuQi; Si, HengGang; Yang, Hao; Zhang, Lan; Huang, DongFang; Chen, BaiYi; Xu, Fang; Hu, YongMei; Han, BaoJun

2018-01-01

According to the decoupling hypothesis for magnetic grains, the coercivity in sintered Nd-Fe-B magnets is increased after Cu doping, which is due to the formation of non-magnetic grain boundaries. However, this method partially fails, and ferromagnetic Fe-segregation occurs at the grain boundary. We discovered both experimentally and through calculation that the Fe content at the grain boundaries can be tuned across a wide range by introducing another element of Ag. Segregated Fe at high temperature at the grain boundary re-dissolves into Nd2Fe14B grains during annealing at low temperature. Both configurable and magnetic entropies contribute a large driving force for the formation of nonmagnetic grain boundaries. Almost zero Fe content could be achieved at the grain boundaries of sintered Nd-Fe-B magnet.

Features of structural changes in the near-surface aluminum layer under various schemes of ion implantation

NASA Astrophysics Data System (ADS)

Kryzhevich, Dmitrij S.; Zolnikov, Konstantin P.; Korchuganov, Aleksandr V.

2017-10-01

The molecular dynamics simulation of structural rearrangements in the surface layer of aluminum samples under ion implantation of various intensities was carried out. The features of the internal structure and the crystallographic orientation of the irradiated crystallite were taken into account. To describe the interatomic interaction many-body potentials obtained in the framework of the embedded atom method were used. Irradiation of the {100} surface results in much less number of formed defects than irradiation of the {110} and {111} ones. When irradiating surfaces with beams of relatively low energy grains remain unchanged in the surface region and the formation of stacking faults was not observed. At a high intensity of irradiation, the near-surface layer of the crystallite melts. In the absence of heat removal, the centers of crystallization become grains lying on the boundary of the solid and liquid phases. Those grains increase due to the adjustment of the atoms of the liquid phase to their lattice. As a result, the grain size in the near-surface region increases.

Algorithm based on regional separation for automatic grain boundary extraction using improved mean shift method

NASA Astrophysics Data System (ADS)

Zhenying, Xu; Jiandong, Zhu; Qi, Zhang; Yamba, Philip

2018-06-01

Metallographic microscopy shows that the vast majority of metal materials are composed of many small grains; the grain size of a metal is important for determining the tensile strength, toughness, plasticity, and other mechanical properties. In order to quantitatively evaluate grain size in metals, grain boundaries must be identified in metallographic images. Based on the phenomenon of grain boundary blurring or disconnection in metallographic images, this study develops an algorithm based on regional separation for automatically extracting grain boundaries by an improved mean shift method. Experimental observation shows that the grain boundaries obtained by the proposed algorithm are highly complete and accurate. This research has practical value because the proposed algorithm is suitable for grain boundary extraction from most metallographic images.

Dynamics of Nanoscale Grain-Boundary Decohesion in Aluminum by Molecular-Dynamics Simulation

NASA Technical Reports Server (NTRS)

Yamakov, V.; Saether, E.; Phillips, D. R.; Glaessegen, E. H.

2007-01-01

The dynamics and energetics of intergranular crack growth along a flat grain boundary in aluminum is studied by a molecular-dynamics simulation model for crack propagation under steady-state conditions. Using the ability of the molecular-dynamics simulation to identify atoms involved in different atomistic mechanisms, it was possible to identify the energy contribution of different processes taking place during crack growth. The energy contributions were divided as: elastic energy, defined as the potential energy of the atoms in fcc crystallographic state; and plastically stored energy, the energy of stacking faults and twin boundaries; grain-boundary and surface energy. In addition, monitoring the amount of heat exchange with the molecular-dynamics thermostat gives the energy dissipated as heat in the system. The energetic analysis indicates that the majority of energy in a fast growing crack is dissipated as heat. This dissipation increases linearly at low speed, and faster than linear at speeds approaching 1/3 the Rayleigh wave speed when the crack tip becomes dynamically unstable producing periodic dislocation bursts until the crack is blunted.

Grain boundary oxidation and its effects on high temperature fatigue life

NASA Technical Reports Server (NTRS)

Liu, H. W.; Oshida, Yoshiki

1986-01-01

Fatigue lives at elevated temperatures are often shortened by creep and/or oxidation. Creep causes grain boundary void nucleation and grain boundary cavitation. Grain boundary voids and cavities will accelerate fatigue crack nucleation and propagation, and thereby shorten fatigue life. The functional relationships between the damage rate of fatigue crack nucleation and propagation and the kinetic process of oxygen diffusion depend on the detailed physical processes. The kinetics of grain boundary oxidation penetration was investigated. The statistical distribution of grain boundary penetration depth was analyzed. Its effect on high temperature fatigue life are discussed. A model of intermittent micro-ruptures of grain boundary oxide was proposed for high temperature fatigue crack growth. The details of these studies are reported.

Laser cladding assisted by friction stir processing for preparation of deformed crack-free Ni-Cr-Fe coating with nanostructure

NASA Astrophysics Data System (ADS)

Xie, Siyao; Li, Ruidi; Yuan, Tiechui; Chen, Chao; Zhou, Kechao; Song, Bo; Shi, Yusheng

2018-02-01

Although laser cladding has find its widespread application in surface hardening, this technology has been significantly limited by the solidification crack, which usually initiates along grain boundary due to the brittle precipitation in grain boundary and networks formation during the laser rapid melting/solidification process. This paper proposed a novel laser cladding technology assisted by friction stir processing (FSP) to eliminate the usual metallurgical defects by the thermomechanical coupling effect of FSP with the Ni-Cr-Fe as representative coating material. By the FSP assisted laser cladding, the crack in laser cladding Ni-Cr-Fe coating was eliminated and the coarse networks of laser cladding coating was transformed into dispersed nanoparticles. Moreover, the plastic layers with thicknesses 47-140 μm can be observed, with gradient grain refinement from substrate to the top surface in which grain size reached 300 nm and laser photocoagulation net second phase crushed in the layer. In addition, cracks closed in the plastic zone. The refinement of grain resulted the hardness increased to over 400 HV, much higher than the 300 HV of the laser cladding structure. After FSP, the friction coefficient decreased from 0.6167 to 0.5645 which promoted the wear resistance.

Correlation between grain boundary misorientation and M{sub 23}C{sub 6} precipitation behaviors in a wrought Ni-based superalloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, Bin, E-mail: toby198489@163.com; Jiang, Li; Hu, Rui

2013-04-15

The correlation between the grain boundary misorientation and the precipitation behaviors of intergranular M{sub 23}C{sub 6} carbides in a wrought Ni–Cr–W superalloy was investigated by using the electron backscattered diffraction (EBSD) technique. It was observed that the grain boundaries with a misorientation angle less than 20°, as well as all coincidence site lattice (CSL) boundaries, are immune to precipitation of the M{sub 23}C{sub 6} carbides; in contrast, the random high-angle grain boundaries with a misorientation angle of 20°–40° provide preferential precipitation sites of the M{sub 23}C{sub 6} carbides at the random high-angle grain boundaries with a higher misorientation angle ofmore » 55°–60°/[2 2 3] turn to retard precipitation of M{sub 23}C{sub 6} carbides owing to their nature like the Σ3 grain boundaries and retard the precipitation of M{sub 23}C{sub 6} carbides. The low-angle and certain random grain boundary segments induced by twins were found to interrupt the precipitation of the M{sub 23}C{sub 6} carbides along the high-angle grain boundaries. - Highlights: ► The low angle grain boundaries and CSL boundaries are immune to precipitation. ► M23C6 precipitate preferentially at random grain boundaries within 20°–40°. ► Some certain random grain boundary segments interrupt M23C6 precipitation.« less

On the role of grain boundary character distribution in grain growth of Al-Mg alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matsumoto, K.; Shibayanagi, T.; Umakoshi, Y.

1997-02-01

Grain growth behavior of recrystallized Al-Mg alloys containing 0.3 and 2.7 mass% Mg was investigated, focusing on the interconnection between development of the texture and grain boundary character distribution. An Al-0.3 mass% Mg alloy showed two stages in the change of microstructure during grain growth: the frequency of cube oriented grains and the {Sigma}1 boundary significantly increased at an early stage and then decreased. In the second stage a small amount of isolated large grains with the non-cube component grew and consumed the surrounding cube grains. In contrast, the frequency of cube oriented grains and the grain boundary character distributionmore » showed no significant change during grain growth of Al-2.7 mass% Mg. Small clusters composed of several cube grains containing {Sigma}1 boundaries were formed and their spatial distribution played an important role in the change of microstructure during grain growth. The effect of the spatial distribution on the grain growth behavior was discussed considering the energy balance at triple junctions of grain boundaries.« less

The role of microstructure on deformation and damage mechanisms in a Nickel-based superalloy at elevated temperatures

NASA Astrophysics Data System (ADS)

Maciejewski, Kimberly E.

The overall objective of this research work is the development and implementation of a mechanistic based time-dependent crack growth model which considers the role of creep, fatigue and environment interactions on both the bulk and the grain boundary phase in ME3 disk material. The model is established by considering a moving crack tip along a grain boundary path in which damage events are described in terms of the grain boundary deformation and related accommodation processes. Modeling of these events was achieved by adapting a cohesive zone approach (an interface with internal singular surfaces) in which the grain boundary dislocation network is smeared into a Newtonian fluid element. The deformation behavior of this element is controlled by the continuum in both far field (internal state variable model) and near field (crystal plasticity model) and the intrinsic grain boundary viscosity which is characterized by microstructural parameters, including grain boundary precipitates and morphology, and is able to define the mobility of the element by scaling the motion of dislocations into a mesoscopic scale. Within the cohesive zone element, the motion of gliding dislocations in the tangential direction relates to the observed grain boundary sliding displacement, the rate of which is limited by the climb of dislocations over grain boundary obstacles. Effects of microstructural variation and orientation of the surrounding continuum are embedded in the tangential stress developing in the grain boundary. The mobility of the element in the tangential direction (i.e. by grain boundary sliding) characterizes the accumulation of irreversible displacement while the vertical movement (migration), although present, is assumed to alter stress by relaxation and, thus, is not considered a contributing factor in the damage process. This process is controlled by the rate at which the time-dependent sliding reaches a critical displacement and as such, a damage criterion is introduced by considering the mobility limit in the tangential direction leading to strain incompatibility and failure. This limit is diminished by environmental effects which are introduced as a dynamic embrittlement process that hinders grain boundary mobility due to oxygen diffusion. The concepts described herein indicate that implementation of the cohesive zone model requires the knowledge of the grain boundary external and internal deformation fields. The external field is generated by developing and coupling two continuum constitutive models including (i) a microstructure-explicit coarse scale crystal plasticity model with strength provided by tertiary and secondary gamma' precipitates. This scale is appropriate for the representation of the continuum region at the immediate crack tip, and (ii) a macroscopic internal state variable model for the purpose of modeling the response of the far field region located several grains away from the crack path. The hardening contributions of the gamma' precipitates consider dislocation/precipitate interactions in terms of gamma' particles shearing and/or Orowan by-passing mechanisms. The material parameters for these models are obtained from results of low cycle fatigue tests which were performed at three temperatures; 650, 704 and 760°C. Furthermore, a series of microstructure controlled experiments were carried out in order to develop and validate the microstructure dependency feature of the continuum constitutive models. The second requirement in the implementation of the cohesive zone model is a grain boundary deformation model which has been developed, as described above, on the basis of viscous flow rules of the boundary material. This model is supported by dwell crack growth experiments carried out at the three temperatures mentioned above, in both air and vacuum environments. Results of these tests have identified the frequency range in which the grain boundary cohesive zone model is applicable and also provided data to calculate the grain boundary activation energy as well as identifying the relative contributions of creep and environment in the critical sliding displacement leading to failure. Validation of the cohesive zone model has been carried out by comparing the simulated crack growth data with that obtained experimentally. This comparison is used to optimize the different model components and to provide a route to assess the relative significance of each of these components in relation to the intergranular damage associated with dwell fatigue crack growth in the ME3 alloy. For this purpose, a set of case studies were performed in order to illustrate the sensitivity of the cohesive zone model to variations in microstructure parameters (gamma ' statistics and grain boundary morphology) examined within the range of temperatures utilized in this study.

Mechanical behaviour near grain boundaries of He-implanted UO2 ceramic polycrystals

NASA Astrophysics Data System (ADS)

Ibrahim, M.; Castelier, É.; Palancher, H.; Bornert, M.; Caré, S.; Micha, J.-S.

2017-01-01

For studying the micromechanical behaviour of UO2 and characterising the intergranular interaction, polycrystals are implanted with helium ions, inducing strains in a thin surface layer. Laue X-ray micro-diffraction is used to measure the strain field in this implanted layer with a spatial resolution of about 1 μm. It allows a 2D mapping of the strain field in a dozen of grains. These measurements show that the induced strain depends mainly on the crystal orientation, and can be evaluated by a semi-analytical mechanical model. A mechanical interaction of the neighbouring grains has also been evidenced near the grain boundaries, which has been well reproduced by a finite element model. This interaction is shown to increase with the implantation energy (i.e. the implantation depth): it can be neglected at low implantation energy (60 keV), but not at higher energy (500 keV).

Formation of Nanostructures in Severely Deformed High-Strength Steel Induced by High-Frequency Ultrasonic Impact Treatment

NASA Astrophysics Data System (ADS)

Dutta, R. K.; Malet, L.; Gao, H.; Hermans, M. J. M.; Godet, S.; Richardson, I. M.

2015-02-01

Surface modification by the generation of a nanostructured surface layer induced via ultrasonic impact treatment was performed at the weld toe of a welded high-strength quenched and tempered structural steel, S690QL1 (Fe-0.16C-0.2Si-0.87Mn-0.33Cr-0.21Mo (wt pct)). Such high-frequency peening techniques are known to improve the fatigue life of welded components. The nanocrystallized structure as a function of depth from the top-treated surface was characterized via a recently developed automated crystal orientation mapping in transmission electron microscopy. Based on the experimental observations, a grain refinement mechanism induced by plastic deformation during the ultrasonic impact treatment is proposed. It involves the formation of low-angle misoriented lamellae displaying a high density of dislocations followed by the subdivision of microbands into blocks and the resulting formation of polygonal submicronic grains. These submicronic grains further breakdown into nano grains. The results show the presence of retained austenite even after severe surface plastic deformation. The average grain size of the retained austenite and martensite is 17 and 35 nm, respectively. The in-grain deformation mechanisms are different in larger and smaller grains. Larger grains show long-range lattice rotations, while smaller grains show plastic deformation through grain rotation. Also the smaller nano grains exhibit the presence of short-range disorder. Surface nanocrystallization also leads to an increased fraction of low angle and low energy coincident site lattice boundaries especially in the smaller grains ( nm).

Energetics and structural properties of twist grain boundaries in Cu

NASA Technical Reports Server (NTRS)

Karimi, Majid

1992-01-01

Structural and energetics properties of atoms near a grain boundary are of great importance from theoretical and experimental standpoints. From various experimental work it is concluded that diffusion at low temperatures at polycrystalline materials take place near grain boundary. Experimental and theoretical results also indicate changes of up to 70 percent in physical properties near a grain boundary. The Embedded Atom Method (EAM) calculations on structural properties of Au twist grain boundaries are in quite good agreement with their experimental counterparts. The EAM is believed to predict reliable values for the single vacancy formation energy as well as migration energy. However, it is not clear whether the EAM functions which are fitted to the bulk properties of a perfect crystalline solid can produce reliable results on grain boundaries. One of the objectives of this work is to construct the EAM functions for Cu and use them in conjunction with the molecular static simulation to study structures and energetics of atoms near twist grain boundaries in Cu. This provides tests of the EAM functions near a grain boundary. In particular, we determine structure, single vacancy formation energy, migration energy, single vacancy activation energy, and interlayer spacing as a function of distance from grain boundary. Our results are compared with the available experimental and theoretical results from grain boundaries and bulk.

Improved thermoelectric performance of p-type polycrystalline bismuth telluride via hydrothermal treatment with alkali metal salts

NASA Astrophysics Data System (ADS)

Su, Zhe

The field of thermoelectric research has attracted a lot of interest in hope of helping address the energy crisis. In recent years, low-dimensional thermoelectric materials have been found promising and thus become a popular school of thought. However, the high complexity and cost for fabricating low-dimensional materials give rise to the attempt to further improve conventional bulk polycrystalline materials. Polycrystals are featured by numerous grain boundaries that can scatter heat-carrying phonons to significantly reduce the thermal conductivity kappa whereas at the same time can unfortunately deteriorate the electrical resistivity rho. Aiming at the dualism of the grain boundaries in determining the transport properties of polycrystalline materials, a novel concept of "grain boundary engineering" has been proposed in order to have a thermoelectrically favorable grain boundary. In this dissertation, a polycrystalline p-type Bi2Te 3 system has been intensively investigated in light of such a concept that was realized through a hydrothermal nano-coating treatment technique. P-type Bi0.4Sb1.6Te3 powder was hydrothermally treated with alkali metal salt XBH4 ( X = Na, K or Rb) solution. After the treatment, there formed an alkali-metal-containing surface layer of nanometers thick on the p-Bi2Te3 grains. The Na-treatment, leaving the Seebeck coefficient alpha almost untouched, lowered kappa the most while the Rb-treatment at the same time increased alpha slightly and decreased rho the most. Compared to the untreated sample, Na- and Rb-treatments improved the dimensionless figure of merit ZT by ˜ 30% due to the reduced kappa and ˜ 38% owing to the improved the power factor PF, respectively. The grain boundary phase provides a new avenue by which one can potentially decouple the otherwise inter-related alpha, rho and kappa within one thermoelectric material. The morphologic investigation showed this surface layer lacked crystallinity, if any, and was possibly an amorphous phase. Once Na- and Rb-treatments with various molar ratios were applied to the same sample, a similar grain boundary layer formed with a compositional gradient along the depth direction. The Hall effect measurements showed that the grain boundary phase introduced new carriers into the system and thereby compensated the loss in mobility. With alpha almost untouched, the rho to kappa ratio has been optimized by varying the Na:Rb ratio in the starting solution. As a result, the Na:Rb = 1:2 ratio yielded the best ZT value of ˜ 0.92 at 350K, comparable with that of the state-of-the-art p-Bi2Te3 commercial ingot. Besides ZT, the hydrothermal treatment lessened the temperature dependence of compatibility factor S of as-treated polycrystalline samples, helping a thermoelectric device have overall better performance even if it did not work under its optimal condition.

Complete grain boundaries from incomplete EBSD maps: the influence of segmentation on grain size determinations

NASA Astrophysics Data System (ADS)

Heilbronner, Renée; Kilian, Ruediger

2017-04-01

Grain size analyses are carried out for a number of reasons, for example, the dynamically recrystallized grain size of quartz is used to assess the flow stresses during deformation. Typically a thin section or polished surface is used. If the expected grain size is large enough (10 µm or larger), the images can be obtained on a light microscope, if the grain size is smaller, the SEM is used. The grain boundaries are traced (the process is called segmentation and can be done manually or via image processing) and the size of the cross sectional areas (segments) is determined. From the resulting size distributions, 'the grain size' or 'average grain size', usually a mean diameter or similar, is derived. When carrying out such grain size analyses, a number of aspects are critical for the reproducibility of the result: the resolution of the imaging equipment (light microscope or SEM), the type of images that are used for segmentation (cross polarized, partial or full orientation images, CIP versus EBSD), the segmentation procedure (algorithm) itself, the quality of the segmentation and the mathematical definition and calculation of 'the average grain size'. The quality of the segmentation depends very strongly on the criteria that are used for identifying grain boundaries (for example, angles of misorientation versus shape considerations), on pre- and post-processing (filtering) and on the quality of the recorded images (most notably on the indexing ratio). In this contribution, we consider experimentally deformed Black Hills quartzite with dynamically re-crystallized grain sizes in the range of 2 - 15 µm. We compare two basic methods of segmentations of EBSD maps (orientation based versus shape based) and explore how the choice of methods influences the result of the grain size analysis. We also compare different measures for grain size (mean versus mode versus RMS, and 2D versus 3D) in order to determine which of the definitions of 'average grain size yields the most stable results.

On the equilibrium charge density at tilt grain boundaries

NASA Astrophysics Data System (ADS)

Srikant, V.; Clarke, D. R.

1998-05-01

The equilibrium charge density and free energy of tilt grain boundaries as a function of their misorientation is computed using a Monte Carlo simulation that takes into account both the electrostatic and configurational energies associated with charges at the grain boundary. The computed equilibrium charge density increases with the grain-boundary angle and approaches a saturation value. The equilibrium charge density at large-angle grain boundaries compares well with experimental values for large-angle tilt boundaries in GaAs. The computed grain-boundary electrostatic energy is in agreement with the analytical solution to a one-dimensional Poisson equation at high donor densities but indicates that the analytical solution overestimates the electrostatic energy at lower donor densities.

Study of the corrosion behaviors of 304 austenite stainless steel specimens exposed to static liquid lithium at 600 K

NASA Astrophysics Data System (ADS)

Meng, Xiancai; Zuo, Guizhong; Ren, Jun; Xu, Wei; Sun, Zhen; Huang, Ming; Hu, Wangyu; Hu, Jiansheng; Deng, Huiqiu

2016-11-01

Investigation of corrosion behavior of stainless steel served as one kind of structure materials exposed to liquid lithium (Li) is one of the keys to apply liquid Li as potential plasma facing materials (PFM) or blanket coolant in the fusion device. Corrosion experiments of 304 austenite stainless steel (304 SS) were carried out in static liquid Li at 600 K and up to1584 h at high vacuum with pressure less than 4 × 10-4 Pa. After exposure to liquid Li, it was found that the weight of 304 SS slightly decreased with weight loss rate of 5.7 × 10-4 g/m2/h and surface hardness increased by about 50 HV. Lots of spinel-like grains and holes were observed on the surface of specimens measured by SEM. By further EDS, XRD and metallographic analyzing, it was confirmed that the main compositions of spinel-like grains were M23C6 carbides, and 304 SS produced a non-uniform corrosion behavior by preferential grain boundary attack, possibly due to the easy formation of M23C6 carbides and/or formation of Li compound at grain boundaries.

Variations in planetary convection via the effect of climate on damage

NASA Astrophysics Data System (ADS)

Landuyt, W.; Bercovici, D.

2008-12-01

The generation of plate tectonics on Earth and its absence on the other terrestrial planets (especially Venus) remains a significant conundrum in geophysics. We propose a model for the generation of plate tectonics that suggests an important interaction between a planet's climate and its lithospheric damage behavior; and thus provides a simple explanation for the tectonic difference between Earth and Venus. We propose that high surface temperatures will lead to higher healing rates (e.g. grain growth) in the lithosphere that will act to suppress localization, plate boundary formation, and subduction. This leads to episodic or stagnant lid convection on Venus because of its hotter climate. In contrast, Earth's cooler climate promotes damage and plate boundary formation. The damage rheology presented in this paper attempts to describe the evolution of grain size by allowing for grain reduction via deformational work input and grain growth via surface tension- driven coarsening. We present results from convection simulations and a simple "drip-instability" model to test our hypothesis. The results suggest the feasibility of our proposed hypothesis that the influence of climate on damage may control the mode of tectonics on a planet.

Mechanistic Study of Delamination Fracture in Al-Li Alloy C458 (2099)

NASA Technical Reports Server (NTRS)

Tayon, W. A.; Crooks, R. E.; Domack, M. S.; Wagner, J. A.; Beaudoin, A. J.; McDonald, R. J.

2009-01-01

Delamination fracture has limited the use of lightweight Al-Li alloys. In the present study, electron backscattered diffraction (EBSD) methods were used to characterize crack paths in Al-Li alloy C458 (2099). Secondary delamination cracks in fracture toughness samples showed a pronounced tendency for fracture between grain variants of the same deformation texture component. These results were analyzed by EBSD mapping methods and simulated with finite element analyses. Simulation procedures include a description of material anisotropy, local grain orientations, and fracture utilizing crystal plasticity and cohesive zone elements. Taylor factors computed for each grain orientation subjected to normal and shear stresses indicated that grain pairs with the largest Taylor factor differences were adjacent to boundaries that failed by delamination. Examination of matching delamination fracture surface pairs revealed pronounced slip bands in only one of the grains bordering the delamination. These results, along with EBSD studies, plasticity simulations, and Auger electron spectroscopy observations support a hypothesis that delamination fracture occurs due to poor slip accommodation along boundaries between grains with greatly differing plastic response.

Effect of grain size on the melting point of confined thin aluminum films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wejrzanowski, Tomasz; Lewandowska, Malgorzata; Sikorski, Krzysztof

2014-10-28

The melting of aluminum thin film was studied by a molecular dynamics (MD) simulation technique. The effect of the grain size and type of confinement was investigated for aluminum film with a constant thickness of 4 nm. The results show that coherent intercrystalline interface suppress the transition of solid aluminum into liquid, while free-surface gives melting point depression. The mechanism of melting of polycrystalline aluminum thin film was investigated. It was found that melting starts at grain boundaries and propagates to grain interiors. The melting point was calculated from the Lindemann index criterion, taking into account only atoms near to grainmore » boundaries. This made it possible to extend melting point calculations to bigger grains, which require a long time (in the MD scale) to be fully molten. The results show that 4 nm thick film of aluminum melts at a temperature lower than the melting point of bulk aluminum (933 K) only when the grain size is reduced to 6 nm.« less

Continuum understanding of twin formation near grain boundaries of FCC metals with low stacking fault energy

NASA Astrophysics Data System (ADS)

Jung, Jaimyun; Yoon, Jae Ik; Kim, Jung Gi; Latypov, Marat I.; Kim, Jin You; Kim, Hyoung Seop

2017-12-01

Deformation twinning from grain boundaries is often observed in face-centered cubic metals with low stacking fault energy. One of the possible factors that contribute to twinning origination from grain boundaries is the intergranular interactions during deformation. Nonetheless, the influence of mechanical interaction among grains on twin evolution has not been fully understood. In spite of extensive experimental and modeling efforts on correlating microstructural features with their twinning behavior, a clear relation among the large aggregate of grains is still lacking. In this work, we characterize the micromechanics of grain-to-grain interactions that contribute to twin evolution by investigating the mechanical twins near grain boundaries using a full-field crystal plasticity simulation of a twinning-induced plasticity steel deformed in uniaxial tension at room temperature. Microstructures are first observed through electron backscatter diffraction technique to obtain data to reconstruct a statistically equivalent microstructure through synthetic microstructure building. Grain-to-grain micromechanical response is analyzed to assess the collective twinning behavior of the microstructural volume element under tensile deformation. Examination of the simulated results reveal that grain interactions are capable of changing the local mechanical behavior near grain boundaries by transferring strain across grain boundary or localizing strain near grain boundary.

Optical Fluorescence Microscopy for Spatially Characterizing Electron Transfer across a Solid-Liquid Interface on Heterogeneous Electrodes.

PubMed

Choudhary, Eric; Velmurugan, Jeyavel; Marr, James M; Liddle, James A; Szalai, Veronika

2016-01-01

Heterogeneous catalytic materials and electrodes are used for (electro)chemical transformations, including those important for energy storage and utilization. 1, 2 Due to the heterogeneous nature of these materials, activity measurements with sufficient spatial resolution are needed to obtain structure/activity correlations across the different surface features (exposed facets, step edges, lattice defects, grain boundaries, etc.). These measurements will help lead to an understanding of the underlying reaction mechanisms and enable engineering of more active materials. Because (electro)catalytic surfaces restructure with changing environments, 1 it is important to perform measurements in operando . Sub-diffraction fluorescence microscopy is well suited for these requirements because it can operate in solution with resolution down to a few nm. We have applied sub-diffraction fluorescence microscopy to a thin cell containing an electrocatalyst and a solution containing the redox sensitive dye p-aminophenyl fluorescein to characterize reaction at the solid-liquid interface. Our chosen dye switches between a nonfluorescent reduced state and a one-electron oxidized bright state, a process that occurs at the electrode surface. This scheme is used to investigate the activity differences on the surface of polycrystalline Pt, in particular to differentiate reactivity at grain faces and grain boundaries. Ultimately, this method will be extended to study other dye systems and electrode materials.

Effect of the cadmium chloride treatment on RF sputtered Cd{sub 0.6}Zn{sub 0.4}Te films for application in multijunction solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shimpi, Tushar M., E-mail: mechanical.tushar@gmail.com; Kephart, Jason M.; Swanson, Drew E.

Single phase Cd{sub 0.6}Zn{sub 0.4}Te (CdZnTe) films of 1 μm thickness were deposited by radio frequency planar magnetron sputter deposition on commercial soda lime glass samples coated with fluorine-doped tin oxide and cadmium sulphide (CdS). The stack was then treated with cadmium chloride (CdCl{sub 2}) at different temperatures using a constant treatment time. The effect of the CdCl{sub 2} treatment was studied using optical, materials, and electrical characterization of the samples and compared with the as-deposited CdZnTe film with the same stack configuration. The band gap deduced from Tauc plots on the as-deposited CdZnTe thin film was 1.72 eV. The depositedmore » film had good crystalline quality with a preferred orientation along the {111} plane. After the CdCl{sub 2} treatment, the absorption edge shifted toward longer wavelength region and new peaks corresponding to cadmium telluride (CdTe) emerged in the x-ray diffraction pattern. This suggested loss of zinc after the CdCl{sub 2} treatment. The cross sectional transmission electron microscope images of the sample treated at 400 °C and the energy dispersive elemental maps revealed the absence of chlorine along the grain boundaries of CdZnTe and residual CdTe. The presence of chlorine in the CdTe devices plays a vital role in drastically improving the device performance which was not observed in CdZnTe samples treated with CdCl{sub 2}. The loss of zinc from the surface and incomplete recrystallization of the grains together with the presence of high densities of stacking faults were observed. The surface images using scanning electron microscopy showed that the morphology of the grains changed from small spherical shape to large grains formed due to the fusion of small grains with distinct grain boundaries visible at the higher CdCl{sub 2} treatment temperatures. The absence of chlorine along the grain boundaries, incomplete recrystallization and distinct grain boundaries is understood to cause the poor performance of the fabricated devices.« less

Grain boundary character distribution in nanocrystalline metals produced by different processing routes

DOE PAGES

Bober, David B.; Kumar, Mukal; Rupert, Timothy J.; ...

2015-12-28

Nanocrystalline materials are defined by their fine grain size, but details of the grain boundary character distribution should also be important. Grain boundary character distributions are reported for ball-milled, sputter-deposited, and electrodeposited Ni and Ni-based alloys, all with average grain sizes of ~20 nm, to study the influence of processing route. The two deposited materials had nearly identical grain boundary character distributions, both marked by a Σ3 length percentage of 23 to 25 pct. In contrast, the ball-milled material had only 3 pct Σ3-type grain boundaries and a large fraction of low-angle boundaries (16 pct), with the remainder being predominantlymore » random high angle (73 pct). Furthermore, these grain boundary character measurements are connected to the physical events that control their respective processing routes. Consequences for material properties are also discussed with a focus on nanocrystalline corrosion. As a whole, the results presented here show that grain boundary character distribution, which has often been overlooked in nanocrystalline metals, can vary significantly and influence material properties in profound ways.« less

Characterization of erosion of metallic materials under cavitation attack in a mineral oil

NASA Technical Reports Server (NTRS)

Rao, B. C. S.; Buckley, D. H.

1984-01-01

Cavitation erosion and erosion rates of eight metallic materials representing three crystal structures were studied using a 20-kHz ultrasonic magnetostrictive oscillator in viscous mineral oil. The erosion rates of the metals with an fcc matrix were 10 to 100 times higher than that of an hcp-matrix titanium alloy. The erosion rates of iron and molybdenum, with bcc matrices, were higher than that of the titanium alloy but lower than those of the fcc metals. Scanning electron microscopy indicates that the cavitation pits are initially formed at the grain boundaries and precipitates and that the pits that formed at the triple points grew faster than the others. Transcrystalline craters formed by cavitation attack over the surface of grains and roughened the surfaces by multiple slip and twinning. Surface roughness measurements show that the pits that formed over the grain boundaries deepended faster than other pits. Computer analysis revealed that a geometric expression describes the nondimensional erosion curves during the time period 0.5 t(0) t 2.5 t(0), where t(0) is the incubation period. The fcc metals had very short incubation periods; the titanium alloy had the longest incubation period.

A first-principles analysis of ballistic conductance, grain boundary scattering and vertical resistance in aluminum interconnects

NASA Astrophysics Data System (ADS)

Zhou, Tianji; Lanzillo, Nicholas A.; Bhosale, Prasad; Gall, Daniel; Quon, Roger

2018-05-01

We present an ab initio evaluation of electron scattering mechanisms in Al interconnects from a back-end-of-line (BEOL) perspective. We consider the ballistic conductance as a function of nanowire size, as well as the impact of surface oxidation on electron transport. We also consider several representative twin grain boundaries and calculate the specific resistivity and reflection coefficients for each case. Lastly, we calculate the vertical resistance across the Al/Ta(N)/Al and Cu/Ta(N)/Cu interfaces, which are representative of typical vertical interconnect structures with diffusion barriers. Despite a high ballistic conductance, the calculated specific resistivities at grain boundaries are 70-100% higher in Al than in Cu, and the vertical resistance across Ta(N) diffusion barriers are 60-100% larger for Al than for Cu. These results suggest that in addition to the well-known electromigration limitations in Al interconnects, electron scattering represents a major problem in achieving low interconnect line resistance at fine dimensions.

Determination of the five parameter grain boundary character distribution of nanocrystalline alpha-zirconium thin films using transmission electron microscopy

DOE PAGES

Ghamarian, I.; Samani, P.; Rohrer, G. S.; ...

2017-03-24

Grain boundary engineering and other fundamental materials science problems (e.g., phase transformations and physical properties) require an improvement in the understanding of the type and population of grain boundaries in a given system – yet, databases are limited in number and spare in detail, including for hcp crystals such as zirconium. One way to rapidly obtain databases to analyze is to use small-grained materials and high spatial resolution orientation microscopy techniques, such as ASTAR™/precession electron diffraction. To demonstrate this, a study of grain boundary character distributions was conducted for α-zirconium deposited at room temperature on fused silica substrates using physicalmore » vapor deposition. The orientation maps of the nanocrystalline thin films were acquired by the ASTARα/precession electron diffraction technique, a new transmission electron microscope based orientation microscopy method. The reconstructed grain boundaries were classified as pure tilt, pure twist, 180°-twist and 180°-tilt grain boundaries based on the distribution of grain boundary planes with respect to the angle/axis of misorientation associated with grain boundaries. The results of the current study were compared to the results of a similar study on α-titanium and the molecular dynamics results of grain boundary energy for α-titanium.« less

Electromigration of intergranular voids in metal films for microelectronic interconnects

NASA Astrophysics Data System (ADS)

Averbuch, Amir; Israeli, Moshe; Ravve, Igor

2003-04-01

Voids and cracks often occur in the interconnect lines of microelectronic devices. They increase the resistance of the circuits and may even lead to a fatal failure. Voids may occur inside a single grain, but often they appear on the boundary between two grains. In this work, we model and analyze numerically the migration and evolution of an intergranular void subjected to surface diffusion forces and external voltage applied to the interconnect. The grain-void interface is considered one-dimensional, and the physical formulation of the electromigration and diffusion model results in two coupled fourth-order one-dimensional time-dependent PDEs. The boundary conditions are specified at the triple points, which are common to both neighboring grains and the void. The solution of these equations uses a finite difference scheme in space and a Runge-Kutta integration scheme in time, and is also coupled to the solution of a static Laplace equation describing the voltage distribution throughout the grain. Since the voltage distribution is required only along the interface line, the two-dimensional discretization of the grain interior is not needed, and the static problem is solved by the boundary element method at each time step. The motion of the intergranular void was studied for different ratios between the diffusion and the electric field forces, and for different initial configurations of the void.

A novel two-step sintering for nano-hydroxyapatite scaffolds for bone tissue engineering

PubMed Central

Feng, Pei; Niu, Man; Gao, Chengde; Peng, Shuping; Shuai, Cijun

2014-01-01

In this study, nano-hydroxyapatite scaffolds with high mechanical strength and an interconnected porous structure were prepared using NTSS for the first time. The first step was performed using a laser characterized by the rapid heating to skip the surface diffusion and to obtain the driving force for grain boundary diffusion. Additionally, the interconnected porous structure was achieved by SLS. The second step consisted of isothermal heating in a furnace at a lower temperature (T2) than that of the laser beam to further increase the density and to suppress grain growth by exploiting the difference in kinetics between grain-boundary diffusion and grain-boundary migration. The results indicated that the mechanical properties first increased and then decreased as T2 was increased from 1050 to 1250°C. The optimal fracture toughness, compressive strength and stiffness were 1.69 MPam1/2, 18.68 MPa and 245.79 MPa, respectively. At the optimal point, the T2 was 1100°C, the grain size was 60 nm and the relative density was 97.6%. The decrease in mechanical properties was due to the growth of grains and the decomposition of HAP. The cytocompatibility test results indicated that cells adhered and spread well on the scaffolds. A bone-like apatite layer formed, indicating good bioactivity. PMID:24998362

Crystalline orientation engineering and charge transport in thin film YBa(2)Cu(3)O(7-x) superconducting surface-coated conductors

NASA Astrophysics Data System (ADS)

Chudzik, Michael Patrick

The weak-link behavior of grain boundaries in polycrystalline high-T c superconductors adversely affects the current density in these materials. The development of wire technology based on polycrystalline high-Tc materials requires understanding and controlling the development of low-angle grain boundaries in these conductors. The research goal is to comprehensively examine the methodology in fabrication and characterization to understand the structure-transport correlation in YBa2Cu3O 7-x (YBCO) surface-coated conductors. High current density YBCO coated conductors were fabricated and characterized as candidates for second generation high-Tc wire technology. Critical current densities (Jc) greater than 1 x 106 A/cm2 at 77 K and zero magnetic field were obtained using thin films epitaxially grown by metalorganic chemical vapor deposition (MOCVD) and pulsed laser deposition (PLD) on oriented buffer layers. The biaxially textured oxide buffer layers were deposited by ion-beam-assisted deposition (IBAD). The transport properties of coated conductors were evaluated in high magnetic fields for intrinsic and extrinsic flux vortex pinning effects for improved high-field properties. Transport Jc's of these coated conductors at 7 tesla (77 K) were measured at values greater than 105 A/cm 2 with the magnetic field perpendicular to the YBCO c-axis (B⊥ c) in both MOCVD and PLD derived conductors. The Jc's in B || c orientation fell an order of magnitude lower at 7 tesla to values near 10 4 A/cm2 due to decreased intrinsic flux pinning. The critical current densities as a function of grain boundary misorientation were found to deviate from the general trend determined for single grain boundary junctions, due to the mosaic structure, which allows meandering current flow. Extensive parametric investigations of relevant thin film growth techniques were utilized to establish growth-property relationships that led to optimized fabrication of high-Tc conductors. The work contained in this dissertation successfully addresses the challenge in engineering low-angle grain boundary polycrystalline conductors for high-current high-field applications and develops a structure-property correlation, which is essential for advancing this technology.

Kapitza resistance at segregated boundaries in β-SiC

NASA Astrophysics Data System (ADS)

Goel, Nipun; Webb, Edmund, III; Oztekin, Alparslan; Rickman, Jeffrey; Neti, Sudhakar

Silicon Carbide is a candidate material for high-temperature thermoelectric applications for harvesting waste heat associated with exhaust from automotive and furnaces as well hot surfaces in solar towers and power electronics. However, for SiC to be a viable thermoelectric material, its thermoelectric figure of merit must be improved significantly. In this talk we examine the role of grain-boundary segregation on phononic thermal transport, an important factor in determining the figure of merit, via non-equilibrium molecular dynamics simulations. In particular, we consider the role of dopant concentration and dopant/matrix interactions on the enhancement of the Kapitza resistance of symmetric tilt grain boundaries. We find that the calculated resistance depends on the segregation profile, with increases of more than a factor of 50 (relative to an unsegregated boundary) at the highest dopant concentrations. Finally, we relate the calculated phonon density of states to changes in the Kapitza resistance.

Analysis of defect structure in silicon. Effect of grain boundary density on carrier mobility in UCP material

NASA Technical Reports Server (NTRS)

Dunn, J.; Stringfellow, G. B.; Natesh, R.

1982-01-01

The relationships between hole mobility and grain boundary density were studied. Mobility was measured using the van der Pauw technique, and grain boundary density was measured using a quantitative microscopy technique. Mobility was found to decrease with increasing grain boundary density.

Defect character at grain boundary facet junctions: Analysis of an asymmetric Σ = 5 grain boundary in Fe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Medlin, D. L.; Hattar, K.; Zimmerman, J. A.

Grain boundaries often develop faceted morphologies in systems for which the interfacial free energy depends on the boundary inclination. Although the mesoscale thermodynamic basis for such morphological evolution has been extensively studied, the influence of line defects, such as secondary grain boundary dislocations, on the facet configurations has not been thoroughly explored. In this paper, through a combination of atomistic simulations and electron microscopic observations, we examine in detail the structure of an asymmetric Σ = 5 [001] grain boundary in well-annealed, body-centered cubic (BCC) Fe. The observed boundary forms with a hill-and-valley morphology composed of nanoscale {310} and {210}more » facets. Our analysis clarifies the atomic structure of the {310}/{210} facet junctions and identifies the presence of an array of secondary grain boundary dislocations that are localized to these junctions. Analysis of the Burgers vectors of the grain boundary dislocations, which are of type (1/5)<310> and (1/5)<120>, shows that the defect density is consistent with that required to accommodate a small observed angular deviation from the exact Σ = 5 orientation relationship. As a result, these observations and analysis suggest a crucial role for secondary grain boundary dislocations in dictating the length-scale of grain boundary facets, a consideration which has not been included in prior analyses of facet evolution and equilibrium facet length.« less

Defect character at grain boundary facet junctions: Analysis of an asymmetric Σ = 5 grain boundary in Fe

DOE PAGES

Medlin, D. L.; Hattar, K.; Zimmerman, J. A.; ...

2016-11-16

Grain boundaries often develop faceted morphologies in systems for which the interfacial free energy depends on the boundary inclination. Although the mesoscale thermodynamic basis for such morphological evolution has been extensively studied, the influence of line defects, such as secondary grain boundary dislocations, on the facet configurations has not been thoroughly explored. In this paper, through a combination of atomistic simulations and electron microscopic observations, we examine in detail the structure of an asymmetric Σ = 5 [001] grain boundary in well-annealed, body-centered cubic (BCC) Fe. The observed boundary forms with a hill-and-valley morphology composed of nanoscale {310} and {210}more » facets. Our analysis clarifies the atomic structure of the {310}/{210} facet junctions and identifies the presence of an array of secondary grain boundary dislocations that are localized to these junctions. Analysis of the Burgers vectors of the grain boundary dislocations, which are of type (1/5)<310> and (1/5)<120>, shows that the defect density is consistent with that required to accommodate a small observed angular deviation from the exact Σ = 5 orientation relationship. As a result, these observations and analysis suggest a crucial role for secondary grain boundary dislocations in dictating the length-scale of grain boundary facets, a consideration which has not been included in prior analyses of facet evolution and equilibrium facet length.« less

Electric field-assisted sintering of nanocrystalline hydroxyapatite for biomedical applications

NASA Astrophysics Data System (ADS)

Tran, Tien Bich

As the main inorganic component of bone, hydroxyapatite (HA, Ca 10(PO4)6(OH)2) should be an ideal candidate in biomaterials selection. When grain sizes are in the nanometric regime, protein adsorption and cell adhesion are enhanced, while strength, hardness, and wear resistance are improved. Unfortunately, low phase stability, poor sinterability, and a tendency towards exaggerated grain coarsening challenge full densification of nanocrystalline hydroxyapatite by conventional sintering methods. The field-assisted sintering technique (FAST) has successfully consolidated a variety of nanocrystalline metals and ceramics in dramatically reduced times. The sintering enhancements observed during FAST can be attributed to thermal and athermal effects. The rapid heating rates (up to ˜1000ºC/min) afforded by FAST contribute a significant thermal effect. Since fast heating rates reduce powder exposure to sub-sintering temperatures, non-densifying surface diffusion is limited. The athermal effects of FAST are less well understood and can include plasma generation, dielectric breakdown, particle surface cleaning, grain boundary pinning, and space charge effects. Applying the field-assisted sintering technique to nanocrystalline hydroxyapatite yielded surprising results. Deviations from conventional densification behavior were observed, with dehydroxylation identified as the most deleterious process to densification as well as mechanical and biological performance. Since hydroxyapatite is not a stable phase at high temperatures and low water partial pressure atmospheres, desintering due to dehydroxylation-related pore formation became apparent during Stage III sintering. In fact, the degree of desintering and pore formation increased with the extent of Stage III sintering and grain growth. The atomic rearrangements taking place during grain boundary migration are believed to favor the formation of more-stable oxyapatite through hydroxyapatite dehydroxylation. This behavior was consistent during varied heating rate (50--400ºC/min) and varied pressure application (25--90 MPa) studies. While in vitro cytocompatibility studies using MG63 osteoblast-like cells demonstrated the biocompatibility of the FAST-processed specimens, bioactivity was sensitive to processing parameters. Since extensive dehydroxylation reduces the surface charge of the sintered materials, apatite deposition during simulated body fluid immersion only occurred when dehydroxylation was mild---i.e., on specimens sintered at low temperatures (800--900ºC) or for short periods. Microstructural investigations revealed that HA sintered at temperatures above 900ºC under an applied electric field contained nanometric residual pores in grain interiors, as well as micron-sized dehydroxylation-related pores at grain boundaries and grain boundary junctions. These larger pores were responsible for the increasing embrittlement of specimens sintered at higher temperatures. Although grain size dependence could not be found in the 60--100 nm grain size range, fracture toughness (KIC = 1.92 MPa√m, maximum) increased with decreasing sintering temperature. Results from the suite of investigations conducted demonstrate that biocompatible and bioactive nanocrystalline hydroxyapatite with enhanced mechanical properties can be efficiently manufactured by field-assisted sintering under controlled processing conditions.

Grain Boundary Plane Orientation Fundamental Zones and Structure-Property Relationships

PubMed Central

Homer, Eric R.; Patala, Srikanth; Priedeman, Jonathan L.

2015-01-01

Grain boundary plane orientation is a profoundly important determinant of character in polycrystalline materials that is not well understood. This work demonstrates how boundary plane orientation fundamental zones, which capture the natural crystallographic symmetries of a grain boundary, can be used to establish structure-property relationships. Using the fundamental zone representation, trends in computed energy, excess volume at the grain boundary, and temperature-dependent mobility naturally emerge and show a strong dependence on the boundary plane orientation. Analysis of common misorientation axes even suggests broader trends of grain boundary energy as a function of misorientation angle and plane orientation. Due to the strong structure-property relationships that naturally emerge from this work, boundary plane fundamental zones are expected to simplify analysis of both computational and experimental data. This standardized representation has the potential to significantly accelerate research in the topologically complex and vast five-dimensional phase space of grain boundaries. PMID:26498715

Grain boundary plane orientation fundamental zones and structure-property relationships

DOE Office of Scientific and Technical Information (OSTI.GOV)

Homer, Eric R.; Patala, Srikanth; Priedeman, Jonathan L.

2015-10-26

Grain boundary plane orientation is a profoundly important determinant of character in polycrystalline materials that is not well understood. This work demonstrates how boundary plane orientation fundamental zones, which capture the natural crystallographic symmetries of a grain boundary, can be used to establish structure-property relationships. Using the fundamental zone representation, trends in computed energy, excess volume at the grain boundary, and temperature-dependent mobility naturally emerge and show a strong dependence on the boundary plane orientation. Analysis of common misorientation axes even suggests broader trends of grain boundary energy as a function of misorientation angle and plane orientation. Due to themore » strong structure-property relationships that naturally emerge from this work, boundary plane fundamental zones are expected to simplify analysis of both computational and experimental data. This standardized representation has the potential to significantly accelerate research in the topologically complex and vast five-dimensional phase space of grain boundaries.« less

Determination of grain boundary mobility during recrystallization by statistical evaluation of electron backscatter diffraction measurements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Basu, I., E-mail: basu@imm.rwth-aachen.de; Chen, M.; Loeck, M.

One of the key aspects influencing microstructural design pathways in metallic systems is grain boundary motion. The present work introduces a method by means of which direct measurement of grain boundary mobility vs. misorientation dependence is made possible. The technique utilizes datasets acquired by means of serial electron backscatter diffraction (EBSD) measurements. The experimental EBSD measurements are collectively analyzed, whereby datasets were used to obtain grain boundary mobility and grain aspect ratio with respect to grain boundary misorientation. The proposed method is further validated using cellular automata (CA) simulations. Single crystal aluminium was cold rolled and scratched in order tomore » nucleate random orientations. Subsequent annealing at 300 °C resulted in grains growing, in the direction normal to the scratch, into a single deformed orientation. Growth selection was observed, wherein the boundaries with misorientations close to Σ7 CSL orientation relationship (38° 〈111〉) migrated considerably faster. The obtained boundary mobility distribution exhibited a non-monotonic behavior with a maximum corresponding to misorientation of 38° ± 2° about 〈111〉 axes ± 4°, which was 10–100 times higher than the mobility values of random high angle boundaries. Correlation with the grain aspect ratio values indicated a strong growth anisotropy displayed by the fast growing grains. The observations have been discussed in terms of the influence of grain boundary character on grain boundary motion during recrystallization. - Highlights: • Statistical microstructure method to measure grain boundary mobility during recrystallization • Method implementation independent of material or crystal structure • Mobility of the Σ7 boundaries in 5N Al was calculated as 4.7 × 10{sup –8} m{sup 4}/J ⋅ s. • Pronounced growth selection in the recrystallizing nuclei in Al • Boundary mobility values during recrystallization 2–3 orders of magnitude larger vis-à-vis curvature driven motion.« less

Grain boundary and triple junction diffusion in nanocrystalline copper

NASA Astrophysics Data System (ADS)

Wegner, M.; Leuthold, J.; Peterlechner, M.; Song, X.; Divinski, S. V.; Wilde, G.

2014-09-01

Grain boundary and triple junction diffusion in nanocrystalline Cu samples with grain sizes, , of ˜35 and ˜44 nm produced by spark plasma sintering were investigated by the radiotracer method using the 63Ni isotope. The measured diffusivities, Deff, are comparable with those determined previously for Ni grain boundary diffusion in well-annealed, high purity, coarse grained, polycrystalline copper, substantiating the absence of a grain size effect on the kinetic properties of grain boundaries in a nanocrystalline material at grain sizes d ≥ 35 nm. Simultaneously, the analysis predicts that if triple junction diffusion of Ni in Cu is enhanced with respect to the corresponding grain boundary diffusion rate, it is still less than 500ṡDgb within the temperature interval from 420 K to 470 K.

Fabrication and characterization of controllable grain boundary arrays in solution-processed small molecule organic semiconductor films

NASA Astrophysics Data System (ADS)

Wo, Songtao; Headrick, Randall L.; Anthony, John E.

2012-04-01

We have produced solution-processed thin films of 6,13-bis(tri-isopropyl-silylethynyl) pentacene with grain sizes from a few micrometers up to millimeter scale by lateral crystallization from a rectangular stylus. Grains are oriented along the crystallization direction, and the grain size transverse to the crystallization direction depends inversely on the writing speed, hence forming a regular array of oriented grain boundaries with controllable spacing. We utilize these controllable arrays to systematically study the role of large-angle grain boundaries in carrier transport and charge trapping in thin film transistors. The effective mobility scales with the grain size, leading to an estimate of the potential drop at individual large-angle grain boundaries of more than 1 volt. This result indicates that the structure of grain boundaries is not molecularly abrupt, which may be a general feature of solution-processed small molecule organic semiconductor thin films, where relatively high energy grain boundaries are typically formed. Transient measurements after switching from positive to negative gate bias or between large and small negative gate bias reveal reversible charge trapping, with time constants on the order of 10 s and trap densities that are correlated with grain boundary density. We suggest that charge diffusion along grain boundaries and other defects is the rate-determining mechanism of the reversible trapping.

Effect of He implantation on fracture behavior and microstructural evolution in F82H

NASA Astrophysics Data System (ADS)

Yabuuchi, Kiyohiro; Sato, Kiminori; Nogami, Shuhei; Hasegawa, Akira; Ando, Masami; Tanigawa, Hiroyasu

2014-12-01

Reduced-activation ferritic/martensitic steels (RAFMs) are the primary candidate structural materials for fusion reactor blanket components. He bubbles, which formed under 14 MeV neutron irradiation, is considered to cause some mechanical property changes. In a previous study, Hasegawa et al. investigated the fracture behavior using Charpy impact test of He implanted F82H by 50 MeV α-particles with cyclotron accelerator, and the ductile brittle transition temperature (DBTT) was increased and intergranular fracture (IGF) was observed. However, the cause of the IGF was not shown in the previous study. To clarify the cause of the IGF of the He implanted F82H by 50 MeV α-particles with cyclotron accelerator, the microstructure of the He implanted F82H was investigated. After Charpy impact test at 233 K, the brittle fracture surface of the He implanted specimen was observed by SEM and TEM. By SEM observation, grain boundary surface was clearly observed from the bottom of the notch to a depth of about 400 μm. This area correspond to the He implanted region. On the other hand, at unimplanted region, river pattern was observed and transgranular fracture occurred. TEM observation revealed the He bubbles agglomeration at dislocations, lath boundaries, and grain boundaries, and the coarsening of precipitates on grain boundaries. IGF of the He implanted F82H was caused by both He bubbles and coarsening precipitates.

Grain boundary microstructure, chemistry, and IGSCC in Alloy 600 and Alloy 690

DOE Office of Scientific and Technical Information (OSTI.GOV)

Norring, K.; Stiller, K.; Nilsson, J.O.

1992-12-31

The resistance to intergranular stress corrosion cracking of six different Alloy 600 and Alloy 690 steam generator tubes has been investigated. The composition of the materials at grain boundaries has been investigated using analytical transmission electron microscopy and atom probe field ion microscopy techniques. The depletion of chromium at the grain boundaries has been related to the type of grain boundary precipitates. Segregation of carbon and boron to the grain boundaries has been observed and quantified.

Surface modifications on toughened, fine-grained, recrystallized tungsten with repetitive ELM-like pulsed plasma irradiation

NASA Astrophysics Data System (ADS)

Kikuchi, Y.; Sakuma, I.; Kitagawa, Y.; Asai, Y.; Onishi, K.; Fukumoto, N.; Nagata, M.; Ueda, Y.; Kurishita, H.

2015-08-01

Surface modifications of toughened, fine-grained, recrystallized tungsten (TFGR W) materials with 1.1 wt.% TiC and 3.3 wt.% TaC dispersoids due to repetitive ELM-like pulsed (∼0.15 ms) helium plasma irradiation have been investigated by using a magnetized coaxial plasma gun. No surface cracking at the center part of the TFGR W samples exposed to 20 plasma pulses of ∼0.3 MJ m-2 was observed. The suppression of surface crack formation due to the increase of the grain boundary strength by addition of TiC and TaC dispersoids was confirmed in comparison with a pure W material. On the other hand, surface cracks and small pits appeared at the edge part of the TFGR W sample after the pulsed plasma irradiation. Erosion of the TiC and TaC dispersoids due to the pulsed plasma irradiation could cause the small pits on the surface, resulting in the surface crack formation.

Multiscale Modeling of Grain-Boundary Fracture: Cohesive Zone Models Parameterized From Atomistic Simulations

NASA Technical Reports Server (NTRS)

Glaessgen, Edward H.; Saether, Erik; Phillips, Dawn R.; Yamakov, Vesselin

2006-01-01

A multiscale modeling strategy is developed to study grain boundary fracture in polycrystalline aluminum. Atomistic simulation is used to model fundamental nanoscale deformation and fracture mechanisms and to develop a constitutive relationship for separation along a grain boundary interface. The nanoscale constitutive relationship is then parameterized within a cohesive zone model to represent variations in grain boundary properties. These variations arise from the presence of vacancies, intersticies, and other defects in addition to deviations in grain boundary angle from the baseline configuration considered in the molecular dynamics simulation. The parameterized cohesive zone models are then used to model grain boundaries within finite element analyses of aluminum polycrystals.

Grain-size-yield stress relationship: Analysis and computation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meyers, M.A.; Benson, D.J.; Fu, H.H.

1999-07-01

The seminal contributions of Julia Weertman to the understanding of the mechanical properties of nanocrystalline materials will be briefly outlined. A constitutive equation predicting the effect of grain size on the yield stress of metals, based on the model proposed by M.A. Meyers and E. Ashworth, is discussed and extended to the nanocrystalline regime. At large grain sizes, it has the Hall-Petch form, and in the nanocrystalline domain the slope gradually decreases until it asymptotically approaches the flow stress of the grain boundaries. The material is envisaged as a composite, comprised of the grain interior, with flow stress {sigma}{sub fB},more » and grain boundary work-hardened layer, with flow stress {sigma}{sub fGB}. Three principal factors contribute to the grain-boundary hardening: (1) the grain boundaries act as barriers to plastic flow; (2) the grain boundaries act as dislocation sources; and (3) elastic anisotropy causes additional stresses in grain-boundary surroundings. The predictions of this model are compared with experimental measurements over the mono, micro, and nanocrystalline domains. Computational predictions are made of plastic flow as a function of grain size incorporating elastic and plastic anisotropy as well as differences of dislocation accumulation rate in grain boundary regions and grain interiors. This is the first plasticity calculation that accounts for grain size effects in a physically-based manner. 58 refs., 7 figs., 1 tab.« less

Hydrogen segregation to inclined Σ3 < 110 >twin grain boundaries in nickel

DOE PAGES

O’Brien, Christopher J.; Foiles, Stephen M.

2016-08-04

Low-mobility twin grain boundaries dominate the microstructure of grain boundary-engineered materials and are critical to understanding their plastic deformation behaviour. The presence of solutes, such as hydrogen, has a profound effect on the thermodynamic stability of the grain boundaries. This work examines the case of a Σ3 grain boundary at inclinations from 0° ≤ Φ ≤ 90°. The angle Φ corresponds to the rotation of the Σ3 (1 1 1) < 1 1 0 > (coherent) into the Σ3 (1 1 2) < 1 1 0 > (lateral) twin boundary. To this end, atomistic models of inclined grain boundaries, utilisingmore » empirical potentials, are used to elucidate the finite-temperature boundary structure while grand canonical Monte Carlo models are applied to determine the degree of hydrogen segregation. In order to understand the boundary structure and segregation behaviour of hydrogen, the structural unit description of inclined twin grain boundaries is found to provide insight into explaining the observed variation of excess enthalpy and excess hydrogen concentration on inclination angle, but the explanatory power is limited by how the enthalpy of segregation is affected by hydrogen concentration. At higher concentrations, the grain boundaries undergo a defaceting transition. In order to develop a more complete mesoscale model of the interfacial behaviour, an analytical model of boundary energy and hydrogen segregation that relies on modelling the boundary as arrays of discrete 1/3 < 1 1 1 > disconnections is constructed. Lastly, the complex interaction of boundary reconstruction and concentration-dependent segregation behaviour exhibited by inclined twin grain boundaries limits the range of applicability of such an analytical model and illustrates the fundamental limitations for a structural unit model description of segregation in lower stacking fault energy materials.« less

First-principles study of the effect of phosphorus on nickel grain boundary

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Wenguan; Ren, Cuilan; Han, Han, E-mail: hanhan@sinap.ac.cn, E-mail: xuhongjie@sinap.ac.cn

2014-01-28

Based on first-principles quantum-mechanical calculations, the impurity-dopant effects of phosphorus on Σ5(012) symmetrical tilt grain boundary in nickel have been studied. The calculated binding energy suggests that phosphorus has a strong tendency to segregate to the grain boundary. Phosphorus forms strong and covalent-like bonding with nickel, which is beneficial to the grain boundary cohesion. However, a too high phosphorus content can result in a thin and fragile zone in the grain boundary, due to the repulsion between phosphorus atoms. As the concentration of phosphorus increases, the strength of the grain boundary increases first and then decreases. Obviously, there exists anmore » optimum concentration for phosphorus segregation, which is consistent with observed segregation behaviors of phosphorus in the grain boundary of nickel. This work is very helpful to understand the comprehensive effects of phosphorus.« less

Introducing Overlapping Grain Boundaries in Chemical Vapor Deposited Hexagonal Boron Nitride Monolayer Films

PubMed Central

2017-01-01

We demonstrate the growth of overlapping grain boundaries in continuous, polycrystalline hexagonal boron nitride (h-BN) monolayer films via scalable catalytic chemical vapor deposition. Unlike the commonly reported atomically stitched grain boundaries, these overlapping grain boundaries do not consist of defect lines within the monolayer films but are composed of self-sealing bilayer regions of limited width. We characterize this overlapping h-BN grain boundary structure in detail by complementary (scanning) transmission electron microscopy techniques and propose a catalytic growth mechanism linked to the subsurface/bulk of the process catalyst and its boron and nitrogen solubilities. Our data suggest that the overlapping grain boundaries are comparatively resilient against deleterious pinhole formation associated with grain boundary defect lines and thus may reduce detrimental breakdown effects when polycrystalline h-BN monolayer films are used as ultrathin dielectrics, barrier layers, or separation membranes. PMID:28410557

Direct mapping of ion diffusion times on LiCoO2 surfaces with nanometer resolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo, Senli; Jesse, Stephen; Kalnaus, Sergiy

2011-01-01

The strong coupling between the molar volume and mobile ion concentration in ionically-conductive solids is used for spatially-resolved studies of ionic transport on the polycrystalline LiCoO2 surface by time-resolved spectroscopy. Strong variability between ionic transport at the grain boundaries and within the grains is observed, and the relationship between relaxation and hysteresis loop formation is established. The use of the strain measurements allows ionic transport be probed on the nanoscale, and suggests enormous potential for probing ionic materials and devices.

Atomistic modelling of magnetic nano-granular thin films

NASA Astrophysics Data System (ADS)

Agudelo-Giraldo, J. D.; Arbeláez-Echeverry, O. D.; Restrepo-Parra, E.

2018-03-01

In this work, a complete model for studying the magnetic behaviour of polycrystalline thin films at nanoscale was processed. This model includes terms as exchange interaction, dipolar interaction and various types of anisotropies. For the first term, exchange interaction dependence of the distance n was used with purpose of quantify the interaction, mainly in grain boundaries. The third term includes crystalline, surface and boundary anisotropies. Special attention was paid to the disorder vector that determines the loss of cubic symmetry in the crystalline structure. For the case of the dipolar interaction, a similar implementation of the fast multiple method (FMM) was performed. Using these tools, modelling and simulations were developed varying the number of grains, and the results obtained presented a great dependence of the magnetic properties on this parameter. Comparisons between critical temperature and magnetization of saturation depending on the number of grains were performed for samples with and without factors as the surface and boundary anisotropies, and the dipolar interaction. It was observed that the inclusion of these parameters produced a decrease in the critical temperature and the magnetization of saturation; furthermore, in both cases, including and not including the disorder parameters, not only the critical temperature, but also the magnetization of saturation exhibited a range of values that also depend on the number of grains. This presence of a critical interval is due to each grain can transit toward the ferromagnetic state at different values of critical temperature. The processes of Zero field cooling (ZFC), Field cooling (FCC) and field cooling in warming mode (FCW) were necessary for understanding the mono-domain regime around of transition temperature, due to the high probabilities of a Super-paramagnetic (SPM) state.

Central role of TiO2 anatase grain boundaries on resistivity of CaCu3Ti4O12-based materials probed by Raman spectroscopy

NASA Astrophysics Data System (ADS)

De Almeida-Didry, Sonia; Autret, Cécile; Honstettre, Christophe; Lucas, Anthony; Zaghrioui, Mustapha; Pacreau, François; Gervais, François

2016-11-01

This study focuses on characterization and control of grain boundaries to enhance the properties of CaCu3Ti4O12 (CCTO) ceramics capacitors for industrial applications. A novel factor deals with TiO2 anatase revealed by Raman scattering in grain boundaries, found as a dominant parameter of largest sample resistivity, consistent with higher grain boundary resistivity and higher breakdown voltage. Four selected samples of CCTO-based compositions showing very different properties in terms of permittivity ranging from 1000 to 684 000 measured at 1 kHz, capacitance of grain boundaries ranging from 8 10-10 to 4.5 10-7 F cm-1, grain boundary resistivity ranging from 193 to 30,000,000 Ω cm and sample resistivity extending from 450 to 1011 Ω cm. The relationship between permittivity weighted by grain size and capacitance of grain boundaries confirms the internal barrier layer capacitance model over 5 orders of magnitude.

Electrical characterization of grain boundaries of CZTS thin films using conductive atomic force microscopy techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muhunthan, N.; Singh, Om Pal; Toutam, Vijaykumar, E-mail: toutamvk@nplindia.org

2015-10-15

Graphical abstract: Experimental setup for conducting AFM (C-AFM). - Highlights: • Cu{sub 2}ZnSnS{sub 4} (CZTS) thin film was grown by reactive co-sputtering. • The electronic properties were probed using conducting atomic force microscope, scanning Kelvin probe microscopy and scanning capacitance microscopy. • C-AFM current flow mainly through grain boundaries rather than grain interiors. • SKPM indicated higher potential along the GBs compared to grain interiors. • The SCM explains that charge separation takes place at the interface of grain and grain boundary. - Abstract: Electrical characterization of grain boundaries (GB) of Cu-deficient CZTS (Copper Zinc Tin Sulfide) thin films wasmore » done using atomic force microscopic (AFM) techniques like Conductive atomic force microscopy (CAFM), Kelvin probe force microscopy (KPFM) and scanning capacitance microscopy (SCM). Absorbance spectroscopy was done for optical band gap calculations and Raman, XRD and EDS for structural and compositional characterization. Hall measurements were done for estimation of carrier mobility. CAFM and KPFM measurements showed that the currents flow mainly through grain boundaries (GB) rather than grain interiors. SCM results showed that charge separation mainly occurs at the interface of grain and grain boundaries and not all along the grain boundaries.« less

Evidence of sealing and brine distribution at grain boundaries in natural fine-grained Halite (Qum Kuh salt fountain, Central Iran): implications for rheology of salt extrusions

NASA Astrophysics Data System (ADS)

Desbois, Guillaume; Urai, Janos L.; de Bresser, J. H. P.

2010-05-01

When grain boundary movement is stopped, surface energy related forces reassert themselves driving the system to its equilibrium conditions ([2], [6], [7], [8]). This could result in growth of islands and shrinking of channels and hence in healing the boundary by internal redistribution of fluid and solid in the contact region. Such islands are proposed to grow preferentially close to the contact rim and promote the healing of the grain-grain contact, which in turn prevents transport in or out the boundary region and thus traps the fluids in isolated inclusions. This contribution is focused on observation of grain boundary microstructures in natural mylonitic rocksalt collected from the distal part of Kum-Quh salt fountain (central Iran) in order to give unprecedented insight of grain boundary microstructures using argon-beam cross-sectioning to prepare high quality polished surfaces suitable for high-resolution SEM imaging. The possibility to use our SEM under cryogenic conditions allows also imaging the in-situ distribution of fluids. Results show that brine at grain boundaries occurs as thick layers (> µm in scale) corresponding to cross-sectioned wetted triple junction tubes, as filling at triple junction and as array of isolated fluids inclusions at grain-grain contacts. Close observations at islands contacts suggest the presence of a very thin fluid film (<100 nm). The most remarkable is evidence for sealing of pore space appearing as subhedral crystals filling the void space and decoupled from surrounding crystals by a thin brine layer. In parallel to this microstructural study, we deformed the same samples in order to simulate the simple shear flow at very low mean stress as in the salt fountain. First results suggest a complicated rheology. Samples loaded at σ < 0.7 MPa show no measurable deformation in a month, indicating strain rates less than 10-12 s-1 though, in fully activated pressure-solution (PS) creep, strain rates of several orders of magnitude are expected for similar grain size ([5]). Other samples, which were loaded to 1 MPa before reducing the stress to 0.5 MPa deformed at much higher but variable rates, up to 10-8 s-1, in good agreement with activated PS creep. If, at first look, our pilot deformation experiments seem to reflect a kind of "yield stress" for activation PS creep ([7]); the experimental stress does not reach the theoritical condition to enable activation of PS. Thus, we interpret that the apparent "yielding stress" may not reflect strictu senso the "yielding stress" as described in [7] but rather to a "yielding stress" corresponding to the elastic reassessment of the grain system before the initiation of PS at privileged seal-brine-grain contacts. In salt fountain conditions, mylonitic samples are expected to be in the healing domain, but "jumps" in active stress required to activate PS creep is hardly probable. Thus, we suggest that rainwater influx plays a fundamental role in activation of PS. Rainwater should enable the marginal dissolution of healed contacts and then decreases in the area fraction of grain boundary occupied by solid island contact causing an increase in island stress. Therefore, this points to cyclic deformation of salt fountain: (1) during rainy periods the fountain will deformed at relative high strain rate by dominant PS; while (2) during dry seasons, it will not significantly flow because the grain boundary healing will prevent PS and lead to dominant dislocation creep. This interpretation is in good agreement with recent structural studies ([1], [4]), which gives evidence for both dynamic dislocation and pressure-solution creeps, and measurement of rapid flow after rainy periods with flow rates compatible with fully activated PS ([3]). [1] Desbois G., Zavada P., Schleder Z. and Urai J.L. (In review). Deformation and recrystallization mechanisms in naturally deformed salt fountain: microstructural evidence for a switch in deformation mechanisms with increased availability of meteoric water and decreased grain size (Qum Kuh, central Iran). Submitted to Journal of Structural Geology. [2] Ghoussoub J., and Leroy Y.M. (2001), Solid-fluid phase transformation within grain boundaries during compaction by pressure solution, J. Mech. Phys. Solids, 49, 737 2385-2430. 738 [3] Jackson, M.P.A., (1985). Natural strain in diapiric and glacial rock salt, with emphasis on Oakwood dome, East Texas, Bureau of Economic Geology, The University of Texas at Austin, Texas. [4] Schléder Z. and Urai J.L. (2007). Deformation and recrystallization mechanisms in mylonitic shear zones in naturally deformed extrusive Eocene-Oligocene rock salt from Eyvanekey plateau and Garmsar hills (central Iran). Journal of structural geology, 29, 241-255. [5] Spiers C.J. and Carter N.L. (1988). Microphysics of rock salt flow in nature. In: M. Aubertin and H.R. Hardy, Editors, The Mechanical Behaviour of Salt: Proceedings of the Fourth Conference Series on Rock and Soil Mechanics, TTP Trans Tech Publications, Clausthal-Zellerfeld, 22: 115-128. [6] Urai J. L. (1983). Water assisted dynamic recrystallization and weakening in polycrystalline bischofite. Tectonophysics 96 (1-2): 125-157. [7] Van Noort R., Visser H.J.M., Spiers C.J. (2008) Influence of grain boundary structure on dissolution controlled pressure solution and retarding effects of grain boundary healing. Journal of Geophysical Research, 113, B03201. [8] Visser, H. J. M. (1999). Mass transfer processes in crystalline aggregates containing a fluid phase, Ph. D. thesis, Utrecht University, Utrecht.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghamarian, I.; Samani, P.; Rohrer, G. S.

Grain boundary engineering and other fundamental materials science problems (e.g., phase transformations and physical properties) require an improvement in the understanding of the type and population of grain boundaries in a given system – yet, databases are limited in number and spare in detail, including for hcp crystals such as zirconium. One way to rapidly obtain databases to analyze is to use small-grained materials and high spatial resolution orientation microscopy techniques, such as ASTAR™/precession electron diffraction. To demonstrate this, a study of grain boundary character distributions was conducted for α-zirconium deposited at room temperature on fused silica substrates using physicalmore » vapor deposition. The orientation maps of the nanocrystalline thin films were acquired by the ASTARα/precession electron diffraction technique, a new transmission electron microscope based orientation microscopy method. The reconstructed grain boundaries were classified as pure tilt, pure twist, 180°-twist and 180°-tilt grain boundaries based on the distribution of grain boundary planes with respect to the angle/axis of misorientation associated with grain boundaries. The results of the current study were compared to the results of a similar study on α-titanium and the molecular dynamics results of grain boundary energy for α-titanium.« less

A primer on selecting grain boundary sets for comparison of interfacial fracture properties in molecular dynamics simulations

DOE PAGES

Dingreville, Remi; Aksoy, Doruk; Spearot, Douglas E.

2017-08-21

In this study, all grain boundaries are not equal in their predisposition for fracture due to the complex coupling between lattice geometry, interfacial structure, and mechanical properties. The ability to understand these relationships is crucial to engineer materials resilient to grain boundary fracture. Here, a methodology is presented to isolate the role of grain boundary structure on interfacial fracture properties, such as the tensile strength and work of separation, using atomistic simulations. Instead of constructing sets of grain boundary models within the misorientation/structure space by simply varying the misorientation angle around a fixed misorientation axis, the proposed method creates setsmore » of grain boundary models by means of isocurves associated with important fracture-related properties of the adjoining lattices. Such properties may include anisotropic elastic moduli, the Schmid factor for primary slip, and the propensity for simultaneous slip on multiple slip systems. This approach eliminates the effect of lattice properties from the comparative analysis of interfacial fracture properties and thus enables the identification of structure-property relationships for grain boundaries. As an example, this methodology is implemented to study crack propagation along Ni grain boundaries. Segregated H is used as a means to emphasize differences in the selected grain boundary structures while keeping lattice properties fixed.« less

A primer on selecting grain boundary sets for comparison of interfacial fracture properties in molecular dynamics simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dingreville, Remi; Aksoy, Doruk; Spearot, Douglas E.

In this study, all grain boundaries are not equal in their predisposition for fracture due to the complex coupling between lattice geometry, interfacial structure, and mechanical properties. The ability to understand these relationships is crucial to engineer materials resilient to grain boundary fracture. Here, a methodology is presented to isolate the role of grain boundary structure on interfacial fracture properties, such as the tensile strength and work of separation, using atomistic simulations. Instead of constructing sets of grain boundary models within the misorientation/structure space by simply varying the misorientation angle around a fixed misorientation axis, the proposed method creates setsmore » of grain boundary models by means of isocurves associated with important fracture-related properties of the adjoining lattices. Such properties may include anisotropic elastic moduli, the Schmid factor for primary slip, and the propensity for simultaneous slip on multiple slip systems. This approach eliminates the effect of lattice properties from the comparative analysis of interfacial fracture properties and thus enables the identification of structure-property relationships for grain boundaries. As an example, this methodology is implemented to study crack propagation along Ni grain boundaries. Segregated H is used as a means to emphasize differences in the selected grain boundary structures while keeping lattice properties fixed.« less

Site energies and charge transfer rates near pentacene grain boundaries from first-principles calculations

NASA Astrophysics Data System (ADS)

Kobayashi, Hajime; Tokita, Yuichi

2015-03-01

Charge transfer rates near pentacene grain boundaries are derived by calculating the site energies and transfer integrals of 37 pentacene molecules using first-principles calculations. The site energies decrease considerably near the grain boundaries, and electron traps of up to 300 meV and hole barriers of up to 400 meV are generated. The charge transfer rates across the grain boundaries are found to be reduced by three to five orders of magnitude with a grain boundary gap of 4 Å because of the reduction in the transfer integrals. The electron traps and hole barriers also reduce the electron and hole transfer rates by factors of up to 10 and 50, respectively. It is essential to take the site energies into consideration to determine charge transport near the grain boundaries. We show that the complex site energy distributions near the grain boundaries can be represented by an equivalent site energy difference, which is a constant for any charge transfer pass. When equivalent site energy differences are obtained for various grain boundary structures by first-principles calculations, the effects of the grain boundaries on the charge transfer rates are introduced exactly into charge transport simulations, such as the kinetic Monte Carlo method.

Atomistic simulation of the trapping capability of He-vacancy defects at Ni {\\sum}^{}3\\left(1\\bar{1}2\\right)[110] grain boundary

NASA Astrophysics Data System (ADS)

Gong, Hengfeng; Wang, Chengbin; Zhang, Wei; Huai, Ping; Lu, Wei; Zhu, Zhiyuan

2016-12-01

He atoms tend to cluster and precipitate into bubbles that prefer to grow in the grain boundaries, resulting in high temperature He embrittlement with significantly degraded material properties. This is a major bottleneck in employing Ni-based alloys for applications such as molten salt reactors (MSRs). This paper focuses on understanding how the local grain boundary structure interacts with He atoms and how the local atomistic environment in the grain boundary influences the binding energy of He defects. Using molecular dynamics simulations, we have investigated the trapping capability of the Ni {\\sum}3≤ft(1 \\bar{1} 2\\right)≤ft[1 1 0\\right] grain boundary to He defects (He N ) and to He-vacancy defects (He N V M ). The two defects in the Ni grain boundary exhibit geometries with high symmetry. The binding energy of an interstitial He atom to He N V M defects is found to be generally larger in pure Ni than that in the grain boundary. We compared the binding energy of He N defects to the Ni vacancy and to the Ni grain boundary, finding that the Ni vacancy possesses a higher trapping strength to He N . We also found that the binding strength of He N to the grain boundary is stronger than that of He N V M to the grain boundary. The He-vacancy ratio in He N V M defects does not significantly affect the binding energy in the grain boundary plane. The current work will provide insight in understanding the experimentally observed He bubble formation in Ni-based alloys and bridge atomic scale events and damage with macroscopic failure.

Grain boundary engineering to control the discontinuous precipitation in multicomponent U10Mo alloy

DOE PAGES

Devaraj, Arun; Kovarik, Libor; Kautz, Elizabeth; ...

2018-03-30

Here, we demonstrate here that locally stabilized structure and compositional segregation at grain boundaries in a complex multicomponent alloy can be modified using high temperature homogenization treatment to influence the kinetics of phase transformations initiating from grain boundaries during subsequent low temperature annealing. Using aberration-corrected scanning transmission electron microscopy and atom probe tomography of a model multicomponent metallic alloy —uranium-10 wt% molybdenum (U-10Mo) a nuclear fuel, that is highly relevant to worldwide nuclear non-proliferation efforts, we demonstrate the ability to change the structure and compositional segregation at grain boundary, which then controls the subsequent discontinuous precipitation kinetics during sub-eutectoid annealing.more » A change in grain boundary from one characterized by segregation of Mo and impurities at grain boundary to a phase boundary with a distinct U 2MoSi 2C wetting phase precipitates introducing Ni and Al rich interphase complexions caused a pronounced reduction in area fraction of subsequent discontinuous precipitation. The broader implication of this work is in highlighting the role of grain boundary structure and composition in metallic alloys on dictating the fate of grain boundary initiated phase transformations like discontinuous precipitation or cellular transformation. This work highlights a new pathway to tune the grain boundary structure and composition to tailor the final microstructure of multicomponent metallic alloys.« less

Grain boundary engineering to control the discontinuous precipitation in multicomponent U10Mo alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Devaraj, Arun; Kovarik, Libor; Kautz, Elizabeth

Here, we demonstrate here that locally stabilized structure and compositional segregation at grain boundaries in a complex multicomponent alloy can be modified using high temperature homogenization treatment to influence the kinetics of phase transformations initiating from grain boundaries during subsequent low temperature annealing. Using aberration-corrected scanning transmission electron microscopy and atom probe tomography of a model multicomponent metallic alloy —uranium-10 wt% molybdenum (U-10Mo) a nuclear fuel, that is highly relevant to worldwide nuclear non-proliferation efforts, we demonstrate the ability to change the structure and compositional segregation at grain boundary, which then controls the subsequent discontinuous precipitation kinetics during sub-eutectoid annealing.more » A change in grain boundary from one characterized by segregation of Mo and impurities at grain boundary to a phase boundary with a distinct U 2MoSi 2C wetting phase precipitates introducing Ni and Al rich interphase complexions caused a pronounced reduction in area fraction of subsequent discontinuous precipitation. The broader implication of this work is in highlighting the role of grain boundary structure and composition in metallic alloys on dictating the fate of grain boundary initiated phase transformations like discontinuous precipitation or cellular transformation. This work highlights a new pathway to tune the grain boundary structure and composition to tailor the final microstructure of multicomponent metallic alloys.« less

A Numerical Model of Anisotropic Mass Transport Through Grain Boundary Networks

NASA Astrophysics Data System (ADS)

Wang, Yibo

Tin (Sn) thin films are commonly used in electronic circuit applications as coatings on contacts and solders for joining components. It is widely observed, for some such system, that whiskers---long, thin crystalline structures---emerge and grow from the film. The Sn whisker phenomenon has become a highly active research area since Sn whiskers have caused a large amount of damage and loss in manufacturing, military, medical and power industries. Though lead (Pb) addition to Sn has been used to solve this problem for over five decades, the adverse environmental and health effects of Pb have motivated legislation to severely constrain Pb use in society. People are researching and seeking the reasons which cause whiskers and corresponding methods to solve the problem. The contributing factors to cause a Sn whisker are potentially many and much still remains unknown. Better understanding of fundamental driving forces should point toward strategies to improve (a) the accuracy with which we can predict whisker formation, and (b) our ability to mitigate the phenomenon. This thesis summarizes recent important research achievements in understanding Sn whisker formation and growth, both experimentally and theoretically. Focus is then placed on examining the role that anisotropy in grain boundary diffusivity plays in determining whisker characteristics (specifically, whether they form and, if so, where on a surface). To study this aspect of the problem and to enable future studies on stress driven grain boundary diffusion, this thesis presents a numerical anisotropic mass transport model. In addition to presenting details of the model and implementation, model predictions for a set of increasingly complex grain boundary networks are discussed. Preliminary results from the model provide evidence that anisotropic grain boundary diffusion may be a primary driving mechanism in whisker formation.

Extreme grain size reduction in dolomite: microstructures and mechanisms.

NASA Astrophysics Data System (ADS)

Kennedy, L.; White, J. C.

2007-12-01

Pure dolomite sample were deformed at room temperature and under a variety of confining pressures (0 - 100MPa) to examine the processes of grain size reduction. The dolomite is composed of > 97 vol. % dolomite with accessory quartz, calcite, tremolite, and muscovite and has been metamorphosed to amphibolite facies and subsequently annealed. At the hand sample scale, the rock is isotropic, except for minor, randomly oriented tremolite porphyroblasts, and weakly aligned muscovite. At the thin section scale, coarser grains have lobate grain boundaries, exhibit minor to no undulose extinction and few deformation twins, although well- developed subgrains are present. Growth twins are common, as is the presence of well developed {1011} cleavage. Mean grain size 476 microns, and porosity is essentially zero (Austin and Kennedy, 2006). Samples contain diagonal to subvertical faults. Fractures are lined with an exceptionally fine-grained, powdered dolomite. Even experiments done at no confining pressure and stopped before sliding on the fracture surfaces occurred had significant powdered gouge developed along the surfaces. In this regard, fracturing of low porosity, pure dolomite, with metamorphic textures (e.g. lobate, interlocking grain boundaries) results in the development of fine-grained gouge. As expected the dolomite exhibited an increase in strength with increasing confining pressure, with a maximum differential stress of ~400MPa at 100 MPa confining pressure. At each chosen confining pressure, two experiments were performed and stopped at different stages along the load-displacement curve: just before yield stress and at peak stress. Microstructures at each stage were observed in order to determine the possible mechanisms for extreme grain size reduction. SEM work shows that in samples with little to no apparent displacement along microfractures, extreme grain size reduction still exists, suggesting that frictional sliding and subsequent cataclasis may not be the mechanism responsible for grain size reduction. Within individual dolomite clasts, apparent Mode I cracks are also lined with powedered gouge. Alternative mechanisms for grain size reduction are explored. Austin et al. 2005, Geological Society, London, Special Publications, 243, 51-66.3.

Enhanced Hydrogen Transport over Palladium Ultrathin Films through Surface Nanostructure Engineering.

PubMed

Abate, Salvatore; Giorgianni, Gianfranco; Gentiluomo, Serena; Centi, Gabriele; Perathoner, Siglinda

2015-11-01

Palladium ultrathin films (around 2 μm) with different surface nanostructures are characterized by TEM, SEM, AFM, and temperature programmed reduction (TPR), and evaluated in terms of H2 permeability and H2-N2 separation. A change in the characteristics of Pd seeds by controlled oxidation-reduction treatments produces films with the same thickness, but different surface and bulk nanostructure. In particular, the films have finer and more homogeneous Pd grains, which results in lower surface roughness. Although all samples show high permeo-selectivity to H2 , the samples with finer grains exhibit enhanced permeance and lower activation energy for H2 transport. The analysis of the data suggests that grain boundaries between the Pd grains at the surface favor H2 transfer from surface to subsurface. Thus, the surface nanostructure plays a relevant role in enhancing the transport of H2 over the Pd ultrathin film, which is an important aspect to develop improved membranes that function at low temperatures and toward new integrated process architectures in H2 and syngas production with enhanced sustainability. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study of Etching Pits in a Large-grain Single Cell Bulk Niobium Cavity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Xin; Ciovati, Gianluigi; Reece, Charles E.

2009-11-01

Performance of SRF cavities are limited by non-linear localized effects. The variation of local material characters between "hot" and "cold" spots is thus of intense interest. Such locations were identified in a BCP-etched large-grain single-cell cavity and removed for examination by high resolution electron microscopy (SEM), electron-back scattering diffraction microscopy (EBSD), optical microscopy, and 3D profilometry. Pits with clearly discernable crystal facets were observed in both "hotspot" and "coldspot" specimens. The pits were found in-grain, at bi-crystal boundaries, and on tri-crystal junctions. They are interpreted as etch pits induced by surface crystal defects (e.g. dislocations). All "coldspots" examined had qualitativelymore » low density of etching pits or very shallow tri-crystal boundary junction. EBSD revealed crystal structure surrounding the pits via crystal phase orientation mapping, while 3D profilometry gave information on the depth and size of the pits. In addition, a survey of the samples by energy dispersive X-ray analysis (EDX) did not show any significant contamination of the samples surface.« less

Competing Grain Boundary and Interior Deformation Mechanisms with Varying Sizes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Wei; Gao, Yanfei; Nieh, T. G.

In typical coarse-grained alloys, the dominant plastic deformations are dislocation gliding or climbing, and material strengths can be tuned by dislocation interactions with grain boundaries, precipitates, solid solutions, and other defects. With the reduction of grain size, the increase of material strengths follows the classic Hall-Petch relationship up to nano-grained materials. Even at room temperatures, nano-grained materials exhibit strength softening, or called the inverse Hall-Petch effect, as grain boundary processes take over as the dominant deformation mechanisms. On the other hand, at elevated temperatures, grain boundary processes compete with grain interior deformation mechanisms over a wide range of the appliedmore » stress and grain sizes. This book chapter reviews and compares the rate equation model and the microstructure-based finite element simulations. The latter explicitly accounts for the grain boundary sliding, grain boundary diffusion and migration, as well as the grain interior dislocation creep. Therefore the explicit finite element method has clear advantages in problems where microstructural heterogeneities play a critical role, such as in the gradient microstructure in shot peening or weldment. Furthermore, combined with the Hall-Petch effect and its breakdown, the above competing processes help construct deformation mechanism maps by extending from the classic Frost-Ashby type to the ones with the dependence of grain size.« less

Evolution of Grain Boundary Precipitates in an Al-Cu-Li Alloy During Aging

NASA Astrophysics Data System (ADS)

Ott, Noémie; Kairy, Shravan K.; Yan, Yuanming; Birbilis, Nick

2017-01-01

The grain boundary microstructure of Al-Cu-Li alloy AA2050 was investigated for different isothermal aging times to rationalize intergranular corrosion (IGC) characteristics. In the underaged condition, the dominant grain boundary precipitates are fine T1 (Al2CuLi). Extended aging revealed that grain boundaries were decorated by large T1 precipitates and S' phase (Al2CuMg), with S' growth not dimensionally constrained. Such a transition in the precipitate type at grain boundaries is a unique feature of the Al-Cu-Li system.

Effect of irradiation on mechanical properties of symmetrical grain boundaries investigated by atomic simulations

NASA Astrophysics Data System (ADS)

Wang, X. Y.; Gao, N.; Setyawan, W.; Xu, B.; Liu, W.; Wang, Z. G.

2017-08-01

Tensile response of irradiated symmetric grain boundaries to the externally applied strain has been studied using atomic simulation methods. The absorption of irradiation induced defects by grain boundaries has been confirmed to degrade the mechanical properties of grain boundaries through the change of its undertaken deformation mechanism. Atomic rearrangement, the formations of a stress accumulation region and vacancy-rich zone and the nucleation and movement of dislocations under stress effect have been observed after the displacement cascades in grain boundaries, which are considered as main reasons to induce above degradation. These results suggest the necessity of considering both trapping efficiency to defects and the mechanical property change of irradiated grain boundaries for further development of radiation resistant materials.

Observation of a brine layer on an ice surface with an environmental scanning electron microscope at higher pressures and temperatures.

PubMed

Krausko, Ján; Runštuk, Jiří; Neděla, Vilém; Klán, Petr; Heger, Dominik

2014-05-20

Observation of a uranyl-salt brine layer on an ice surface using backscattered electron detection and ice surface morphology using secondary-electron detection under equilibrium conditions was facilitated using an environmental scanning electron microscope (ESEM) at temperatures above 250 K and pressures of hundreds of Pa. The micrographs of a brine layer over ice grains prepared by either slow or shock freezing provided a complementary picture of the contaminated ice grain boundaries. Fluorescence spectroscopy of the uranyl ions in the brine layer confirmed that the species exists predominately in the solvated state under experimental conditions of ESEM.

Spatially resolved mapping of electrical conductivity across individual domain (grain) boundaries in graphene.

PubMed

Clark, Kendal W; Zhang, X-G; Vlassiouk, Ivan V; He, Guowei; Feenstra, Randall M; Li, An-Ping

2013-09-24

All large-scale graphene films contain extended topological defects dividing graphene into domains or grains. Here, we spatially map electronic transport near specific domain and grain boundaries in both epitaxial graphene grown on SiC and CVD graphene on Cu subsequently transferred to a SiO2 substrate, with one-to-one correspondence to boundary structures. Boundaries coinciding with the substrate step on SiC exhibit a significant potential barrier for electron transport of epitaxial graphene due to the reduced charge transfer from the substrate near the step edge. Moreover, monolayer-bilayer boundaries exhibit a high resistance that can change depending on the height of substrate step coinciding at the boundary. In CVD graphene, the resistance of a grain boundary changes with the width of the disordered transition region between adjacent grains. A quantitative modeling of boundary resistance reveals the increased electron Fermi wave vector within the boundary region, possibly due to boundary induced charge density variation. Understanding how resistance change with domain (grain) boundary structure in graphene is a crucial first step for controlled engineering of defects in large-scale graphene films.

Grain boundary modification to suppress lithium penetration through garnet-type solid electrolyte

NASA Astrophysics Data System (ADS)

Hongahally Basappa, Rajendra; Ito, Tomoko; Morimura, Takao; Bekarevich, Raman; Mitsuishi, Kazutaka; Yamada, Hirotoshi

2017-09-01

Garnet-type solid electrolytes are one of key materials to enable practical usage of lithium metal anode for high-energy-density batteries. However, it suffers from lithium growth in pellets on charging, which causes short circuit. In this study, grain boundaries of Li6.5La3Zr1.5Ta0.5O12 (LLZT) pellets are modified with Li2CO3 and LiOH to investigate the influence of the microstructure of grain boundaries on lithium growth and to study the mechanism of the lithium growth. In spite of similar properties (relative density of ca. 96% and total ionic conductivity of 7 × 10-4 S cm-1 at 25 °C), the obtained pellets exhibit different tolerance on the short circuit. The LLZT pellets prepared from LiOH-modified LLZT powders exhibit rather high critical current density of 0.6 mA cm-2, at which short circuit occurs. On the other hand, the LLZT pellets without grain boundary modification short-circuited at 0.15 mA cm-2. Microstructural analyses by means of SEM, STEM and EIS suggest that lithium grows through interconnected open voids, and reveal that surface layers such as Li2CO3 and LiOH are not only plug voids but also facilitate the sintering of LLZT to suppress the lithium growth. The results indicate a strategy towards short-circuit-free lithium metal batteries.

Influence of structural parameters on the tendency of VVER-1000 reactor pressure vessel steel to temper embrittlement

NASA Astrophysics Data System (ADS)

Gurovich, B.; Kuleshova, E.; Zabusov, O.; Fedotova, S.; Frolov, A.; Saltykov, M.; Maltsev, D.

2013-04-01

In this paper the influence of structural parameters on the tendency of steels to reversible temper embrittlement was studied for assessment of performance properties of reactor pressure vessel steels with extended service life. It is shown that the growth of prior austenite grain size leads to an increase of the critical embrittlement temperature in the initial state. An embrittlement heat treatment at the temperature of maximum manifestation of temper embrittlement (480 °C) shifts critical embrittlement temperature to higher values due to the increase of the phosphorus concentration on grain boundaries. There is a correlation between phosphorus concentration on boundaries of primary austenite grains and the share of brittle intergranular fracture (that, in turn, depends on impact test temperature) in the fracture surfaces of the tested Charpy specimens.

Effect of Sn on the oxide subscale structure formed on a 3% Si steel

NASA Astrophysics Data System (ADS)

Cesar, Maria das G. M. M.; Silveira, Carolina C.; Paolinelli, Sebastião C.; Cicale, Stefano

2018-04-01

Addition of tin in 3% Si steel is a method to improve magnetic properties since tin in steel is known as an element that segregates at grain boundaries, inhibits grain growth and has a dragging effect on grain boundary movement. However, tin is generally known as an element that has a harmful effect on surface coating properties. The oxide subscale formed on the decarburization annealing of a 3% Si steel containing tin was investigated by SEM, EDS, GDS and FTIR. The forsterite film was evaluated by SEM, EDS and GDS. The higher tin content decreased thickness, oxygen and fayalite/silica ratio in the subscale and resulted into a discontinuous forsterite film with poor oxidation resistance. After secondary coating the samples presented a reddish color due to the formation of iron oxide and poor dielectric property.

Grain boundary phases in bcc metals

DOE PAGES

Frolov, T.; Setyawan, W.; Kurtz, R. J.; ...

2018-01-01

Evolutionary grand-canonical search predicts novel grain boundary structures and multiple grain boundary phases in elemental body-centered cubic (bcc) metals represented by tungsten, tantalum and molybdenum.

Grain Cluster Microstructure and Grain Boundary Character Distribution in Alloy 690

NASA Astrophysics Data System (ADS)

Xia, Shuang; Zhou, Bangxin; Chen, Wenjue

2009-12-01

The effects of thermal-mechanical processing (TMP) on microstructure evolution during recrystallization and grain boundary character distribution (GBCD) in aged Alloy 690 were investigated by the electron backscatter diffraction (EBSD) technique and optical microscopy. The original grain boundaries of the deformed microstructure did not play an important role in the manipulation of the proportion of the Σ3 n ( n = 1, 2, 3…) type boundaries. Instead, the grain cluster formed by multiple twinning starting from a single nucleus during recrystallization was the key microstructural feature affecting the GBCD. All of the grains in this kind of cluster had Σ3 n mutual misorientations regardless of whether they were adjacent. A large grain cluster containing 91 grains was found in the sample after a small-strain (5 pct) and a high-temperature (1100 °C) recrystallization anneal, and twin relationships up to the ninth generation (Σ39) were found in this cluster. The ratio of cluster size over grain size (including all types of boundaries as defining individual grains) dictated the proportion of Σ3 n boundaries.

Structure and transport at grain boundaries in polycrystalline olivine: An atomic-scale perspective

NASA Astrophysics Data System (ADS)

Mantisi, Boris; Sator, Nicolas; Guillot, Bertrand

2017-12-01

Structure and transport properties at grain boundaries in polycrystalline olivine have been investigated at the atomic scale by molecular dynamics simulation (MD) using an empirical ionocovalent interaction potential. On the time scale of the simulation (a few tens of nanoseconds for a system size of ∼650,000 atoms) grain boundaries and grain interior were identified by mapping the atomic displacements along the simulation run. In the investigated temperature range (1300-1700 K) the mean thickness of the grain boundary phase is evaluated between 0.5 and 2 nm, a value which depends on temperature and grain size. The structure of the grain boundary phase is found to be disordered (amorphous-like) and is different from the one exhibited by the supercooled liquid. The self-diffusion coefficients of major elements in the intergranular region range from ∼10-13 to 10-10 m2/s between 1300 and 1700 K (with DSigb < DOgb < DFegb < DMggb) and are only one order of magnitude smaller than those evaluated in the supercooled melt. In using a newly derived expression for the bulk self-diffusion coefficient it is concluded that the latter one is driven by the grain boundary contribution as long as the grain size is smaller than a centimeter. In assuming that the electrical conduction at grain boundaries is purely ionic, the macroscopic grain boundary conductivity is found to be two orders of magnitude lower than in molten olivine, and one order of magnitude higher than the lattice conductivity. A consequence is that the conductivity of the olivine polycrystal is dominated by the grain interior contribution as soon as the grain size is larger than a micrometer or so. The grain boundary viscosity has been evaluated from the Green-Kubo relation expressing the viscosity as function of the stress tensor time correlation function. In spite of a slow convergence of the calculation by MD, the grain boundary viscosity was estimated about ∼105 Pa s at 1500 K, a value in agreement with high-temperature viscoelastic relaxation data. An interesting information gained from MD is that sliding at grain boundaries is essentially controlled by the internal friction between the intergranular phase and the grain edges.

The effect of water on recrystallization behavior and grain boundary morphology in calcite observations of natural marble mylonites

NASA Astrophysics Data System (ADS)

Schenk, Oliver; Urai, Janos L.; Evans, Brian

2005-10-01

Fluids are inferred to play a major role in the deformation and recrystallization of many minerals (e.g. quartz, olivine, halite, feldspar). In this study, we sought to identify the effect of fluids on grain boundary morphology and recrystallization processes in marble mylonites during shear zone evolution. We compared the chemistry, microstructure and mesostructure of calcite marble mylonites from the Schneeberg Complex, Southern Tyrole, Italy, to that from the Naxos Metamorphic Core Complex, Greece. These two areas were selected for comparison because they have similar lithology and resemble each other in chemical composition. In addition, calcite-dolomite geothermometry indicates similar temperatures for shear zone formation: 279±25 °C (Schneeberg Complex) and 271±15 °C (Naxos high-grade core). However, the two settings are different in the nature of the fluids present during the shear zone evolution. In the Schneeberg mylonites, both the alteration of minerals during retrograde metamorphism in the neighboring micaschists and the existence of veins suggest that aqueous fluids were present during mylonitization. The absence of these features in the Naxos samples indicates that aqueous fluids were not as prevalent during deformation. This conclusion is also supported by the stable isotope signature. Observations of broken and planar surfaces using optical and scanning electron microscopes did not indicate major differences between the two mylonites: grain boundaries in both settings display pores with shapes controlled by crystallography, and have pore morphologies that are similar to observations from crack and grain-boundary healing experiments. Grain size reduction was predominantly the result of subgrain rotation recrystallization. However, the coarse grains inside the wet protomylonites (Schneeberg) are characterized by intracrystalline shear zones.

Grain-Boundary Resistance in Copper Interconnects: From an Atomistic Model to a Neural Network

NASA Astrophysics Data System (ADS)

Valencia, Daniel; Wilson, Evan; Jiang, Zhengping; Valencia-Zapata, Gustavo A.; Wang, Kuang-Chung; Klimeck, Gerhard; Povolotskyi, Michael

2018-04-01

Orientation effects on the specific resistance of copper grain boundaries are studied systematically with two different atomistic tight-binding methods. A methodology is developed to model the specific resistance of grain boundaries in the ballistic limit using the embedded atom model, tight- binding methods, and nonequilibrium Green's functions. The methodology is validated against first-principles calculations for thin films with a single coincident grain boundary, with 6.4% deviation in the specific resistance. A statistical ensemble of 600 large, random structures with grains is studied. For structures with three grains, it is found that the distribution of specific resistances is close to normal. Finally, a compact model for grain-boundary-specific resistance is constructed based on a neural network.

Investigation of olivine and orthopyroxene grain boundaries by atom probe tomography

NASA Astrophysics Data System (ADS)

Krawczynski, M.; Skemer, P. A.; Bachhav, M.; Dong, Y.; Marquis, E. A.

2016-12-01

Accurate chemical analysis at grain boundaries is challenging by traditional microscopic techniques, especially for poor conducting geological samples. Atom probe tomography (APT) is a unique technique that can elucidate chemistry and 3-D distribution of elements within a sample volume at the sub-nanometer length scale. With advances in laser and sample preparation techniques in the last decade, APT is now successfully applied to a wide range of poor conducting materials like metal oxides, ceramics, and biological minerals. In this study, we apply the APT technique to investigate the grain boundary chemistry of orthopyroxene (opx) and olivine. These minerals are the most abundant in the upper mantle and their grain boundaries may be important geochemical reservoirs in Earth. Moreover, physical properties such as grain boundary diffusivity, conductivity, and mobility, are likely influenced by the presence or absence of impurities. Single crystals of opx and olivine grains, separated from a San Carlos xenolith, were deformed at 1 GPa and 1500 K. Plastic deformation promoted dynamic recrystallization, creating new grain boundaries within a chemically homogeneous medium. Needle shaped specimens of opx-opx and olivine-olivine grain boundaries were prepared using standard lift out techniques and a dual beam focused ion beam (FIB). APT analyses were performed in laser mode with laser energy of 50 pJ/pulse, repetition rate of 200 kHz, and detection rate of 1%. A 3-D distribution of elements was reconstructed and 1-D profiles across the grain boundary have been calculated. Fe, Al, and Ca show enrichments at the grain boundaries for both phases, consistent with previous studies that used STEM/EDX or EPMA techniques. Although qualitatively similar, the spatial resolution of the APT method is significantly better than other methods, and our data show that the grain-boundary enrichment of minor elements in both olivine and pyroxene compositions is limited to a region no greater than 2-4 nm thick. These new data place constraints on the thickness of the grain boundary zone with unparalleled precision, allowing more accurate calculation of partition coefficients as well as diffusion coefficients from experimental studies of grain boundary diffusion.

Improvement of the Reliability of Dielectrics for MLCC

NASA Astrophysics Data System (ADS)

Nakamura, Tomoyuki; Yao, Takayuki; Ikeda, Jun; Kubodera, Noriyuki; Takagi, Hiroshi

2011-10-01

To achieve enough reliability of monolithic ceramic capacitor, it is important to know the contribution of grain boundary and grain interior to its reliability and insulation resistance. As the number of grain boundaries per layer increased, mean time to failure (MTTF) increased. In addition, as the number of grain boundaries per layer increased, samples showed lower current leakage in the measured electric field range. Using these data, the grain boundary E-J curves were determined by simulation. As a result, temperature and electric field dependence of insulation resistance of grain boundary were very low. The insulation characteristics of one BaTiO3 grain per layer were examined. The resistance and reliability of grain interior were very low. To improve the degradation resistance of grain interior, Ca-doped BaTiO3-based dielectrics were developed. The influence of Ca substitution on MTTF was investigated and it was found out that MTTF increased with the increase of Ca substitution.

How to interpret current-voltage relationships of blocking grain boundaries in oxygen ionic conductors.

PubMed

Kim, Seong K; Khodorov, Sergey; Chen, Chien-Ting; Kim, Sangtae; Lubomirsky, Igor

2013-06-14

A new model based on a linear diffusion equation is proposed to explain the current-voltage characteristics of blocking grain boundaries in Y-doped CeO2 in particular. One can also expect that the model can be applicable to the ionic conductors with blocking grain boundaries, in general. The model considers an infinitely long chain of identical grains separated by grain boundaries, which are treated as regions in which depletion layers of mobile ions are formed due to trapping of immobile charges that do not depend on the applied voltage as well as temperature. The model assumes that (1) the grain boundaries do not represent physical blocking layers, which implies that if there is a second phase at the grain boundaries, then it is too thin to impede ion diffusion and (2) the ions follow Boltzmann distribution throughout the materials. Despite its simplicity, the model successfully reproduces the "power law": current proportional to voltage power n and illustrated with the experimental example of Y-doped ceria. The model also correctly predicts that the product nT, where T is the temperature in K, is constant and is proportional to the grain boundary potential as long as the charge at the grain boundaries remains trapped. The latter allows its direct determination from the current-voltage characteristics and promises considerable simplification in the analysis of the electrical characteristics of the grain boundaries with respect to the models currently in use.

Local texture and grain boundary misorientations in high H(C) oxide superconductors

NASA Astrophysics Data System (ADS)

Kroeger, D. M.; Goyal, A.; Specht, E. D.; Tkaczyk, J. E.; Sutliff, J.; Deluca, J. A.; Wang, Z. L.; Riley, G. N., Jr.

The orientations of hundreds of contiguous grains in high J(C) TlBa2Ca2Cu3O(x) deposits and (Bi, Pb)2 Sr2Ca2Cu3O(y) powder-in-tube tapes have been determined from electron back scatter diffraction patterns (EBSP). The misorientation angles and axes of rotation (angle/axis pairs) for grain boundaries connecting these grains were calculated. For both materials the population of low angle boundaries was found to be much larger than expected from calculations based on the macroscopic texture. The TlBa2Ca2Cu3O(x) deposits exhibit pronounced local texture which has been defined by EBSP and x-ray diffraction. Locally grains show significant in-plane (a-axis) alignment even though macroscopically a-axes are random, indicating the presence of colonies of grains with similar a-axis orientations. In (Bi, Pb)2 Sr2Ca2Cu3O(x) tapes no local texture was observed. In both materials the existence of connected networks of small angle grain boundaries can be inferred. Coincident site lattice (CSL) grain boundaries are also present in higher than expected numbers. Grain boundary energy thus appears to play a significant role in enhancing the population of potentially strongly-linked boundaries. We propose that long range strongly-linked conduction occurs through a percolative network small angle (and perhaps CSL) grain boundaries.

Impact of Wide-Ranging Nanoscale Chemistry on Band Structure at Cu(In, Ga)Se 2 Grain Boundaries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stokes, Adam; Al-Jassim, Mowafak; Diercks, David

The relative chemistry from grain interiors to grain boundaries help explain why grain boundaries may be beneficial, detrimental or benign towards device performance. 3D Nanoscale chemical analysis extracted from atom probe tomography (APT) (10’s of parts-per-million chemical sensitivity and sub-nanometer spatial resolution) of twenty grain boundaries in a high-efficiency Cu(In, Ga)Se 2 solar cell shows the matrix and alkali concentrations are wide-ranging. The concentration profiles are then related to band structure which provide a unique insight into grain boundary electrical performance. Fluctuating Cu, In and Ga concentrations result in a wide distribution of potential barriers at the valence band maximummore » (VBM) (-10 to -160 meV) and the conduction band minimum (CBM) (-20 to -70 meV). Furthermore, Na and K segregation is not correlated to hampering donors, (In, Ga) Cu and V Se, contrary to what has been previously reported. In addition, Na and K are predicted to be n-type dopants at grain boundaries. An overall band structure at grain boundaries is presented.« less

Impact of Wide-Ranging Nanoscale Chemistry on Band Structure at Cu(In, Ga)Se 2 Grain Boundaries

DOE PAGES

Stokes, Adam; Al-Jassim, Mowafak; Diercks, David; ...

2017-10-26

The relative chemistry from grain interiors to grain boundaries help explain why grain boundaries may be beneficial, detrimental or benign towards device performance. 3D Nanoscale chemical analysis extracted from atom probe tomography (APT) (10’s of parts-per-million chemical sensitivity and sub-nanometer spatial resolution) of twenty grain boundaries in a high-efficiency Cu(In, Ga)Se 2 solar cell shows the matrix and alkali concentrations are wide-ranging. The concentration profiles are then related to band structure which provide a unique insight into grain boundary electrical performance. Fluctuating Cu, In and Ga concentrations result in a wide distribution of potential barriers at the valence band maximummore » (VBM) (-10 to -160 meV) and the conduction band minimum (CBM) (-20 to -70 meV). Furthermore, Na and K segregation is not correlated to hampering donors, (In, Ga) Cu and V Se, contrary to what has been previously reported. In addition, Na and K are predicted to be n-type dopants at grain boundaries. An overall band structure at grain boundaries is presented.« less

The role of boundary variability in polycrystalline grain-boundary diffusion

NASA Astrophysics Data System (ADS)

Moghadam, M. M.; Rickman, J. M.; Harmer, M. P.; Chan, H. M.

2015-01-01

We investigate the impact of grain-boundary variability on mass transport in a polycrystal. More specifically, we perform both numerical and analytical studies of steady-state diffusion in prototypical microstructures in which there is either a discrete spectrum of grain-boundary activation energies or else a complex distribution of grain-boundary character, and hence a continuous spectrum of boundary activation energies. An effective diffusivity is calculated for these structures using simplified multi-state models and, for the case of a continuous spectrum, employing experimentally obtained grain-boundary energy data. We identify different diffusive regimes for these cases and quantify deviations from Arrhenius behavior using effective medium theory. Finally, we examine the diffusion kinetics of a simplified model of an interfacial layering (i.e., complexion) transition.

Effect of one-step recrystallization on the grain boundary evolution of CoCrFeMnNi high entropy alloy and its subsystems.

PubMed

Chen, Bo-Ru; Yeh, An-Chou; Yeh, Jien-Wei

2016-02-29

In this study, the grain boundary evolution of equiatomic CoCrFeMnNi, CoCrFeNi, and FeCoNi alloys after one-step recrystallization were investigated. The special boundary fraction and twin density of these alloys were evaluated by electron backscatter diffraction analysis. Among the three alloys tested, FeCoNi exhibited the highest special boundary fraction and twin density after one-step recrystallization. The special boundary increment after one-step recrystallization was mainly affected by grain boundary velocity, while twin density was mainly affected by average grain boundary energy and twin boundary energy.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Yongli; Wang, Xianjie; Sui, Yu

Here in this article, we investigated the dielectric properties of (In + Nb) co-doped rutile TiO 2 single crystal and polycrystalline ceramics. Both of them showed colossal, up to 10 4, dielectric permittivity at room temperature. The single crystal sample showed one dielectric relaxation process with a large dielectric loss. The voltage-dependence of dielectric permittivity and the impedance spectrum suggest that the high dielectric permittivity of single crystal originated from the surface barrier layer capacitor (SBLC). The impedance spectroscopy at different temperature confirmed that the (In+Nb) co-doped rutile TiO 2 polycrystalline ceramic had semiconductor grains and insulating grain boundaries, andmore » that the activation energies were calculated to be 0.052 eV and 0.35 eV for grain and grain boundary, respectively. The dielectric behavior and impedance spectrum of the polycrystalline ceramic sample indicated that the internal barrier layer capacitor (IBLC) mode made a major contribution to the high ceramic dielectric permittivity, instead of the electron-pinned defect-dipoles.« less

Insight into the grain boundary effect on the ionic transport of yttria-stabilized zirconia at elevated temperatures from a molecular modeling perspective

NASA Astrophysics Data System (ADS)

Chang, Kai-Shiun; Lin, Yi-Feng; Tung, Kuo-Lun

A molecular dynamics (MD) simulation is used to reveal the grain boundary effect on the ionic transport of yttria-stabilized zirconia (YSZ). The oxygen ion displacements and diffusivities of the ideal and grain boundary-inserted YSZ models are analyzed at elevated temperatures. An optimized Y 2O 3 concentration within YSZ for the best ionic conductivity is achieved by balancing the trade-off between the increased vacancies and the decreased accessible free space. The mass transfer resistance of the grain boundary in YSZ can be more easily found at higher temperatures by observing the oxygen ion diffusivities or traveling trajectories. At lower temperatures, the grain interior and the grain boundary control the ionic transport. In contrast, the grain boundary effect on the diffusion barrier is gradually eliminated at elevated temperatures. The modeled results in this work agree well with previous experimental data.

Understanding luminescence properties of grain boundaries in GaN thin films and their atomistic origin

NASA Astrophysics Data System (ADS)

Yoo, Hyobin; Yoon, Sangmoon; Chung, Kunook; Kang, Seoung-Hun; Kwon, Young-Kyun; Yi, Gyu-Chul; Kim, Miyoung

2018-03-01

We report our findings on the optical properties of grain boundaries in GaN films grown on graphene layers and discuss their atomistic origin. We combine electron backscatter diffraction with cathodoluminescence to directly correlate the structural defects with their optical properties, enabling the high-precision local luminescence measurement of the grain boundaries in GaN films. To further understand the atomistic origin of the luminescence properties, we carefully probed atomic core structures of the grain boundaries by exploiting aberration-corrected scanning transmission electron microscopy. The atomic core structures of grain boundaries show different ordering behaviors compared with those observed previously in threading dislocations. Energetics of the grain boundary core structures and their correlation with electronic structures were studied by first principles calculation.

Effective search for stable segregation configurations at grain boundaries with data-mining techniques

NASA Astrophysics Data System (ADS)

Kiyohara, Shin; Mizoguchi, Teruyasu

2018-03-01

Grain boundary segregation of dopants plays a crucial role in materials properties. To investigate the dopant segregation behavior at the grain boundary, an enormous number of combinations have to be considered in the segregation of multiple dopants at the complex grain boundary structures. Here, two data mining techniques, the random-forests regression and the genetic algorithm, were applied to determine stable segregation sites at grain boundaries efficiently. Using the random-forests method, a predictive model was constructed from 2% of the segregation configurations and it has been shown that this model could determine the stable segregation configurations. Furthermore, the genetic algorithm also successfully determined the most stable segregation configuration with great efficiency. We demonstrate that these approaches are quite effective to investigate the dopant segregation behaviors at grain boundaries.

Effect of irradiation on mechanical properties of symmetrical grain boundaries investigated by atomic simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, X. Y.; Gao, N.; Setyawan, W.

Tensile response of irradiated symmetric grain boundaries to externally applied strain has been studied using atomic simulation methods. The absorption of irradiation induced defects by grain boundaries has been confirmed to degrade the mechanical properties of grain boundaries through the change of its under- taken deformation mechanism. Atomic rearrangement, the formations of a stress accumulation region and vacancy-rich zone and the nucleation and movement of dislocations under stress effect have been observed after the displacement cascades in grain boundaries, which are considered as main reasons to induce above degradation. These results suggest the necessity of considering both trap- ping efficiencymore » to defects and the mechanical property change of irradiated grain boundaries for further development of radiation resistant materials.« less

An Analysis of Hole Trapping at Grain Boundary or Poly-Si Floating-Body MOSFET.

PubMed

Jang, Taejin; Baek, Myung-Hyun; Kim, Hyungjin; Park, Byung-Gook

2018-09-01

In this paper, we demonstrate the characteristics of the floating body effect of poly-silicon with grain boundary by SENTAURUS™ TCAD simulation. As drain voltage increases, impact ionization occurs at the drain-channel junction. And these holes created by impact ionization are deposited on the bottom of the body to change the threshold voltage. This feature, the kink effect, is also observed in fully depleted silicon on insulator because grain boundary of the poly-silicon serve as a storage to trap the holes. We simulate the transfer curve depending on the density and position of the grain boundary. The trap density of the grain boundary affects the device characteristics significantly. However similar properties appear except where the grain boundary is located on the drain side.

Encapsulated Annealing: Enhancing the Plasmon Quality Factor in Lithographically–Defined Nanostructures

PubMed Central

Bosman, Michel; Zhang, Lei; Duan, Huigao; Tan, Shu Fen; Nijhuis, Christian A.; Qiu, Cheng–Wei; Yang, Joel K. W.

2014-01-01

Lithography provides the precision to pattern large arrays of metallic nanostructures with varying geometries, enabling systematic studies and discoveries of new phenomena in plasmonics. However, surface plasmon resonances experience more damping in lithographically–defined structures than in chemically–synthesized nanoparticles of comparable geometries. Grain boundaries, surface roughness, substrate effects, and adhesion layers have been reported as causes of plasmon damping, but it is difficult to isolate these effects. Using monochromated electron energy–loss spectroscopy (EELS) and numerical analysis, we demonstrate an experimental technique that allows the study of these effects individually, to significantly reduce the plasmon damping in lithographically–defined structures. We introduce a method of encapsulated annealing that preserves the shape of polycrystalline gold nanostructures, while their grain-boundary density is reduced. We demonstrate enhanced Q–factors in lithographically–defined nanostructures, with intrinsic damping that matches the theoretical Drude damping limit. PMID:24986023

High-temperature stability of Au/Pd/Cu and Au/Pd(P)/Cu surface finishes

NASA Astrophysics Data System (ADS)

Ho, C. E.; Hsieh, W. Z.; Lee, P. T.; Huang, Y. H.; Kuo, T. T.

2018-03-01

Thermal reliability of Au/Pd/Cu and Au/Pd(4-6 wt.% P)/Cu trilayers in the isothermal annealing at 180 °C were investigated by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), and transmission electron microscopy (TEM). The pure Pd film possessed a nanocrystalline structure with numerous grain boundaries, thereby facilitating the interdiffusion between Au and Cu. Out-diffusion of Cu through Pd and Au grain boundaries yielded a significant amount of Cu oxides (CuO and Cu2O) over the Au surface and gave rise to void formation in the Cu film. By contrast, the Pd(P) film was amorphous and served as a good diffusion barrier against Cu diffusion. The results of this study indicated that amorphous Pd(P) possessed better oxidation resistance and thermal reliability than crystalline Pd.

Tilt Grain Boundary Topology Induced by Substrate Topography.

PubMed

Yu, Henry; Gupta, Nitant; Hu, Zhili; Wang, Kai; Srijanto, Bernadeta R; Xiao, Kai; Geohegan, David B; Yakobson, Boris I

2017-09-26

Synthesis of two-dimensional (2D) crystals is a topic of great current interest, since their chemical makeup, electronic, mechanical, catalytic, and optical properties are so diverse. A universal challenge, however, is the generally random formation of defects caused by various growth factors on flat surfaces. Here we show through theoretical analysis and experimental demonstration that nonplanar, curved-topography substrates permit the intentional and controllable creation of topological defects within 2D materials. We augment a common phase-field method by adding a geometric phase to track the crystal misorientation on a curved surface and to detect the formation of grain boundaries, especially when a growing monocrystal "catches its own tail" on a nontrivial topographical feature. It is specifically illustrated by simulated growth of a trigonal symmetry crystal on a conical-planar substrate, to match the experimental synthesis of WS 2 on silicon template, with satisfactory and in some cases remarkable agreement of theory predictions and experimental evidence.

Detection of expansion at large angle grain boundaries using electron diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balluffi, R.W.; Bristowe, P.D.

1984-02-01

Lamarre and Sass (LS) (Scripta Metall. 17: 1141(1983)) observed a grain boundary electron diffraction effect from a large angle twist boundary which they claim can be used to obtain the volume expansion at the grain boundary in a direction normal to it. This paper considers the case where the intensity from the grain boundary region, is close to lattice reflections on the same element of the boundary diffraction lattice. Analysis of this complex problem show that the simplified model of LS is misleading in this case. (DLC)

Revealing Grain Boundary Sliding from Textures of a Deformed Nanocrystalline Pd–Au Alloy

PubMed Central

Skrotzki, Werner; Zhao, Yajun; Pukenas, Aurimas; Birringer, Rainer

2018-01-01

Employing a recent modeling scheme for grain boundary sliding [Zhao et al. Adv. Eng. Mater. 2017, doi:10.1002/adem.201700212], crystallographic textures were simulated for nanocrystalline fcc metals deformed in shear compression. It is shown that, as grain boundary sliding increases, the texture strength decreases while the signature of the texture type remains the same. Grain boundary sliding affects the texture components differently with respect to intensity and angular position. A comparison of a simulation and an experiment on a Pd–10 atom % Au alloy with a 15 nm grain size reveals that, at room temperature, the predominant deformation mode is grain boundary sliding contributing to strain by about 60%. PMID:29370130

Grain boundary misorientations and percolative current paths in high-{ital J}{sub {ital c}} powder-in-tube (Bi,Pb){sub 2}Sr{sub 3}Ca{sub 3}Cu{sub 3}O{sub {ital x}}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goyal, A.; Specht, E.D.; Kroeger, D.M.

1995-05-22

Grain orientations and grain boundary misorientations in high-{ital J}{sub {ital c}}, powder-in-tube (PIT) (Bi,Pb){sub 2}Sr{sub 2}Ca{sub 2}Cu{sub 3}O{sub {ital x}} (Bi-2223) were determined using electron backscatter Kikuchi diffraction and x-ray microdiffraction. Data collected from over 113 spatially correlated grains, resulting in 227 grain boundaries, show that over 40% of the boundaries are {Sigma}1 or small angle (less than 15{degree}). In addition, 8% of the boundaries are within the Brandon criterion for CSLs (sigma larger than 1 and less than 50). Grain boundary ``texture maps`` derived from the electron microscope image and orientation data reveal the presence of percolative paths betweenmore » low energy boundaries.« less

Grain boundary oxidation and fatigue crack growth at elevated temperatures

NASA Technical Reports Server (NTRS)

Liu, H. W.; Oshida, Y.

1986-01-01

Fatigue crack growth rate at elevated temperatures can be accelerated by grain boundary oxidation. Grain boundary oxidation kinetics and the statistical distribution of grain boundary oxide penetration depth were studied. At a constant delta K-level and at a constant test temperature, fatigue crack growth rate, da/dN, is a function of cyclic frequency, nu. A fatigue crack growth model of intermittent micro-ruptures of grain boundary oxide is constructed. The model is consistent with the experimental observations that, in the low frequency region, da/dN is inversely proportional to nu, and fatigue crack growth is intergranular.

Kinetics and thermodynamics associated with Bi adsorption transitions at Cu and Ni grain boundaries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tai, Kaiping; Feng, Lin; Dillon, Shen J.

The grain boundary diffusivity of Au in Cu and Cu-Bi, and Cu in Ni and Ni-Bi are characterized by secondary ion mass spectroscopy depth profiling. Samples are equilibrated in a Bi containing atmosphere at temperatures above and below the onset of grain boundary adsorption transitions, sometimes called complexion transitions. A simple thermo-kinetic model is used to estimate the relative entropic contributions to the grain boundary energies. The results indicate that the entropy term plays a major role in promoting thermally and chemically induced grain boundary complexion transition.

Grain boundary character, and carbide size and spatial distribution in a ternary nickel alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, H.; Gao, M.; Harlow, D.G.

1995-06-01

A preliminary investigation of the grain boundary character and its relationship to carbide distribution in a Ni-18Cr-18Fe ternary alloy was conducted. The results showed that there was a strong preference for the formation of {Sigma}3 (44.6%) and twin-related {Sigma}9 and {Sigma}27 CSL boundaries. If the coherent {Sigma}3{sub c} twin and the twin-related boundaries are excluded, then the distribution would consist of nearly 80% random (high angle) boundaries and about 20% CSL (with {Sigma} {<=} 49) boundaries. The size and spacing of grain boundary carbides were influenced by grain boundary {Sigma}; the carbides being smaller and more closely spaced on themore » {Sigma}1, {Sigma}9 and {Sigma}27 boundaries, and none could be resolved on the coherent {Sigma}3 twin boundaries. The results could be understood, in part, in terms of the influence of grain boundary energy, but the understanding is incomplete. Further studies are in progress and will be reported.« less

O(minus 2) grain boundary diffusion and grain growth in pure dense MgO

NASA Technical Reports Server (NTRS)

Kapadia, C. M.; Leipold, M. H.

1973-01-01

Grain growth behavior in fully dense compacts of MgO of very high purity was studied, and the results compared with other similar behaving materials. The activation energy for the intrinsic self-diffusion of Mg(2minus) is discussed along with the grain boundary diffusion of O(2minus). Grain boundary diffusion of O(2minus) is proposed as the controlling mechanism for grain growth.

Microshear in the deep EDML ice core analyzed using cryogenic EBSD

NASA Astrophysics Data System (ADS)

Kuiper, Ernst-Jan; Pennock, Gill; Drury, Martyn; Kipfstuhl, Sepp; Faria, Sérgio; Weikusat, Ilka

2017-04-01

Ice sheets play an important role in sea level evolution by storing large amounts of fresh water on land. The ice in an ice sheet flows from the interior of the ice sheet to the edges where it either melts or calves into the ocean. This flow of ice results from internal deformation of the ice aggregate. Dislocation creep is assumed to be the dominant deformation mechanism for polar ice and is grain size insensitive. Recently, a different deformation mechanism was identified in the deeper part of the EDML ice core (Antarctica) where, at a depth of 2385 meters, the grain size strongly decreases, the grain aspect ratio increase and, the inclination of the grain elongation changes (Faria et al., 2006; Weikusat et al., 2017). At this depth the borehole displacement increases strongly (Weikusat et al., 2017), which indicates a relatively high strain rate. Part of this EDML ice core section was studied using cryogenic electron backscattered diffraction (cryo-EBSD) (Weikusat et al, 2011). EBSD produces high resolution, full crystallographic (a-axis and c-axis) maps of the ice core samples. EBSD samples were taken from an ice core section at 2392.2 meter depth. This section was chosen for its very small grain size and the strongly aligned grain boundaries. The EBSD maps show a very low orientation gradient of <0.3° per millimetre inside the grains, which is 5-10 times lower than the orientation gradients found in other parts of the ice core. Furthermore, close to some grain boundaries, a relatively strong orientation gradient of 1°-2° per millimetre was found. The subgrain boundaries developed such that they elongate the sliding boundaries in order to accommodate the incompatibilities and maintain the strongly aligned grain boundary network. We identify the dominant deformation mechanism in this part of the ice core as grain boundary sliding accommodated by localized dislocation creep, which is a process similar to microshear (Drury and Humpreys, 1988). The existence of layers of soft ice has serious implications for ice core dating, related paleoclimate studies and ice flow modelling with respect to ice sheet mass balance and sea level predictions. References: - Drury and Humphreys, 1988. Microstructural shear criteria associated with grain boundary sliding during ductile deformation. J. of Struc. Geol. 10, 1, 83-89. - Faria et al., 2006. Is Antarctica like a birthday cake?, Max Planck Institute of Mathematics and the Sciences - Weikusat et al., 2011. Cryogenic EBSD on ice: preserving a stable surface in a low pressure SEM. J. Micros. 242, 3, 295-310. (doi: 10.1111/j.1365-2818.2010.03471.x) - Weikusat et al., 2017. Physical analysis of an Antarctic ice core-towards an integration of micro- and macrodynamics of polar ice. Phil. Trans. R. Soc. A 375, 2015347. (doi:10.1098/rsta.2015.0347)

Atomistic Simulations of Grain Boundary Pinning in CuFe Alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zepeda-Ruiz, L A; Gilmer, G H; Sadigh, B

2005-05-22

The authors apply a hybrid Monte Carlo-molecular dynamics code to the study of grain boundary motion upon annealing of pure Cu and Cu with low concentrations of Fe. The hybrid simulations account for segregation and precipitation of the low solubility Fe, together with curvature driven grain boundary motion. Grain boundaries in two different systems, a {Sigma}7+U-shaped half-loop grain and a nanocrystalline sample, were found to be pinned in the presence of Fe concentrations exceeding 3%.

DOE Office of Scientific and Technical Information (OSTI.GOV)

O’Brien, Christopher J.; Foiles, Stephen M.

Low-mobility twin grain boundaries dominate the microstructure of grain boundary-engineered materials and are critical to understanding their plastic deformation behaviour. The presence of solutes, such as hydrogen, has a profound effect on the thermodynamic stability of the grain boundaries. This work examines the case of a Σ3 grain boundary at inclinations from 0° ≤ Φ ≤ 90°. The angle Φ corresponds to the rotation of the Σ3 (1 1 1) < 1 1 0 > (coherent) into the Σ3 (1 1 2) < 1 1 0 > (lateral) twin boundary. To this end, atomistic models of inclined grain boundaries, utilisingmore » empirical potentials, are used to elucidate the finite-temperature boundary structure while grand canonical Monte Carlo models are applied to determine the degree of hydrogen segregation. In order to understand the boundary structure and segregation behaviour of hydrogen, the structural unit description of inclined twin grain boundaries is found to provide insight into explaining the observed variation of excess enthalpy and excess hydrogen concentration on inclination angle, but the explanatory power is limited by how the enthalpy of segregation is affected by hydrogen concentration. At higher concentrations, the grain boundaries undergo a defaceting transition. In order to develop a more complete mesoscale model of the interfacial behaviour, an analytical model of boundary energy and hydrogen segregation that relies on modelling the boundary as arrays of discrete 1/3 < 1 1 1 > disconnections is constructed. Lastly, the complex interaction of boundary reconstruction and concentration-dependent segregation behaviour exhibited by inclined twin grain boundaries limits the range of applicability of such an analytical model and illustrates the fundamental limitations for a structural unit model description of segregation in lower stacking fault energy materials.« less

Grain boundary phase transformations in PtAu and relevance to thermal stabilization of bulk nanocrystalline metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

O’Brien, C. J.; Barr, C. M.; Price, P. M.

There has recently been a great deal of interest in employing immiscible solutes to stabilize nanocrystalline microstructures. Existing modeling efforts largely rely on mesoscale Monte Carlo approaches that employ a simplified model of the microstructure and result in highly homogeneous segregation to grain boundaries. However, there is ample evidence from experimental and modeling studies that demonstrates segregation to grain boundaries is highly non-uniform and sensitive to boundary character. This work employs a realistic nanocrystalline microstructure with experimentally relevant global solute concentrations to illustrate inhomogeneous boundary segregation. Furthermore, experiments quantifying segregation in thin films are reported that corroborate the prediction thatmore » grain boundary segregation is highly inhomogeneous. In addition to grain boundary structure modifying the degree of segregation, the existence of a phase transformation between low and high solute content grain boundaries is predicted. In order to conduct this study, new embedded atom method interatomic potentials are developed for Pt, Au, and the PtAu binary alloy.« less

Grain boundary phase transformations in PtAu and relevance to thermal stabilization of bulk nanocrystalline metals

DOE PAGES

O’Brien, C. J.; Barr, C. M.; Price, P. M.; ...

2017-10-31

There has recently been a great deal of interest in employing immiscible solutes to stabilize nanocrystalline microstructures. Existing modeling efforts largely rely on mesoscale Monte Carlo approaches that employ a simplified model of the microstructure and result in highly homogeneous segregation to grain boundaries. However, there is ample evidence from experimental and modeling studies that demonstrates segregation to grain boundaries is highly non-uniform and sensitive to boundary character. This work employs a realistic nanocrystalline microstructure with experimentally relevant global solute concentrations to illustrate inhomogeneous boundary segregation. Furthermore, experiments quantifying segregation in thin films are reported that corroborate the prediction thatmore » grain boundary segregation is highly inhomogeneous. In addition to grain boundary structure modifying the degree of segregation, the existence of a phase transformation between low and high solute content grain boundaries is predicted. In order to conduct this study, new embedded atom method interatomic potentials are developed for Pt, Au, and the PtAu binary alloy.« less

Effect of Alloying Elements on Nano-ordered Wear Property of Magnesium Alloys

NASA Astrophysics Data System (ADS)

Yagi, Takahiro; Hirayama, Tomoko; Matsuoka, Takashi; Somekawa, Hidetoshi

2017-03-01

The effect of alloying elements on nano-ordered wear properties was investigated using fine-grained pure magnesium and several types of 0.3 at. pct X (X = Ag, Al, Ca, Li, Mn, Y, and Zn) binary alloys. They had an average grain size of 3 to 5 μm and a basal texture due to their production by the extrusion process. The specific wear rate was influenced by the alloying element; the Mg-Ca and Mg-Mn alloys showed the best and worst wear property, respectively, among the present alloying elements, which was the same trend as that for indentation hardness. Deformed microstructural observations revealed no formation of deformation twins, because of the high activation of grain boundary-induced plasticity. On the contrary, according to scratched surface observations, when grain boundary sliding partially contributed to deformation, these alloys had large specific wear rates. These results revealed that the wear property of magnesium alloys was closely related to the plastic deformation mechanism. The prevention of grain boundary sliding is important to improve the wear property, which is the same as that of a large-scale wearing configuration. One of the influential factors is the change in the lattice parameter with the chemical composition, i.e., ∂( c/ a)/∂ C. An alloying element that has a large value of ∂( c/ a)/∂ C effectively enhances the wear property.

Liquid impact and fracture of free-standing CVD diamond

NASA Astrophysics Data System (ADS)

Kennedy, Claire F.; Telling, Robert H.; Field, John E.

1999-07-01

The Cavendish Laboratory has developed extensive facilities for studies of liquid and solid particle erosion. This paper describes the high-speed liquid impact erosion of thin CVD diamond discs and the variation with grain sizes of the absolute damage threshold velocity (ADTV), viz., the threshold below which the specimen shows no damage. All specimens fail by rear surface cracking and there is shown to be a shallow dependence of rear surface ADTV on grain size. Fracture propagation in CVD diamond has also been monitored using a specially-designed double-torsion apparatus and data for K1C are presented. Tentatively, the results suggest that finer-grained CVD diamond exhibits a higher fracture toughness, although the differences are slight even over a fourfold variation in the mean grain size. No preference for intergranular fracture was observed and one may conclude from this that the grain boundaries themselves do not seriously weaken the material. The large pre-existing flaws, both within and between grains, whose size varies the grain size are believed to be the dominant source of weakness.

Grain boundary, triple junction and quadruple point mobility controlled normal grain growth

NASA Astrophysics Data System (ADS)

Rios, P. R.; Glicksman, M. E.

2015-07-01

Reduction in stored free energy provides the thermodynamic driving force for grain and bubble growth in polycrystals and foams. Evolution of polycrystalline networks exhibit the additional complication that grain growth may be controlled by several kinetic mechanisms through which the decrease in network energy occurs. Polyhedral boundaries, triple junctions (TJs), and quadruple points (QPs) are the geometrically distinct elements of three dimensional networks that follow Plateau's rules, provided that grain growth is limited by diffusion through, and motion of, cell boundaries. Shvindlerman and co-workers have long recognized the kinetic influences on polycrystalline grain growth of network TJs and QPs. Moreover, the emergence of interesting polycrystalline nanomaterials underscored that TJs can indeed influence grain growth kinetics. Currently there exist few detailed studies concerned either with network distributions of grain size, number of faces per grain, or with 'grain trajectories', when grain growth is limited by the motion of its TJs or QPs. By contrast there exist abundant studies of classical grain growth limited by boundary mobility. This study is focused on a topological/geometrical representation of polycrystals to obtain statistical predictions of the grain size and face number distributions, as well as growth 'trajectories' during steady-state grain growth. Three limits to grain growth are considered, with grain growth kinetics controlled by boundary, TJ, and QP mobilities.

Irradiation stratigraphy in the Apollo 16 deep drill section 60002

NASA Technical Reports Server (NTRS)

Blanford, G. E.; Wood, G. C.

1978-01-01

Particle track density frequency distributions, abundance of track rich grains and minimum track densities are reported for the upper 20 cm of the 60002 section of the Apollo 16 deep drill core. The principal stratigraphic feature is a boundary approximately 7 cm from the top of the section. Experimental evidence does not conclusively determine whether this contact is an ancient regolith surface or is simply a depositional boundary. If it is an ancient surface, it has a model exposure age of 3 to 7 million years and a reworking depth of about 0.5 cm. However, because track density frequency distributions indicate the mixing of soils of different maturities, we favor interpreting this contact as a depositional boundary. There may be a second depositional boundary approximately 19 cm below the top of 60002.

Growth model and structure evolution of Ag layers deposited on Ge films.

PubMed

Ciesielski, Arkadiusz; Skowronski, Lukasz; Górecka, Ewa; Kierdaszuk, Jakub; Szoplik, Tomasz

2018-01-01

We investigated the crystallinity and optical parameters of silver layers of 10-35 nm thickness as a function 2-10 nm thick Ge wetting films deposited on SiO 2 substrates. X-ray reflectometry (XRR) and X-ray diffraction (XRD) measurements proved that segregation of germanium into the surface of the silver film is a result of the gradient growth of silver crystals. The free energy of Ge atoms is reduced by their migration from boundaries of larger grains at the Ag/SiO 2 interface to boundaries of smaller grains near the Ag surface. Annealing at different temperatures and various durations allowed for a controlled distribution of crystal dimensions, thus influencing the segregation rate. Furthermore, using ellipsometric and optical transmission measurements we determined the time-dependent evolution of the film structure. If stored under ambient conditions for the first week after deposition, the changes in the transmission spectra are smaller than the measurement accuracy. Over the course of the following three weeks, the segregation-induced effects result in considerably modified transmission spectra. Two months after deposition, the slope of the silver layer density profile derived from the XRR spectra was found to be inverted due to the completed segregation process, and the optical transmission spectra increased uniformly due to the roughened surfaces, corrosion of silver and ongoing recrystallization. The Raman spectra of the Ge wetted Ag films were measured immediately after deposition and ten days later and demonstrated that the Ge atoms at the Ag grain boundaries form clusters of a few atoms where the Ge-Ge bonds are still present.

Development of {110}<001> annealing texture in Al-free and 0.1 %Mn-added 3 %Si-Fe alloy strips containing 95 ppm sulfur

NASA Astrophysics Data System (ADS)

Heo, N. H.; Yoon, G. G.

2010-04-01

The solubility of sulfur is calculated in 0.1 %Mn-added 3 %Si-Fe alloys. The segregation kinetics of sulfur is compared in the alloy containing 95 ppm sulfur, depending on the annealing atmosphere. The effects of pre-annealing and annealing atmosphere on final annealing texture are investigated. Segregation behaviors of sulfur at free surfaces and grain boundaries are compared and, during the selective growth, the importance of the grain boundary concentration of sulfur is emphasized. Finally, a correlation between the development of the annealing texture and segregation kinetics of sulfur in the alloy strip is discussed.

Diffusion mechanisms in chemical vapor-deposited iridium coated on chemical vapor-deposited rhenium

NASA Technical Reports Server (NTRS)

Hamilton, J. C.; Yang, N. Y. C.; Clift, W. M.; Boehme, D. R.; Mccarty, K. F.; Franklin, J. E.

1992-01-01

Radiation-cooled rocket thruster chambers have been developed which use CVD Re coated with CVD Ir on the interior surface that is exposed to hot combustion gases. The Ir serves as an oxidation barrier which protects the structural integrity-maintaining Re at elevated temperatures. The diffusion kinetics of CVD materials at elevated temperatures is presently studied with a view to the prediction and extension of these thrusters' performance limits. Line scans for Ir and Re were fit on the basis of a diffusion model, in order to extract relevant diffusion constants; the fastest diffusion process is grain-boundary diffusion, where Re diffuses down grain boundaries in the Ir overlayer.

Intergranular fracture in irradiated Inconel X-750 containing very high concentrations of helium and hydrogen

DOE Office of Scientific and Technical Information (OSTI.GOV)

Judge, Colin D.; Gauquelin, Nicolas; Walters, Lori

2015-02-01

In recent years, it has been determined that Inconel X-750 CANDU spacers have lost strength and material ductility following irradiation in reactor. The irradiated fracture behaviour of ex-service material was also found to be entirely intergranular. The heavily thermalized flux spectrum in a CANDU reactor results in transmutation of 58Ni to 59Ni. The 59Ni itself has unusually high thermal neutron reaction cross-sections of the type: (n, γ), (n, p), and (n,α). The latter two reactions, in particular, contribute to a significant enhancement of the atomic displacements in addition to creating high concentrations of hydrogen and helium within the material. Metallographicmore » examinations by transmission electron microscopy (TEM) have confirmed the presence of helium bubbles in the matrix and aligned along grain boundaries and matrix-precipitate interfaces. He bubble size and density are found to be highly dependent on the irradiation temperature and material microstructure; the bubbles are larger within grain boundary precipitates. TEM specimens extracted from fracture surfaces and crack tips give direct evidence linking crack propagation with grain boundary He bubbles.« less

Phase transformation synthesis of TiO2/CdS heterojunction film with high visible-light photoelectrochemical activity

NASA Astrophysics Data System (ADS)

Liu, Canjun; Yang, Yahui; Li, Jie; Chen, Shu

2018-06-01

CdS/TiO2 heterojunction film used as a photoanode has attracted much attention in the past few years due to its good visible light photocatalytic activity. However, CdS/TiO2 films prepared by conventional methods (successive ionic layer adsorption and reaction, chemical bath deposition and electrodeposition) show numerous grain boundaries in the CdS layer and an imperfect contact at the heterojunction interface. In this study, we designed a phase transformation method to fabricate CdS/TiO2 nanorod heterojunction films. The characterization results showed that the CdS layer with fewer grain boundaries was conformally coated on the TiO2 nanorod surface and the formation mechanism has been explained in this manuscript. Moreover, the prepared CdS/TiO2 films show a high photocatalytic activity and the photocurrent density is as high as 9.65 mA cm‑2 at 0.80 V versus RHE. It may be attributed to fewer grain boundaries and a compact heterojunction contact, which can effectively improve charge separation and transportation.

Effect of one-step recrystallization on the grain boundary evolution of CoCrFeMnNi high entropy alloy and its subsystems

PubMed Central

Chen, Bo-Ru; Yeh, An-Chou; Yeh, Jien-Wei

2016-01-01

In this study, the grain boundary evolution of equiatomic CoCrFeMnNi, CoCrFeNi, and FeCoNi alloys after one-step recrystallization were investigated. The special boundary fraction and twin density of these alloys were evaluated by electron backscatter diffraction analysis. Among the three alloys tested, FeCoNi exhibited the highest special boundary fraction and twin density after one-step recrystallization. The special boundary increment after one-step recrystallization was mainly affected by grain boundary velocity, while twin density was mainly affected by average grain boundary energy and twin boundary energy. PMID:26923713

Effect of Grain Boundary Misorientation on Electromigration in Lead-Free Solder Joints

NASA Astrophysics Data System (ADS)

Tasooji, Amaneh; Lara, Leticia; Lee, Kyuoh

2014-12-01

Reduction in microelectronic interconnect size gives rise to solder bumps consisting of few grains, approaching a single- or bicrystal grain morphology in C4 bumps. Single grain anisotropy, individual grain orientation, presence of easy diffusion paths along grain boundaries, and the increased current density in these small solder bumps aggravate electromigration. This reduces the reliability of the entire microelectronic system. This paper focuses on electromigration behavior in Pb-free solder, specifically the Sn-0.7 wt.%Cu alloy. We discuss the effects of texture, grain orientation, and grain boundary misorientation angle on electromigration (EM) and intermetallic compound formation in EM-tested C4 bumps. The detailed electron backscatter diffraction (EBSD) analysis used in this study reveals the greater influence of grain boundary misorientation on solder bump electromigration compared with the effect associated with individual grain orientation.

A theoretical model of grain boundary self-diffusion in metals with phase transitions (case study into titanium and zirconium)

NASA Astrophysics Data System (ADS)

Semenycheva, Alexandra V.; Chuvil'deev, Vladimir N.; Nokhrin, Aleksey V.

2018-05-01

The paper offers a model describing the process of grain boundary self-diffusion in metals with phase transitions in the solid state. The model is based on ideas and approaches found in the theory of non-equilibrium grain boundaries. The range of application of basic relations contained in this theory is shown to expand, as they can be used to calculate the parameters of grain boundary self-diffusion in high-temperature and low-temperature phases of metals with a phase transition. The model constructed is used to calculate grain boundary self-diffusion activation energy in titanium and zirconium and an explanation is provided as to their abnormally low values in the low-temperature phase. The values of grain boundary self-diffusion activation energy are in good agreement with the experiment.

Influence of grain boundaries on the distribution of components in binary alloys

NASA Astrophysics Data System (ADS)

L'vov, P. E.; Svetukhin, V. V.

2017-12-01

Based on the free-energy density functional method (the Cahn-Hilliard equation), a phenomenological model that describes the influence of grain boundaries on the distribution of components in binary alloys has been developed. The model is built on the assumption of the difference between the interaction parameters of solid solution components in the bulk and at the grain boundary. The difference scheme based on the spectral method is proposed to solve the Cahn-Hilliard equation with interaction parameters depending on coordinates. Depending on the ratio between the interaction parameters in the bulk and at the grain boundary, temperature, and alloy composition, the model can give rise to different types of distribution of a dissolved component, namely, either depletion or enrichment of the grain-boundary area, preferential grainboundary precipitation, competitive precipitation in the bulk and at the grain boundary, etc.

TOPICAL REVIEW: Importance of low-angle grain boundaries in YBa2Cu3O7-δ coated conductors

NASA Astrophysics Data System (ADS)

Durrell, J. H.; Rutter, N. A.

2009-01-01

Over the past ten years the perception of grain boundaries in YBa2Cu3O7-δ conductors has changed greatly. They are now not a problem to be eliminated, but an inevitable and potentially favourable part of the material. This change has arisen as a consequence of new manufacturing techniques which result in excellent grain alignment, reducing the spread of grain boundary misorientation angles. At the same time there is considerable recent evidence which indicates that the variation of properties of grain boundaries with mismatch angle is more complex than a simple exponential decrease in critical current. This is due to the fact that low-angle grain boundaries represent a qualitatively different system to high-angle boundaries. The time is therefore right for a targeted review of research into low-angle YBa2Cu3O7-δ grain boundaries. This article does not purport to be a comprehensive review of the physics of grain boundaries as found in YBa2Cu3O7-δ in general; for a broader overview we would recommend that the reader consult the comprehensive review of Hilgenkamp and Mannhart (2002 Rev. Mod. Phys. 74 485). The purpose of this article is to review the origin and properties of the low-angle grain boundaries found in YBa2Cu3O7-δ coated conductors both individually and as a collective system.

Interfacial Engineering of Inorganic Materials for Energy Storage and Conversion Applications

NASA Astrophysics Data System (ADS)

Samiee, Mojtaba

Since the micrometer-sized bulk materials have reached their inherent limits, development of new materials with high performance is essential for low cost and environmentally friendly electrochemical energy storage and conversion devices. One approach is to take advantage of interfacial engineering in order to modify currently developed materials, thus improving their properties for specific applications. The advantage of interfacial engineering is that it can also be applied to newly developed materials to further improve their properties for the specific applications. In first part of this dissertation, a systematic study is performed to investigate the effect of annealing in reducing atmospheres with different oxygen partial pressures and presence of other species (Ar, H2, N2, vacuum or hydrocarbon) on visible-light photocatalytic activity of TiO2. In second part, a facile nitridation method is used to improve the rate capability of TiO 2 as anode material for Li ion batteries. The enhanced high-rate capacities are attributed to moderate surface nitridation with less-disordered nitridated regions, which may enhance the surface electronic conductivity without forming discrete, nanoscale, and surface amorphous films to block the lithium transport. In third part, pseudocapacitive properties of V2O5-based adsorbates supported on TiO2 nanoparticles is systematically measured. Surface amorphous films (SAFs), which form naturally at thermodynamic equilibria at 550-600 °C with self-regulating or "equilibrium" thicknesses on the order of 1 nm, exhibit superior electrochemical performance at moderate and high scan rates (20-500 mV/s) that are of prime importance for supercapacitor applications, as compared with submonolayer and monolayer adsorbates formed at lower equilibration temperatures. In fourth part, we perform a combined experimental and computational investigation into the effects of aliovalent doping in NASICON on both bulk and grain boundary ionic conductivity. Our results show that the dopants with low solid solubility limits in NASICON solid solution lead to the formation of a conducting secondary phase at grain boundaries, thereby improving effective grain boundary conductivity that is otherwise hindered by the poorly-conducting Na3PO4 and ZrO2 secondary phases in undoped NASICON. In fifth part, inline electron holography technique is used to directly observe and investigate the space charge layers at grain boundaries of Y-doped BaZrO3.

Investigations on the mechanical behavior of nanowires with twin boundaries by atomistic simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tian, Xia, E-mail: tianxia@lsec.cc.ac.cn

2015-03-10

Atomistic simulations are used to study the deformation behavior of twinned Cu nanowires with a <111> growth orientation under tension. Due to the existence of the twin boundaries, the strength of the twinned nanowires is higher than that of the twin-free nanowire and the yielding stress of twinned nanowires is inversely proportional to the spacings of the twin boundaries. Moreover, The ductility of the twin-free nanowire is the highest of all and it grows with the increasing spacings of the twin boundaries for twinned nanowires. Besides, we find that the twin boundaries can be served as dislocation sources as wellmore » as the free surfaces and grain boundaries.« less

Modeling of stresses at grain boundaries with respect to occurrence of stress corrosion cracking

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kozaczek, K.J.; Sinharoy, A.; Ruud, C.O.

The distributions of elastic stresses/strains in the grain boundary regions were studied by the analytical and the finite element models. The grain boundaries represent the sites where stress concentration occurs as a result of discontinuity of elastic properties across the grain boundary and the presence of second phase particles elastically different from the surrounding matrix grains. A quantitative analysis of those stresses for steels and nickel based alloys showed that the stress concentrations in the grain boundary regions are high enough to cause a local microplastic deformation even when the material is in the macroscopic elastic regime. The stress redistributionmore » as a result of such a plastic deformation was discussed.« less

Simulation of electron transport across charged grain boundaries

NASA Astrophysics Data System (ADS)

Srikant, V.; Clarke, D. R.; Evans, P. V.

1996-09-01

The I-V (current density-electric field) characteristics of low-angle grain boundaries consisting of periodic arrays of charged dislocations are computed using a quasiclassical molecular dynamics approach. Below a critical value of the grain boundary misorientation, the computed I-V characteristics are linear whereas above they are nonlinear. The degree of nonlinearity and the voltage onset of nonlinearity are found to be dependent on the grain boundary misorientation.

Direct Correlations of Grain Boundary Potentials to Chemical States and Dielectric Properties of Doped CaCu3Ti4O12 Thin Films.

PubMed

Cho, Ahra; Han, Chan Su; Kang, Meenjoo; Choi, Wooseok; Lee, Jihwan; Jeon, Jaecheol; Yu, Sujae; Jung, Ye Seul; Cho, Yong Soo

2018-05-09

Colossal dielectric constant CaCu 3 Ti 4 O 12 has been recognized as one of the rare materials having intrinsic interfacial polarization and thus unusual dielectric characteristics, in which the electrical state of the grain boundary is critical. Here, the direct correlation between the grain boundary potential and relative permittivity is proposed for the CaCu 3 Ti 4 O 12 thin films doped with Zn, Ga, Mn, and Ag as characterized by Kelvin probe force microscopy. The dopants are intended to provide the examples of variable grain boundary potentials that are driven by chemical states including Cu + , Ti 3+ , and oxygen vacancy. Grain boundary potential is nearly linearly proportional to the dielectric constant. This effect is attributed to the increased charge accumulation near the grain boundary, depending on the choice of the dopant. As an example, 1 mol % Ag-doped CaCu 3 Ti 4 O 12 thin films demonstrate the best relative permittivity as associated with a higher grain boundary potential of 120.3 mV compared with 82.6 mV for the reference film. The chemical states across grain boundaries were further verified by using spherical aberration-corrected scanning transmission electron microscopy with the simultaneous electron energy loss spectroscopy.

Dislocation Content Measured Via 3D HR-EBSD Near a Grain Boundary in an AlCu Oligocrystal

NASA Technical Reports Server (NTRS)

Ruggles, Timothy; Hochhalter, Jacob; Homer, Eric

2016-01-01

Interactions between dislocations and grain boundaries are poorly understood and crucial to mesoscale plasticity modeling. Much of our understanding of dislocation-grain boundary interaction comes from atomistic simulations and TEM studies, both of which are extremely limited in scale. High angular resolution EBSD-based continuum dislocation microscopy provides a way of measuring dislocation activity at length scales and accuracies relevant to crystal plasticity, but it is limited as a two-dimensional technique, meaning the character of the grain boundary and the complete dislocation activity is difficult to recover. However, the commercialization of plasma FIB dual-beam microscopes have made 3D EBSD studies all the more feasible. The objective of this work is to apply high angular resolution cross correlation EBSD to a 3D EBSD data set collected by serial sectioning in a FIB to characterize dislocation interaction with a grain boundary. Three dimensional high angular resolution cross correlation EBSD analysis was applied to an AlCu oligocrystal to measure dislocation densities around a grain boundary. Distortion derivatives associated with the plasma FIB serial sectioning were higher than expected, possibly due to geometric uncertainty between layers. Future work will focus on mitigating the geometric uncertainty and examining more regions of interest along the grain boundary to glean information on dislocation-grain boundary interaction.

Stress Distribution During Deformation of Polycrystalline Aluminum by Molecular-Dynamics and Finite-Element Modeling

NASA Technical Reports Server (NTRS)

Yamakov, V.; Saether, E.; Phillips, D.; Glaessgen, E. H.

2004-01-01

In this paper, a multiscale modelling strategy is used to study the effect of grain-boundary sliding on stress localization in a polycrystalline microstructure with an uneven distribution of grain size. The development of the molecular dynamics (MD) analysis used to interrogate idealized grain microstructures with various types of grain boundaries and the multiscale modelling strategies for modelling large systems of grains is discussed. Both molecular-dynamics and finite-element (FE) simulations for idealized polycrystalline models of identical geometry are presented with the purpose of demonstrating the effectiveness of the adapted finite-element method using cohesive zone models to reproduce grain-boundary sliding and its effect on the stress distribution in a polycrystalline metal. The yield properties of the grain-boundary interface, used in the FE simulations, are extracted from a MD simulation on a bicrystal. The models allow for the study of the load transfer between adjacent grains of very different size through grain-boundary sliding during deformation. A large-scale FE simulation of 100 grains of a typical microstructure is then presented to reveal that the stress distribution due to grain-boundary sliding during uniform tensile strain can lead to stress localization of two to three times the background stress, thus suggesting a significant effect on the failure properties of the metal.

Role of Grain Boundaries under Long-Time Radiation

NASA Astrophysics Data System (ADS)

Zhu, Yichao; Luo, Jing; Guo, Xu; Xiang, Yang; Chapman, Stephen Jonathan

2018-06-01

Materials containing a high proportion of grain boundaries offer significant potential for the development of radiation-resistant structural materials. However, a proper understanding of the connection between the radiation-induced microstructural behavior of a grain boundary and its impact at long natural time scales is still missing. In this Letter, point defect absorption at interfaces is summarized by a jump Robin-type condition at a coarse-grained level, wherein the role of interface microstructure is effectively taken into account. Then a concise formula linking the sink strength of a polycrystalline aggregate with its grain size is introduced and is well compared with experimental observation. Based on the derived model, a coarse-grained formulation incorporating the coupled evolution of grain boundaries and point defects is proposed, so as to underpin the study of long-time morphological evolution of grains induced by irradiation. Our simulation results suggest that the presence of point defect sources within a grain further accelerates its shrinking process, and radiation tends to trigger the extension of twin boundary sections.

Pore and grain boundary migration under a temperature gradient: A phase-field model study

DOE PAGES

Biner, S. B.

2016-03-16

In this study, the collective migration behavior of pores and grain boundaries under a temperature gradient is studied for simple single crystal, bi-crystal and polycrystal configurations with a phase-field model formulism. For simulation of the microstructure of solids, composed of pores and grain boundaries, the results indicate that not only the volume fraction of pores, but also its spatial partitioning between the grain boundary junctions and the grain boundary segments appears to be important. In addition to various physical properties, the evolution kinetics, under given temperature gradients, will be strongly influenced with the initial morphology of a poly-crystalline microstructure.

Correlating Atom Probe Tomography with Atomic-Resolved Scanning Transmission Electron Microscopy: Example of Segregation at Silicon Grain Boundaries.

PubMed

Stoffers, Andreas; Barthel, Juri; Liebscher, Christian H; Gault, Baptiste; Cojocaru-Mirédin, Oana; Scheu, Christina; Raabe, Dierk

2017-04-01

In the course of a thorough investigation of the performance-structure-chemistry interdependency at silicon grain boundaries, we successfully developed a method to systematically correlate aberration-corrected scanning transmission electron microscopy and atom probe tomography. The correlative approach is conducted on individual APT and TEM specimens, with the option to perform both investigations on the same specimen in the future. In the present case of a Σ9 grain boundary, joint mapping of the atomistic details of the grain boundary topology, in conjunction with chemical decoration, enables a deeper understanding of the segregation of impurities observed at such grain boundaries.

Self-organized pseudo-graphene on grain boundaries in topological band insulators

NASA Astrophysics Data System (ADS)

Slager, Robert-Jan; Juričić, Vladimir; Lahtinen, Ville; Zaanen, Jan

2016-06-01

Semimetals are characterized by nodal band structures that give rise to exotic electronic properties. The stability of Dirac semimetals, such as graphene in two spatial dimensions, requires the presence of lattice symmetries, while akin to the surface states of topological band insulators, Weyl semimetals in three spatial dimensions are protected by band topology. Here we show that in the bulk of topological band insulators, self-organized topologically protected semimetals can emerge along a grain boundary, a ubiquitous extended lattice defect in any crystalline material. In addition to experimentally accessible electronic transport measurements, these states exhibit a valley anomaly in two dimensions influencing edge spin transport, whereas in three dimensions they appear as graphenelike states that may exhibit an odd-integer quantum Hall effect. The general mechanism underlying these semimetals—the hybridization of spinon modes bound to the grain boundary—suggests that topological semimetals can emerge in any topological material where lattice dislocations bind localized topological modes.

On the small angle twist sub-grain boundaries in Ti3AlC2.

PubMed

Zhang, Hui; Zhang, Chao; Hu, Tao; Zhan, Xun; Wang, Xiaohui; Zhou, Yanchun

2016-04-01

Tilt-dominated grain boundaries have been investigated in depth in the deformation of MAX phases. In stark contrast, another important type of grain boundaries, twist grain boundaries, have long been overlooked. Here, we report on the observation of small angle twist sub-grain boundaries in a typical MAX phase Ti3AlC2 compressed at 1200 °C, which comprise hexagonal screw dislocation networks formed by basal dislocation reactions. By first-principles investigations on atomic-scale deformation and general stacking fault energy landscapes, it is unequivocally demonstrated that the twist sub-grain boundaries are most likely located between Al and Ti4f (Ti located at the 4f Wyckoff sites of P63/mmc) layers, with breaking of the weakly bonded Al-Ti4f. The twist angle increases with the increase of deformation and is estimated to be around 0.5° for a deformation of 26%. This work may shed light on sub-grain boundaries of MAX phases, and provide fundamental information for future atomic-scale simulations.

Enhancing grain boundary ionic conductivity in mixed ionic–electronic conductors

DOE PAGES

Lin, Ye; Fang, Shumin; Su, Dong; ...

2015-04-10

Mixed ionic–electronic conductors are widely used in devices for energy conversion and storage. Grain boundaries in these materials have nanoscale spatial dimensions, which can generate substantial resistance to ionic transport due to dopant segregation. Here, we report the concept of targeted phase formation in a Ce 0.8Gd 0.2O 2₋δ–CoFe 2O 4 composite that serves to enhance the grain boundary ionic conductivity. Using transmission electron microscopy and spectroscopy approaches, we probe the grain boundary charge distribution and chemical environments altered by the phase reaction between the two constituents. The formation of an emergent phase successfully avoids segregation of the Gd dopantmore » and depletion of oxygen vacancies at the Ce 0.8Gd 0.2O 2₋δ–Ce 0.8Gd 0.2O 2₋δ grain boundary. This results in superior grain boundary ionic conductivity as demonstrated by the enhanced oxygen permeation flux. Lastly, this work illustrates the control of mesoscale level transport properties in mixed ionic–electronic conductor composites through processing induced modifications of the grain boundary defect distribution.« less

How grain boundaries affect the efficiency of poly-CdTe solar-cells: A fundamental atomic-scale study of grain boundary dislocation cores using CdTe bi-crystal thin films.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klie, Robert

It is now widely accepted that grain boundaries in poly-crystalline CdTe thin film devices have a detrimental effect on the minority carrier lifetimes, the open circuit voltage and therefore the overall solar-cell performance. The goal of this project was to develop a fundamental understanding of the role of grain boundaries in CdTe on the carrier life-time, open-circuit voltage, Voc, and the diffusion of impurities. To achieve this goal, i) CdTe bi-crystals were fabricated with various misorientation angels, ii) the atomic- and electronic structures of the grain boundaries were characterized using scanning transmission electron microscopy (STEM), and iii) first-principles density functionalmore » theory modeling was performed on the structures determined by STEM to predict the grain boundary potential. The transport properties and minority carrier lifetimes of the bi-crystal grain boundaries were measured using a variety of approaches, including TRPL, and provided feedback to the characterization and modeling effort about the effectiveness of the proposed models.« less

Enhancing grain boundary ionic conductivity in mixed ionic–electronic conductors

PubMed Central

Lin, Ye; Fang, Shumin; Su, Dong; Brinkman, Kyle S; Chen, Fanglin

2015-01-01

Mixed ionic–electronic conductors are widely used in devices for energy conversion and storage. Grain boundaries in these materials have nanoscale spatial dimensions, which can generate substantial resistance to ionic transport due to dopant segregation. Here, we report the concept of targeted phase formation in a Ce0.8Gd0.2O2−δ–CoFe2O4 composite that serves to enhance the grain boundary ionic conductivity. Using transmission electron microscopy and spectroscopy approaches, we probe the grain boundary charge distribution and chemical environments altered by the phase reaction between the two constituents. The formation of an emergent phase successfully avoids segregation of the Gd dopant and depletion of oxygen vacancies at the Ce0.8Gd0.2O2−δ–Ce0.8Gd0.2O2−δ grain boundary. This results in superior grain boundary ionic conductivity as demonstrated by the enhanced oxygen permeation flux. This work illustrates the control of mesoscale level transport properties in mixed ionic–electronic conductor composites through processing induced modifications of the grain boundary defect distribution. PMID:25857355

Enhancing grain boundary ionic conductivity in mixed ionic-electronic conductors.

PubMed

Lin, Ye; Fang, Shumin; Su, Dong; Brinkman, Kyle S; Chen, Fanglin

2015-04-10

Mixed ionic-electronic conductors are widely used in devices for energy conversion and storage. Grain boundaries in these materials have nanoscale spatial dimensions, which can generate substantial resistance to ionic transport due to dopant segregation. Here, we report the concept of targeted phase formation in a Ce0.8Gd0.2O2-δ-CoFe2O4 composite that serves to enhance the grain boundary ionic conductivity. Using transmission electron microscopy and spectroscopy approaches, we probe the grain boundary charge distribution and chemical environments altered by the phase reaction between the two constituents. The formation of an emergent phase successfully avoids segregation of the Gd dopant and depletion of oxygen vacancies at the Ce0.8Gd0.2O2-δ-Ce0.8Gd0.2O2-δ grain boundary. This results in superior grain boundary ionic conductivity as demonstrated by the enhanced oxygen permeation flux. This work illustrates the control of mesoscale level transport properties in mixed ionic-electronic conductor composites through processing induced modifications of the grain boundary defect distribution.

Enhancing grain boundary ionic conductivity in mixed ionic–electronic conductors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Ye; Fang, Shumin; Su, Dong

Mixed ionic–electronic conductors are widely used in devices for energy conversion and storage. Grain boundaries in these materials have nanoscale spatial dimensions, which can generate substantial resistance to ionic transport due to dopant segregation. Here, we report the concept of targeted phase formation in a Ce 0.8Gd 0.2O 2₋δ–CoFe 2O 4 composite that serves to enhance the grain boundary ionic conductivity. Using transmission electron microscopy and spectroscopy approaches, we probe the grain boundary charge distribution and chemical environments altered by the phase reaction between the two constituents. The formation of an emergent phase successfully avoids segregation of the Gd dopantmore » and depletion of oxygen vacancies at the Ce 0.8Gd 0.2O 2₋δ–Ce 0.8Gd 0.2O 2₋δ grain boundary. This results in superior grain boundary ionic conductivity as demonstrated by the enhanced oxygen permeation flux. Lastly, this work illustrates the control of mesoscale level transport properties in mixed ionic–electronic conductor composites through processing induced modifications of the grain boundary defect distribution.« less

Marginally trapped surfaces and AdS/CFT

NASA Astrophysics Data System (ADS)

Grado-White, Brianna; Marolf, Donald

2018-02-01

It has been proposed that the areas of marginally trapped or anti-trapped surfaces (also known as leaves of holographic screens) may encode some notion of entropy. To connect this to AdS/CFT, we study the case of marginally trapped surfaces anchored to an AdS boundary. We establish that such boundary-anchored leaves lie between the causal and extremal surfaces defined by the anchor and that they have area bounded below by that of the minimal extremal surface. This suggests that the area of any leaf represents a coarse-grained von Neumann entropy for the associated region of the dual CFT. We further demonstrate that the leading area-divergence of a boundary-anchored marginally trapped surface agrees with that for the associated extremal surface, though subleading divergences generally differ. Finally, we generalize an argument of Bousso and Engelhardt to show that holographic screens with all leaves anchored to the same boundary set have leaf-areas that increase monotonically along the screen, and we describe a construction through which this monotonicity can take the more standard form of requiring entropy to increase with boundary time. This construction is related to what one might call future causal holographic information, which in such cases also provides an upper bound on the area of the associated leaves.

Softening due to disordered grain boundaries in nanocrystalline Co.

PubMed

Yuasa, Motohiro; Hakamada, Masataka; Nakano, Hiromi; Mabuchi, Mamoru; Chino, Yasumasa

2013-08-28

Nanocrystalline Co consisting of fcc and hcp phases was processed by electrodeposition, and its mechanical properties were investigated by hardness tests. In addition, high-resolution transmission electron microscopy observations and molecular dynamics (MD) simulations were performed to investigate the grain boundary structure and dislocation nucleation from the grain boundaries. A large amount of disorders existed at the grain boundaries and stacking faults were formed from the grain boundaries in the as-deposited Co specimen. The as-deposited specimen showed a lower hardness than did the annealed specimen, although the grain size of the former was smaller than that of the latter. The activation volume of the as-deposited specimen (=1.5b(3)) was lower than that of the annealed specimen (=50b(3)), thus indicating that nucleation of dislocations from grain boundaries is more active in the as-deposited specimen than in the annealed specimens. The MD simulations showed that dislocation nucleation was closely related to a change in the defect structures at the boundary. Therefore, it is suggested that a significant amount of defects enhance changes in the defect structures at the boundary, resulting in softening of the as-deposited specimen.

Softening due to disordered grain boundaries in nanocrystalline Co

NASA Astrophysics Data System (ADS)

Yuasa, Motohiro; Hakamada, Masataka; Nakano, Hiromi; Mabuchi, Mamoru; Chino, Yasumasa

2013-08-01

Nanocrystalline Co consisting of fcc and hcp phases was processed by electrodeposition, and its mechanical properties were investigated by hardness tests. In addition, high-resolution transmission electron microscopy observations and molecular dynamics (MD) simulations were performed to investigate the grain boundary structure and dislocation nucleation from the grain boundaries. A large amount of disorders existed at the grain boundaries and stacking faults were formed from the grain boundaries in the as-deposited Co specimen. The as-deposited specimen showed a lower hardness than did the annealed specimen, although the grain size of the former was smaller than that of the latter. The activation volume of the as-deposited specimen (=1.5b3) was lower than that of the annealed specimen (=50b3), thus indicating that nucleation of dislocations from grain boundaries is more active in the as-deposited specimen than in the annealed specimens. The MD simulations showed that dislocation nucleation was closely related to a change in the defect structures at the boundary. Therefore, it is suggested that a significant amount of defects enhance changes in the defect structures at the boundary, resulting in softening of the as-deposited specimen.

Study on the Toughness of X100 Pipeline Steel Heat Affected Zone

NASA Astrophysics Data System (ADS)

Li, Xueda; Shang, Chengjia; Ma, Xiaoping; Subramanian, S. V.

Microstructure-property correlation of heat affected zone (HAZ) in X100 longitudinal submerged arc welding (LSAW) real weld joint was studied in this paper. Coarse grained (CG) HAZ and intercritically reheated coarse grained (ICCG) HAZ were characterized by optical microscope (OM), electron backscattered diffraction (EBSD). The microstructure of CGHAZ is mostly composed of granular bainite with low density of high angle boundaries (HAB). Prior austenite grain size is 80μm. In ICCGHAZ, coarse prior austenite grains were decorated by coarse necklacing martensite-austenite (M-A) constituents. Different layers were observed within M-A constituent, which may be martensite and austenite layers. Charpy absorbed energy of two different HAZ regions (ICCGHAZ containing and non-containing regions) was recorded using instrumental Charpy impact test machine. The results showed that the existence of ICCGHAZ resulted in the sharp drop of Charpy absorbed energy from 180J to 50J, while the existence of only CGHAZ could still lead to good toughness. The fracture surface was 60% brittle in the absence of ICCGHAZ, and 100% brittle in the presence of ICCGHAZ in the impact tested samples. The underlying reason is the microstructure of ICCGHAZ consisted of granular bainite and upper bainite with necklace-type M-A constituent along the grain boundaries. Cleavage fracture initiated from M-A constituent, either through cracking of M-A or debonding from the matrix, was observed at the fracture surface of ICCGHAZ. The presence of necklace type M-A constituent in ICCGHAZ notably increases the susceptibility of cleavage microcrack nucleation. Furthermore, the study of secondary microcracks beneath the CGHAZ and the ICCGHAZ through EBSD suggested that the fracture mechanism changes from nucleation-controlled in the CGHAZ to propagation-controlled in the ICCGHAZ because of the presence of necklace-type M-A constituent in the ICCGHAZ region. Both fracture mechanism contribute to the poor toughness of the sample contained ICCGHAZ. In conclusion, big prior austenite grains with low density of HAB plus coarse necklacing M-A products along grain boundary is the dominant factor resulting in low toughness.

Atom Probe Tomography of Phase and Grain Boundaries in Experimentally-Deformed and Hot-Pressed Wehrlite

NASA Astrophysics Data System (ADS)

Cukjati, J.; Parman, S. W.; Cooper, R. F.; Zhao, N.

2017-12-01

Atom probe tomography (APT) was used to characterize the chemistry of three grain boundaries: an olivine-olivine (ol-ol) and olivine-clinopyroxene (ol-cpx) boundary in fine-grained experimentally-deformed wehrlite and an ol-cpx boundary in a fine-grained, hot-pressed wehrlite. Grain boundaries were extracted and formed into APT tips using a focused ion beam (FIB). The tips were analyzed in a reflectron-equipped LEAP4000HR (Harvard University) at 1% or 0.5% detection rate, 5pJ laser energy and 100kHz pulse rate. Total ion counts are between 40 and 100 million per tip. Examination of grain and phase boundaries in wehrlite are of interest since slow-diffusing and olivine-incompatible cations present in cpx (e.g. Ca and Al) may control diffusion-accommodated grain boundary sliding and affect mantle rheology (Sundberg & Cooper, 2008). At steady state, ol-cpx aggregates are weaker than either ol or cpx end member, the results of which are not currently well-explained. We investigate grain boundary widths to understand the transport of olivine-incompatible elements. Widths of grain/phase boundary chemical segregation are between 3nm and 6nm for deformed ol-ol and ol-cpx samples; minimally-deformed (hot-pressed) samples having slightly wider chemical segregation widths. Chemical segregation widths were determined from profiles of Na, Al, P, Cl, K, Ca, or Ni, although not all listed elements can be used for all samples (e.g. Na, K segregation profiles can only be observed for ol-ol sample). These estimates are consistent with prior estimates of grain boundary segregation by atom probe tomography on ol-ol and opx-opx samples (Bachhav et al., 2015) and are less than ol-ol interface widths analyzed by STEM/EDX (Hiraga, Anderson, & Kohlstedt, 2007). STEM/EDX will be performed on deformed wehrlite to investigate chemical profile as a function of applied stress orientation and at length scales between those observable by APT and EPMA. Determination of phase boundary chemistry and structure allows for better modeling of the rheology of multiphase aggregates and better understanding of diffusive transport and storage of incompatible elements along grain boundaries.

Local Electronic Structure Changes in Polycrystalline CdTe with CdCl 2 Treatment and Air Exposure

DOE PAGES

Berg, Morgann; Kephart, Jason M.; Munshi, Amit; ...

2018-03-12

Postdeposition CdCl 2 treatment of polycrystalline CdTe is known to increase the photovoltaic device efficiency. However, the precise chemical, structural, and electronic changes that underpin this improvement are still debated. In this work, spectroscopic photoemission electron microscopy was used to spatially map the vacuum level and ionization energy of CdTe films, enabling the identification of electronic structure variations between grains and grain boundaries (GBs). In vacuo preparation and inert transfer of oxide-free CdTe surfaces isolated the separate effects of CdCl 2 treatment and ambient oxygen exposure. Qualitatively, grain boundaries displayed lower work function and downward band bending relative to grainmore » interiors, but only after air exposure of CdCl 2-treated CdTe. Analysis of numerous space charge regions at grain boundaries showed an average depletion width of 290 nm and an average band bending magnitude of 70 meV, corresponding to a GB trap density of 10 11 cm –2 and a net carrier density of 10 15 cm –3. Finally, these results suggest that both CdCl 2 treatment and oxygen exposure may be independently tuned to enhance the CdTe photovoltaic performance by engineering the interface and bulk electronic structure.« less

Local Electronic Structure Changes in Polycrystalline CdTe with CdCl 2 Treatment and Air Exposure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berg, Morgann; Kephart, Jason M.; Munshi, Amit

Postdeposition CdCl 2 treatment of polycrystalline CdTe is known to increase the photovoltaic device efficiency. However, the precise chemical, structural, and electronic changes that underpin this improvement are still debated. In this work, spectroscopic photoemission electron microscopy was used to spatially map the vacuum level and ionization energy of CdTe films, enabling the identification of electronic structure variations between grains and grain boundaries (GBs). In vacuo preparation and inert transfer of oxide-free CdTe surfaces isolated the separate effects of CdCl 2 treatment and ambient oxygen exposure. Qualitatively, grain boundaries displayed lower work function and downward band bending relative to grainmore » interiors, but only after air exposure of CdCl 2-treated CdTe. Analysis of numerous space charge regions at grain boundaries showed an average depletion width of 290 nm and an average band bending magnitude of 70 meV, corresponding to a GB trap density of 10 11 cm –2 and a net carrier density of 10 15 cm –3. Finally, these results suggest that both CdCl 2 treatment and oxygen exposure may be independently tuned to enhance the CdTe photovoltaic performance by engineering the interface and bulk electronic structure.« less

Linear Dichroism and Photoluminescence Microscopy Imaging of Grain Boundaries in Crystalline Metal-Free Phthalocyanine Thin Films

NASA Astrophysics Data System (ADS)

Pan, Zhenwen; Lamarche, Cody; Cour, Ishviene; Rawat, Naveen; Manning, Lane; Headrick, Randall; Furis, Madalina; Physics Dept.; Material Science Program, University of Vermont, Burlington, VT 05405 Team

2011-03-01

We employed a combination of linear dichroism and photoluminescence microscopy with spatial resolution of 5 μ m to study the excitonic properties of solution-processed metal-free phthalocyanine (H2Pc) crystalline thin films with millimeter-sized grains. We observe a highly-localized, sharp, monomer-like emission at the high angle grain boundaries, in contrast to samples with more uniform grain orientation where no such feature has been observed. The energy difference between the grain boundary luminescence and the HOMO-LUMO singlet exciton recombination of the crystalline H2Pc is measured to be 160meV. Our systematic survey of grain boundaries indicates this localized state is never present at low angle boundaries where the π -orbital overlap between adjacent grains is significant. It supports recent results which associated a decrease in carrier mobility with the presence of large angle boundaries in similar crystalline pentacene films. This project is supported by DMR- 0722451; DMR-0348354; DMR- 0821268.

Local probe microscopic studies on Al-doped ZnO: Pseudoferroelectricity and band bending at grain boundaries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Mohit; Basu, Tanmoy; Som, Tapobrata, E-mail: tsom@iopb.res.in

2016-01-07

In this paper, based on piezoforce measurements, we show the presence of opposite polarization at grains and grain boundaries of Al-doped ZnO (AZO). The polarization can be flipped by 180° in phase by switching the polarity of the applied electric field, revealing the existence of nanoscale pseudoferroelectricity in AZO grown on Pt/TiO{sub 2}/SiO{sub 2}/Si substrate. We also demonstrate an experimental evidence on local band bending at grain boundaries of AZO films using conductive atomic force microscopy and Kelvin probe force microscopy. The presence of an opposite polarization at grains and grain boundaries gives rise to a polarization-driven barrier formation atmore » grain boundaries. With the help of conductive atomic force microscopy, we show that the polarization-driven barrier along with the defect-induced electrostatic potential barrier account for the measured local band bending at grain boundaries. The present study opens a new avenue to understand the charge transport in light of both polarization and electrostatic effects.« less

Deformation Twins in Nanocrystalline Body-Centered Cubic Mo as Predicted by Molecular Dynamics Simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Michael Tonks; Bulent biner; Yongfeng Zhang

2012-10-01

This work studies deformation twins in nanocrystalline body-centered cubic Mo, including the nucleation and growth mechanisms as well as their effects on ductility, through molecular dynamics simulations. The deformation processes of nanocrystalline Mo are simulated using a columnar grain model with three different orientations. The deformation mechanisms identified, including dislocation slip, grain-boundary-mediated plasticity, deformation twins and martensitic transformation, are in agreement with previous studies. In (1 1 0) columnar grains, the deformation is dominated by twinning, which nucleates primarily from the grain boundaries by successive emission of twinning partials and thickens by jog nucleation in the grain interiors. Upon arrestmore » by a grain boundary, the twin may either produce continuous plastic strain across the grain boundary by activating compatible twinning/slip systems or result in intergranular failure in the absence of compatible twinning/slip systems in the neighboring grain. Multiple twinning systems can be activated in the same grain, and the competition between them favors those capable of producing continuous deformation across the grain boundary.« less

Evidence for stable grain boundary melt films in experimentally deformed olivine-orthopyroxene rocks

NASA Astrophysics Data System (ADS)

de Kloe, R.; Drury, M. R.; van Roermund, H. L. M.

The microstructure of olivine-olivine grain boundaries has been studied in experimentally deformed (1200-1227°C, 300MPa) partially molten olivine and olivine-orthopyroxene rocks. In-situ melting produced 1vol% melt in all samples studied. Grain boundary analyses were carried out using a number of transmission electron microscopy techniques. The grain boundary chemistry in undeformed olivine-orthopyroxene starting material showed evidence for the presence of an intergranular phase along some, but not all, of the olivine-olivine boundaries. In the deformed samples, ultrathin Si-rich, Al- and Ca-bearing amorphous films have been observed along all investigated olivine-olivine grain boundaries. The chemistry of the grain boundaries, which is considered to be indicative for the presence of a thin film, was measured with energy-dispersive X-ray spectroscopy (EDX) and energy-filtering imaging. The amorphous nature of the films was confirmed with diffuse dark field imaging, Fresnel fringe imaging, and high-resolution electron microscopy. The films range in thickness from 0.6 to 3.0nm, and EDX analyses show that the presence of Al and Ca is restricted to this ultrathin film along the grain boundaries. Because thin melt films have been observed in all the samples, they are thought to be stable features of the melt microstructure in deformed partially molten rocks. The transition from the occasional presence of films in the undeformed starting material to the general occurrence of the films in deformed materials suggests that deformation promotes the formation and distribution of the films. Alternatively, hot-pressing may be too short for films to develop along all grain boundaries. A difference in creep strength between the studied samples could not be attributed to grain boundary melt films, as these have been found in all deformed samples. However, a weakening effect of grain boundary melt films on olivine rheology could not be ruled out due to the lack of confirmed melt-film free experiments.

Evidence of van Hove singularities in ordered grain boundaries of graphene.

PubMed

Ma, Chuanxu; Sun, Haifeng; Zhao, Yeliang; Li, Bin; Li, Qunxiang; Zhao, Aidi; Wang, Xiaoping; Luo, Yi; Yang, Jinlong; Wang, Bing; Hou, J G

2014-06-06

It has long been under debate whether the electron transport performance of graphene could be enhanced by the possible occurrence of van Hove singularities in grain boundaries. Here, we provide direct experimental evidence to confirm the existence of van Hove singularity states close to the Fermi energy in certain ordered grain boundaries using scanning tunneling microscopy. The intrinsic atomic and electronic structures of two ordered grain boundaries, one with alternative pentagon and heptagon rings and the other with alternative pentagon pair and octagon rings, are determined. It is firmly verified that the carrier concentration and, thus, the conductance around ordered grain boundaries can be significantly enhanced by the van Hove singularity states. This finding strongly suggests that a graphene nanoribbon with a properly embedded ordered grain boundary can be a promising structure to improve the performance of graphene-based electronic devices.

Bubble evolution in Kr-irradiated UO2 during annealing

NASA Astrophysics Data System (ADS)

He, L.; Bai, X. M.; Pakarinen, J.; Jaques, B. J.; Gan, J.; Nelson, A. T.; El-Azab, A.; Allen, T. R.

2017-12-01

Transmission electron microscopy observation of Kr bubble evolution in polycrystalline UO2 annealed at high temperature was conducted in order to understand the inert gas behavior in oxide nuclear fuel. The average diameter of intragranular bubbles increased gradually from 0.8 nm in as-irradiated sample at room temperature to 2.6 nm at 1600 °C and the bubble size distribution changed from a uniform distribution to a bimodal distribution above 1300 °C. The size of intergranular bubbles increased more rapidly than intragranular ones and bubble denuded zones near grain boundaries formed in all the annealed samples. It was found that high-angle grain boundaries held bigger bubbles than low-angle grain boundaries. Complementary atomistic modeling was conducted to interpret the effects of grain boundary character on the Kr segregation. The area density of strong segregation sites in the high-angle grain boundaries is much higher than that in the low angle grain boundaries.

Atomic structure and electronic properties of MgO grain boundaries in tunnelling magnetoresistive devices

PubMed Central

Bean, Jonathan J.; Saito, Mitsuhiro; Fukami, Shunsuke; Sato, Hideo; Ikeda, Shoji; Ohno, Hideo; Ikuhara, Yuichi; McKenna, Keith P.

2017-01-01

Polycrystalline metal oxides find diverse applications in areas such as nanoelectronics, photovoltaics and catalysis. Although grain boundary defects are ubiquitous their structure and electronic properties are very poorly understood since it is extremely challenging to probe the structure of buried interfaces directly. In this paper we combine novel plan-view high-resolution transmission electron microscopy and first principles calculations to provide atomic level understanding of the structure and properties of grain boundaries in the barrier layer of a magnetic tunnel junction. We show that the highly [001] textured MgO films contain numerous tilt grain boundaries. First principles calculations reveal how these grain boundaries are associated with locally reduced band gaps (by up to 3 eV). Using a simple model we show how shunting a proportion of the tunnelling current through grain boundaries imposes limits on the maximum magnetoresistance that can be achieved in devices. PMID:28374755

Effect of solute concentration on grain boundary migration with segregation in stainless steel and model alloys

NASA Astrophysics Data System (ADS)

Kanda, H.; Hashimoto, N.; Takahashi, H.

The phenomenon of grain boundary migration due to boundary diffusion via vacancies is a well-known process for recrystallization and grain growth during annealing. This phenomenon is known as diffusion-induced grain boundary migration (DIGM) and has been recognized in various binary systems. On the other hand, grain boundary migration often occurs under irradiation. Furthermore, such radiation-induced grain boundary migration (RIGM) gives rise to solute segregation. In order to investigate the RIGM mechanism and the interaction between solutes and point defects during the migration, stainless steel and Ni-Si model alloys were electron-irradiated using a HVEM. RIGM was often observed in stainless steels during irradiation. The migration rate of boundary varied, and three stages of the migration were recognized. At lower temperatures, incubation periods up to the occurrence of the boundary migration were observed prior to first stage. These behaviors were recognized particularly for lower solute containing alloys. From the relation between the migration rates at stage I and inverse temperatures, activation energies for the boundary migration were estimated. In comparison to the activation energy without irradiation, these values were very low. This suggests that the RIGM is caused by the flow of mixed-dumbbells toward the grain boundary. The interaction between solute and point defects and the effective defect concentration generating segregation will be discussed.

Pulsed-Laser-Induced Melting and Solidification of Thin Metallic Films

NASA Astrophysics Data System (ADS)

Choi, Min Hwan

This thesis focused on investigating excimer-laser induced melting and solidification of thin metallic films on SiO2. Two distinct topics were pursued: (1) microstructural manipulation and optimization of Cu films via SLS of as-deposited Cu films on SiO2, and (2) investigation of oriented heterogeneous nucleation via complete melting and subsequent nucleation-initated solidification of Ni films on SiO2. Close examination of laterally grown grains, which quickly develop rolling direction crystallographic orientation texture due to occlusion of differently oriented grains, reveal, furthermore, that low-angle grain boundaries as well as twins can be generated during the growth. These intra-grain defects are found to appear in a systematic manner (as they are located at specific regions and observed under specific incident energy densities). Significantly longer lateral growth distances observed in Cu films (compared to that of Si films) was attributed to the fact that substantially higher growth rates are expected with simple metallic films at a given interfacial undercooling. The implementation of SLS using Cu films was accomplished quite effectively, as can be expected from the above lateral-growth-related results involving single-shot expeirments. We were able to achieve a variety of large-grained, grain-boundary location and grain-orientation controlled Cu films via various SLS techniques. When performed optimally in accordance with the findings made in chapter 2, the resulting microstructure exhibits large grains, which are primarily devoid of intra-grain defects. For example, 2-shot SLS processed Cu films led to strong rolling direction orientation, while avoiding the formation of low-angle grain boundaries and twin-boundaries. The highlight of SLS on Cu films correspond to a version of SLS (referred to as "2-Shot plus 2-Shot" SLS) in which the second 2-shot SLS is performed in the direction perpendicular to the first one. Through this approach, we were able to achieve grain-boundary-location controlled microstructure with a strong orientation texture in all three dimensions (forming, effectively, an ultra-large quasi-single crystal material). Nucleation of solids in laser-quenched Ni films was investigated using EBSD analysis. The surface orientation analysis of nucleated grains obtained within the complete melting regime reveal a clear sign of texture. From these and additional findings from previous work involving Al films, we were able to conclude that systematic heterogeneous nucleation has taken place, and, furthermore, that oriented nucleation of the solids must have taken place. Although always suspected to be the case, it is typically extremely challenging to prove with certainty, in conventional nucleation experiments, that the mechanism of nucleation corresponds to that of a heterogeneous one. Furthermore, although it has been suspected theoretically for over 50 years, experimental results that clearly show that oriented nucleation actually transpires have not been obtained until our work involving Al films; the present findings involving Ni films further strengthen this conclusion as the Ni system removes some of the experimental uncertainties that are associated with Al films, and, furthermore, suggests that the process of oriented nucleation is a general and rather pervasive phenomenon. Additionally, it was observed that the selected orientation changed as a function of incident energy density; in the low energy density regime (above the completed melting threshold) {110}-surface texture was observed, while {111}-surface texture became more dominent at higher densities. Motivated by our experimental work involving Al and Ni that clearly indicates that oriented heterogeneous nucleation is a major path through which heterogeneous nucleation of solids occurs, we have also carried out a 2-dimensional Winterbottom-type thermodynamic analysis that can be used to obtain a better understanding of the phenomenon. In contrast to the previous work on the subject, we consider in our modelling the anisotropic nature of both the solid-liquid and solid-substrate interfacial energy; we advocate that this is the only physically consistent combination. The results show that oriented nucleation can be systematically accounted for as stemming from the expected anisotropic nature of the involved interfacial energies. Furthermore, the analysis also suggests possible reasons for observing a transition in surface texture from one orientation to another. (Abstract shortened by UMI.).

Role of microstructure in caustic stress corrosion cracking of Alloy 690

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mertz, D.A.; Duda, P.T.; Pica, P.N.

1995-12-31

Alloy 690 has been selected for nuclear heat transport system tubing application in recent commercial reactor plants due to its resistance to multiple types of corrosion attack. Typical corn final heat treatments for this material are a mill-anneal (MA, approximately 1,070 C) to completely dissolve the carbides and develop the final grain structure plus a thermal treatment (TT, approximately 700 C) to precipitate carbides at the grain boundaries. Tubing with grain boundary carbides and no or few intragranular carbides has been found resistant to intergranular stress corrosion cracking (IGSCC) in caustic environments. In this work, first, Alloy 690 plate wasmore » subjected to a variety of MA and MA-TT heat treatments to create microstructures of carbide-decorated grain boundaries and undecorated boundaries. Caustic IGSCC test results were consistent with tubing data. Second, experiments were conducted to understand the mechanism by which caustic-corrosion resistance is imparted to Alloy 690 by grain boundary carbides. Tubing with a fully-developed MA-TT carbide microstructure was strained and heat-treated to create a mixed microstructure of new grain boundaries with no carbide precipitate decoration, intermixed with intragranular carbide strings from prior grain boundaries. Caustic SCC performance of this material was identical to that of material with the MA-TT carbide-decorated grain boundaries. This work suggests that the fundamental cause of good IGSCC resistance of MA-TT Alloy 690 in caustic does not derive solely from grain boundary carbides. It is suggested that matrix strength, as measured by yield stress, could be a controlling factor.« less

Coercivity degradation caused by inhomogeneous grain boundaries in sintered Nd-Fe-B permanent magnets

NASA Astrophysics Data System (ADS)

Chen, Hansheng; Yun, Fan; Qu, Jiangtao; Li, Yingfei; Cheng, Zhenxiang; Fang, Ruhao; Ye, Zhixiao; Ringer, Simon P.; Zheng, Rongkun

2018-05-01

Quantitative correlation between intrinsic coercivity and grain boundaries in three dimensions is critical to further improve the performance of sintered Nd-Fe-B permanent magnets. Here, we quantitatively reveal the local composition variation across and especially along grain boundaries using the powerful atomic-scale analysis technique known as atom probe tomography. We also estimate the saturation magnetization, magnetocrystalline anisotropy constant, and exchange stiffness of the grain boundaries on the basis of the experimentally determined structure and composition. Finally, using micromagnetic simulations, we quantify the intrinsic coercivity degradation caused by inhomogeneous grain boundaries. This approach can be applied to other magnetic materials for the analysis and optimization of magnetic properties.

Size-Dependent Grain-Boundary Structure with Improved Conductive and Mechanical Stabilities in Sub-10-nm Gold Crystals

NASA Astrophysics Data System (ADS)

Wang, Chunyang; Du, Kui; Song, Kepeng; Ye, Xinglong; Qi, Lu; He, Suyun; Tang, Daiming; Lu, Ning; Jin, Haijun; Li, Feng; Ye, Hengqiang

2018-05-01

Low-angle grain boundaries generally exist in the form of dislocation arrays, while high-angle grain boundaries (misorientation angle >15 ° ) exist in the form of structural units in bulk metals. Here, through in situ atomic resolution aberration corrected electron microscopy observations, we report size-dependent grain-boundary structures improving both stabilities of electrical conductivity and mechanical properties in sub-10-nm-sized gold crystals. With the diameter of a nanocrystal decreasing below 10 nm, the high-angle grain boundary in the crystal exists as an array of dislocations. This size effect may be of importance to a new generation of interconnects applications.

Grain boundary stability and influence on ionic conductivity in a disordered perovskite -- a first-principles investigation of lithium lanthanum titanate

DOE PAGES

Alexander, Kathleen C.; Ganesh, P.; Chi, Miaofang; ...

2016-12-01

The origin of ionic conductivity in bulk lithium lanthanum titanate, a promising solid electrolyte for Li-ion batteries, has long been under debate, with experiments showing lower conductivity than predictions. Recent microscopy images show Type I and Type II grain boundaries. Using first-principles based calculations we find that experimentally observed Type I boundaries are more stable compared to the Type II grain boundaries, consistent with their observed relative abundance. Grain boundary stability appears to strongly anti-correlate with the field strength as well as the spatial extent of the space charge region. Ion migration is faster along Type II grain boundaries thanmore » across, consistent with recent experiments of increased conductivity when Type II densities were increased.« less

Influences of granular constraints and surface effects on the heterogeneity of elastic, superelastic, and plastic responses of polycrystalline shape memory alloys

DOE PAGES

Paranjape, Harshad M.; Paul, Partha P.; Sharma, Hemant; ...

2017-02-16

Deformation heterogeneities at the microstructural length-scale developed in polycrystalline shape memory alloys (SMAs) during superelastic loading are studied using both experiments and simulations. In situ X-ray diffraction, specifically the far-field high energy diffraction microscopy (ff-HEDM) technique, was used to non-destructively measure the grain-averaged statistics of position, crystal orientation, elastic strain tensor, and volume for hundreds of austenite grains in a superelastically loaded nickel-titanium (NiTi) SMA. These experimental data were also used to create a synthetic microstructure within a finite element model. The development of intragranular stresses were then simulated during tensile loading of the model using anisotropic elasticity. Driving forcesmore » for phase transformation and slip were calculated from these stresses. The grain-average responses of individual austenite crystals examined before and after multiple stress-induced transformation events showed that grains in the specimen interior carry more axial stress than the surface grains as the superelastic response "shakes down". Examination of the heterogeneity within individual grains showed that regions near grain boundaries exhibit larger stress variation compared to the grain interiors. As a result, this intragranular heterogeneity is more strongly driven by the constraints of neighboring grains than the initial stress state and orientation of the individual grains.« less

Influences of granular constraints and surface effects on the heterogeneity of elastic, superelastic, and plastic responses of polycrystalline shape memory alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paranjape, Harshad M.; Paul, Partha P.; Sharma, Hemant

Deformation heterogeneities at the microstructural length-scale developed in polycrystalline shape memory alloys (SMAs) during superelastic loading are studied using both experiments and simulations. In situ X-ray diffraction, specifically the far-field high energy diffraction microscopy (ff-HEDM) technique, was used to non-destructively measure the grain-averaged statistics of position, crystal orientation, elastic strain tensor, and volume for hundreds of austenite grains in a superelastically loaded nickel-titanium (NiTi) SMA. These experimental data were also used to create a synthetic microstructure within a finite element model. The development of intragranular stresses were then simulated during tensile loading of the model using anisotropic elasticity. Driving forcesmore » for phase transformation and slip were calculated from these stresses. The grain-average responses of individual austenite crystals examined before and after multiple stress-induced transformation events showed that grains in the specimen interior carry more axial stress than the surface grains as the superelastic response "shakes down". Examination of the heterogeneity within individual grains showed that regions near grain boundaries exhibit larger stress variation compared to the grain interiors. As a result, this intragranular heterogeneity is more strongly driven by the constraints of neighboring grains than the initial stress state and orientation of the individual grains.« less

Microscopic observation of laser glazed yttria-stabilized zirconia coatings

NASA Astrophysics Data System (ADS)

Morks, M. F.; Berndt, C. C.; Durandet, Y.; Brandt, M.; Wang, J.

2010-08-01

Thermal barrier coatings (TBCs) are frequently used as insulation system for hot components in gas-turbine, combustors and power plant industries. The corrosive gases which come from combustion of low grade fuels can penetrate into the TBCs and reach the metallic components and bond coat and cause hot corrosion and erosion damage. Glazing the top coat by laser beam is advanced approach to seal TBCs surface. The laser beam has the advantage of forming a dense thin layer composed of micrograins. Plasma-sprayed yttria-stabilized zirconia (YSZ) coating was glazed with Nd-YAG laser at different operating conditions. The surface morphologies, before and after laser treatment, were investigated by scanning electron microscopy. Laser beam assisted the densification of the surface by remelting a thin layer of the exposed surface. The laser glazing converted the rough surface of TBCs into smooth micron-size grains with size of 2-9 μm and narrow grain boundaries. The glazed surfaces showed higher Vickers hardness compared to as-sprayed coatings. The results revealed that the hardness increases as the grain size decreases.

Precession electron diffraction for SiC grain boundary characterization in unirradiated TRISO fuel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lillo, T. M.; van Rooyen, I. J.; Wu, Y. Q.

Precession electron diffraction (PED), a transmission electron microscopy-based technique, has been evaluated for the suitability for evaluating grain boundary character in the SiC layer of tristructural isotropic (TRISO) fuel. Although the ultimate goal is to determine the grain boundary characteristics of fission product containing grain boundaries of neutron irradiated SiC, our work reports the effect of transmission electron microscope (TEM) lamella thickness on quality of data and establishes a baseline comparison on grain boundary characteristics determined previously using a conventional EBSD scanning electron microscope (SEM) based technique. In general, it was determined that the lamella thickness produced using the standardmore » FIB fabrication process, is sufficient to provide reliable PED measurements with thicker lamellae (~120 nm) produce higher quality orientation data. Analysis of grain boundary character from the TEM-based PED data showed a much lower fraction of low angle grain boundaries compared to SEM-based EBSD data from the SiC layer of the same TRISO-coated particle as well as a SiC layer deposited at a slightly lower temperature. The fractions of high angle and CSL-related grain boundaries determined by PED are similar to those found using SEM-based EBSD. Since the grain size of the SiC layer of TRSIO fuel can be as small as 250 nm [12], depending on the fabrication parameters, and grain boundary fission product precipitates can be nano-sized, the TEM-based PED orientation data collection method is preferred to determine an accurate representation of the relative fractions of low angle, high angle and CSL-related grain boundaries. It was concluded that although the resolution of the PED data is better by more than an order of magnitude, data acquisition times may be significantly longer or the number of areas analyzed significantly larger than the SEM-based method to obtain a statistically relevant distribution. Also, grain size could be accurately determined but significantly larger analysis areas than those used in this study would be required.« less

Precession electron diffraction for SiC grain boundary characterization in unirradiated TRISO fuel

DOE PAGES

Lillo, T. M.; van Rooyen, I. J.; Wu, Y. Q.

2016-06-16

Precession electron diffraction (PED), a transmission electron microscopy-based technique, has been evaluated for the suitability for evaluating grain boundary character in the SiC layer of tristructural isotropic (TRISO) fuel. Although the ultimate goal is to determine the grain boundary characteristics of fission product containing grain boundaries of neutron irradiated SiC, our work reports the effect of transmission electron microscope (TEM) lamella thickness on quality of data and establishes a baseline comparison on grain boundary characteristics determined previously using a conventional EBSD scanning electron microscope (SEM) based technique. In general, it was determined that the lamella thickness produced using the standardmore » FIB fabrication process, is sufficient to provide reliable PED measurements with thicker lamellae (~120 nm) produce higher quality orientation data. Analysis of grain boundary character from the TEM-based PED data showed a much lower fraction of low angle grain boundaries compared to SEM-based EBSD data from the SiC layer of the same TRISO-coated particle as well as a SiC layer deposited at a slightly lower temperature. The fractions of high angle and CSL-related grain boundaries determined by PED are similar to those found using SEM-based EBSD. Since the grain size of the SiC layer of TRSIO fuel can be as small as 250 nm [12], depending on the fabrication parameters, and grain boundary fission product precipitates can be nano-sized, the TEM-based PED orientation data collection method is preferred to determine an accurate representation of the relative fractions of low angle, high angle and CSL-related grain boundaries. It was concluded that although the resolution of the PED data is better by more than an order of magnitude, data acquisition times may be significantly longer or the number of areas analyzed significantly larger than the SEM-based method to obtain a statistically relevant distribution. Also, grain size could be accurately determined but significantly larger analysis areas than those used in this study would be required.« less

Extreme limestone weathering rates due to micron-scale grain detachment

NASA Astrophysics Data System (ADS)

Emmanuel, Simon; Levenson, Yael

2014-05-01

Chemical dissolution is often assumed to control the weathering rates of carbonate rocks, although some studies have indicated that mechanical erosion could also play a significant role. Quantifying the rates of the different processes is challenging due to the high degree of variability encountered in both field and lab settings. To measure the rates and mechanisms controlling long-term limestone weathering, we analyse a lidar scan of the Western Wall, a Roman period edifice located in Jerusalem. Surface retreat rates in fine-grained micritic limestone blocks are found to be as much as 2 orders of magnitude higher than the average rates estimated for coarse-grained limestone blocks at the same site. In addition, in experiments that use atomic force microscopy to image dissolving micritic limestone, we show that these elevated reaction rates could be due to rapid dissolution along micron-scale grain boundaries, followed by mechanical detachment of tiny particles from the surface. Our analysis indicates that micron-scale grain detachment, rather than pure chemical dissolution, could be the dominant erosional mode for fine-grained carbonate rocks.

Comparative Laboratory and Numerical Simulations of Shearing Granular Fault Gouge: Micromechanical Processes

NASA Astrophysics Data System (ADS)

Morgan, J. K.; Marone, C. J.; Guo, Y.; Anthony, J. L.; Knuth, M. W.

2004-12-01

Laboratory studies of granular shear zones have provided significant insight into fault zone processes and the mechanics of earthquakes. The micromechanisms of granular deformation are more difficult to ascertain, but have been hypothesized based on known variations in boundary conditions, particle properties and geometries, and mechanical behavior. Numerical simulations using particle dynamics methods (PDM) can offer unique views into deforming granular shear zones, revealing the precise details of granular microstructures, particle interactions, and packings, which can be correlated with macroscopic mechanical behavior. Here, we describe a collaborative program of comparative laboratory and numerical experiments of granular shear using idealized materials, i.e., glass beads, glass rods or pasta, and angular sand. Both sets of experiments are carried out under similar initial and boundary conditions in a non-fracturing stress regime. Phenomenologically, the results of the two sets of experiments are very similar. Peak friction values vary as a function of particle dimensionality (1-D vs. 2-D vs. 3-D), particle angularity, particle size and size distributions, boundary roughness, and shear zone thickness. Fluctuations in shear strength during an experiment, i.e., stick-slip events, can be correlated with distinct changes in the nature, geometries, and durability of grain bridges that support the shear zone walls. Inclined grain bridges are observed to form, and to support increasing loads, during gradual increases in assemblage strength. Collapse of an individual grain bridge leads to distinct localization of strain, generating a rapidly propagating shear surface that cuts across multiple grain bridges, accounting for the sudden drop in strength. The distribution of particle sizes within an assemblage, along with boundary roughness and its periodicity, influence the rate of formation and dissipation of grain bridges, thereby controlling friction variations during shear.

Stress-dependent grain size evolution of nanocrystalline Ni-W and its impact on friction behavior

DOE PAGES

Argibay, N.; Furnish, T. A.; Boyce, B. L.; ...

2016-06-07

The friction behavior of ultra-nanocrystalline Ni-W coatings was investigated. A critical stress threshold was identified below which friction remained low, and above which a time-dependent evolution toward higher friction behavior occurred. Founded on established plasticity models we propose a correlation between surface grain size and applied stress that can be used to predict the critical stress separating the two friction regimes. Lastly, this interpretation of plasticity models suggests that macro-scale low and high friction regimes are respectively associated with the nano-scale mechanisms of grain boundary and dislocation-mediated plasticity.

Adhesion, friction, and wear of a copper bicrystal with (111) and (210) grains

NASA Technical Reports Server (NTRS)

Brainard, W. A.; Buckley, D. H.

1973-01-01

Sliding friction experiments were conducted in air with polycrystalline copper and ruby riders sliding against a copper bicrystal. Friction coefficient was measured across the bicrystal surface, and the initiation of adhesive wear was examined with scanning electron microscopy. Results indicate a marked increase in friction coefficient as the copper rider crossed the grain boundary from the (111) plane to the (210) plane of the bicrystal. Adhesion, friction, and initiation of adhesive wear was notably different in the adjacent grains of differing orientation. A slip-band adhesion-generated fracture mechanism for wear particle formation is proposed.

Method of making quasi-grain boundary-free polycrystalline solar cell structure and solar cell structure obtained thereby

DOEpatents

Gonzalez, Franklin N.; Neugroschel, Arnost

1984-02-14

A new solar cell structure is provided which will increase the efficiency of polycrystalline solar cells by suppressing or completely eliminating the recombination losses due to the presence of grain boundaries. This is achieved by avoiding the formation of the p-n junction (or other types of junctions) in the grain boundaries and by eliminating the grain boundaries from the active area of the cell. This basic concept can be applied to any polycrystalline material; however, it will be most beneficial for cost-effective materials having small grains, including thin film materials.

Effect of Aluminum on the Microstructure and Properties of Two Refractory High-Entropy Alloys (Postprint)

DTIC Science & Technology

2014-04-01

The chemical compositions of the recrystallized ic release; distribution unlimited. Fig. 5. (a) Equiaxed grain structure of the annealed...deformation bands crossing a grain boundary; (c) fine recrystallized grains formed at grain boundaries; (d) a higher magnification image shows the...presence of nano-precipitates at the boundaries of the recrystallized grains. 220 O.N. Senkov et al. / Acta Materialia 68 (2014) 214–228and non

Magnetization due to localized states on graphene grain boundary

PubMed Central

Dutta, Sudipta; Wakabayashi, Katsunori

2015-01-01

Magnetism in graphene has been found to originate from various defects, e.g., vacancy, edge formation, add-atoms etc. Here, we discuss about an alternate route of achieving magnetism in graphene via grain boundary. During chemical vapor deposition of graphene, several graphene nucleation centers grow independently and face themselves with unusual bonding environment, giving rise to the formation of grain boundaries. We investigate the origin of magnetism in such grain boundaries within first-principles calculations, by letting two nucleation centers interact with each other at their interface. We observe formation of unprecedented point defect, consisting of fused three-membered and larger carbon rings, which induces net magnetization to graphene quantum dots. In case of periodic lattices, the appearance of array of point defects leads to the formation of magnetic grain boundaries. The net magnetization on these defects arises due to the deviation from bipartite characteristics of pristine graphene. We observe magnetic grain boundary induced dispersion less flat bands near Fermi energy, showing higher localization of electrons. These flat bands can be accessed via small doping, leading to enhanced magnetism. Moreover, the grain boundaries can induce asymmetric spin conduction behavior along the cross boundary direction. These properties can be exploited for sensor and spin-filtering applications. PMID:26145161

Dislocation creep accommodated Grain Boundary Sliding: A high strain rate/low temperature deformation mechanism in calcite ultramylonites

NASA Astrophysics Data System (ADS)

Rogowitz, Anna; Grasemann, Bernhard

2014-05-01

Grain boundary sliding (GBS) is an important grain size sensitive deformation mechanism that is often associated with extreme strain localization and superplasticity. Another mechanism has to operate simultaneously to GBS in order to prevent overlaps and voids between sliding grains. One of the most common accommodating mechanisms is diffusional creep but, recently, dislocation creep has been reported to operate simultaneous to GBS. Due to the formation of a flanking structure in nearly pure calcite marble on Syros (Cyclades, Greece) at lower greenschist facies conditions, an extremely fine grained ultramylonite developed. The microstructure of the layer is characterized by (1) calcite grains with an average grain size of 3.6 µm (developed by low temperature/high strain rate grain boundary migration recrystallization, BLG), (2) grain boundary triple junctions with nearly 120° angles and (3) small cavities preferentially located at triple junctions and at grain boundaries in extension. These features suggest that the dominant deformation mechanism was GBS. In order to get more information on the accommodation mechanism detailed microstructural and textural analyses have been performed on a FEI Quanta 3D FEG instrument equipped with an EDAX Digiview IV EBSD camera. The misorientation distribution curves for correlated and uncorrelated grains follow almost perfect the calculated theoretical curve for a random distribution, which is typical for polycrystalline material deformed by GBS. However, the crystallographic preferred orientation indicates that dislocation creep might have operated simultaneously. We also report Zener-Stroh cracks resulting from dislocation pile up, indicating that dislocation movement was active. We, therefore, conclude that the dominant deformation mechanism was dislocation creep accommodated grain boundary sliding. This is consistent with the observed grain size range that plots at the field boundary between grain size insensitive and grain size sensitive creep, in a deformation mechanism map for calcite.

The effect of grain boundary misorientation on the intergranular M 23C 6 carbide precipitation in thermally treated Alloy 690

NASA Astrophysics Data System (ADS)

Lim, Yun Soo; Kim, Joung Soo; Kim, Hong Pyo; Cho, Hai Dong

2004-10-01

The precipitation characteristics of chromium carbides on various types of grain boundaries in Alloy 690 thermally treated at 720 °C for 10 h were studied through transmission electron microscopy. Precipitation of the intergranular chromium carbides, identified as Cr-rich M 23C 6, was retarded on the low angle grain boundaries, compared to that on the random high angle grain boundaries on which coarse and discrete ones were found. They were rarely found on the coherent twin boundaries, however, needle-like ones were evolved on the incoherent twin and twin related Σ9 boundaries. Precipitation of the chromium carbides was also suppressed on the nearly exact coincidence site lattice boundaries such as Σ11 and Σ15, for which the Brandon criterion was fulfilled. The results of the intergranular M 23C 6 carbide precipitation were explained in terms of the influence of the grain boundary energy.

Ferromagnetic behaviour of ZnO: the role of grain boundaries

PubMed Central

Protasova, Svetlana G; Mazilkin, Andrei A; Goering, Eberhard; Schütz, Gisela; Straumal, Petr B; Baretzky, Brigitte

2016-01-01

The possibility to attain ferromagnetic properties in transparent semiconductor oxides such as ZnO is very promising for future spintronic applications. We demonstrate in this review that ferromagnetism is not an intrinsic property of the ZnO crystalline lattice but is that of ZnO/ZnO grain boundaries. If a ZnO polycrystal contains enough grain boundaries, it can transform into the ferromagnetic state even without doping with “magnetic atoms” such as Mn, Co, Fe or Ni. However, such doping facilitates the appearance of ferromagnetism in ZnO. It increases the saturation magnetisation and decreases the critical amount of grain boundaries needed for FM. A drastic increase of the total solubility of dopants in ZnO with decreasing grain size has been also observed. It is explained by the multilayer grain boundary segregation. PMID:28144542

Temperature effects in accumulation of deuterium and helium at the grain boundaries of a nano-grained tungsten

NASA Astrophysics Data System (ADS)

Kaganovich, Igor; Krstic, Predrag; Startsev, Edward

2014-10-01

It has been known that defects in tungsten, in particular at the grain boundaries, are preferable sites for deuterium and helium retention. For the case of the nano-grained boundaries, we study by classical molecular dynamics the cumulative retention of deuterium and helium at impact energies below 100 eV as functions of tungsten temperature at models of the dislocation boundaries. We obtain a strong preference of the retention of the impact particles at the boundaries at high temperature of 1000 K. Support of PPPL LDRD grant acknowledged.

Influence of boundary-layer dynamics on pollen dispersion and viability

NASA Astrophysics Data System (ADS)

Arritt, Raymond W.; Viner, Brian J.; Westgate, Mark E.

2013-04-01

Adoption of genetically modified (GM) crops has raised concerns that GM traits can accidentally cross into conventional crops or wild relatives through the transport of wind-borne pollen. In order to evaluate this risk it is necessary to account both for dispersion of the pollen grains and environmental influences on pollen viability. The Lagrangian approach is suited to this problem because it allows tracking the environmental temperature and moisture that pollen grains experience as they travel. Taking advantage of this capability we have combined a high-resolution version of the WRF meteorological model with a Lagrangian particle dispersion model to predict maize pollen dispersion and viability. WRF is used to obtain fields of wind, turbulence kinetic energy, temperature, and humidity which are then used as input to the Lagrangian dispersion model. The dispersion model in turn predicts transport of a statistical sample of a pollen cloud from source plants to receptors. We also use the three-dimensional temperature and moisture fields from WRF to diagnose changes in moisture content of the pollen grains and consequent loss of viability. Results show that turbulent motions in the convective boundary layer counteract the large terminal velocity of maize pollen grains and lift them to heights of several hundred meters, so that they can be transported long distances before settling to the ground. We also found that pollen lifted into the upper part of the boundary layer remains more viable than has been inferred using surface observations of temperature and humidity. This is attributed to the thermal and moisture structure that typifies the daytime atmospheric boundary layer, producing an environment of low vapor pressure deficit in the upper boundary layer which helps maintain pollen viability.

Scanning probe microscopy and field emission schemes for studying electron emission from polycrystalline diamond

NASA Astrophysics Data System (ADS)

Chubenko, Oksana; Baturin, Stanislav S.; Baryshev, Sergey V.

2016-09-01

The letter introduces a diagram that rationalizes tunneling atomic force microscopy (TUNA) observations of electron emission from polycrystalline diamonds as described in the recent publications [Chatterjee et al., Appl. Phys. Lett. 104, 171907 (2014); Harniman et al., Carbon 94, 386 (2015)]. The direct observations of electron emission from the grain boundary sites by TUNA could indeed be the evidence of electrons originating from grain boundaries under external electric fields. At the same time, from the diagram, it follows that TUNA and field emission schemes are complimentary rather than equivalent for results interpretation. It is further proposed that TUNA could provide better insights into emission mechanisms by measuring the detailed structure of the potential barrier on the surface of polycrystalline diamonds.

Study on Iron Distribution and Electrical Activities at Grain Boundaries in Polycrystalline Silicon Substrate for Solar Cells

NASA Astrophysics Data System (ADS)

Arafune, Koji; Ohishi, Eichiro; Sai, Hitoshi; Terada, Yasuko; Ohshita, Yoshio; Yamaguchi, Masafumi

2006-08-01

To clarify the role of grain boundaries in iron sinks and carrier recombination centers, iron distributions and their chemical states were studied before and after gettering. They were measured by the X-ray microprobe fluorescence and the X-ray absorption in the near-edge structure using the beamline 37XU at the SPring-8 third-generation synchrotron facility. To determine the crystallographic orientation of the grain boundaries, electron backscatter diffraction measurements were performed. The distribution of electric active defects was characterized by electron-beam-induced current measurements. Before gettering, the iron was distributed in the small grain and its chemical state was similar to that of iron oxide. After gettering, the iron was redistributed along the small angle grain boundary, and its chemical state was similar to the iron silicide complexed with the iron oxide. Regarding the electrical activity, high carrier recombination was observed along the small-angle grain boundary. On the contrary, Σ 3 grain boundaries were relatively weak impurity sinks and showed low recombination activity.

Magnetization reversal mechanism and coercivity enhancement in three-dimensional granular Nd-Fe-B magnets studied by micromagnetic simulations

NASA Astrophysics Data System (ADS)

Lee, Jae-Hyeok; Choe, Jinhyeok; Hwang, Shinwon; Kim, Sang-Koog

2017-08-01

We studied the mechanism of magnetization reversals and coercivity enhancements in three-dimensional (3D) granular Nd-Fe-B permanent magnets using finite-element micromagnetic simulations. The magnetization reversals in the hard magnets consisting of hard-phase grains separated by relatively soft-phase grain boundaries were analyzed with reference to the simulation results for the magnetic field-dependent distributions of the local magnetizations. The saturation magnetization of the grain-boundary phase plays a crucial role in the transition between nucleation- and domain-wall-propagation-controlled reversal processes. The smaller the saturation magnetization of the grain-boundary phase is, the more preferable is the nucleation-controlled process, which results in a larger coercivity. The exchange stiffness of the grain-boundary phase determines the preferred paths of domain-wall propagations, whether inward into grains or along the grain boundaries for relatively small and large exchange stiffness, respectively. However, the exchange stiffness of the grain-boundary phase alone does not significantly contribute to coercivity enhancement in cases where the size of hard-phase grains is much greater than the exchange length. This work paves the way for the design of high-performance hard magnets of large coercivity and maximum-energy-product values.

Thermodynamics, Diffusion, and Structure of Mg2SiO4 forsterite grain boundaries from atomistic modeling

NASA Astrophysics Data System (ADS)

Adjaoud, O.; Marquardt, K.; Jahn, S.

2011-12-01

Most materials are not single crystals but consist of crystalline grains of various sizes, misorientated with respect to each other and joint by grain boundaries. The latter influence many of the material properties. For instance, grain boundaries are short circuits for diffusion and thus they strongly influence transport properties of materials such as electrical conductivity, or mineral growth rates, creep, or phase transform. Olivine is a major component of the Earth's upper mantle and therefore it is of considerable importance to study its physical and thermodynamic polycrystalline properties. In the present study, we have used molecular dynamics simulations to model thermodynamics, self-diffusion and structure of a series of [100] symmetric tilt grain boundaries in forsterite. The interactions between the atoms are modeled by an advanced ionic interaction potential (Jahn and Madden, 2007). The parameters of the potential are fitted to ab initio results. The model was optimized for the Ca-Mg-Al-Si-O system and shows good transferability in a wide range of pressures, temperatures, and compositions. Thermodynamics and structure were simulated at ambient conditions, and self-diffusion coefficients were determined at ambient pressure and temperatures of 1250, 1500, 1750, and 2000 K. We find that the energy and excess free volume of the grain boundaries in forsterite depend significantly on the misorientation angle of the grain boundary. One of our modeled structures is compared with an high-resolution transmission electron micrograph (HRTEM) (Heinemann et al., 2005). We relate our findings to previous studies of grain boundaries in ionic materials and in metals. For small misorientation angles (up to 22.1°), grain boundary structures consist of an array of c-edge dislocations as suggested by Heinemann et al. (2005) and their energies can be readily fit with the Read-Shockley dislocation model for grain boundaries. For high misorientation angles (32.1° and 60.8°), the cores of dislocations overlap and form repeated structural units. Similar to energies and excess free volumes, the self-diffusion coefficients of Mg and O depend significantly on the misorientation angle of the grain boundaries and they are well fitted with Arrhenius law. We compare our results to MgO grain boundary diffusion in forsterite derived from reaction rim growth experiments (Gardés and Heinrich, 2010).

The habit of crystals in aggregates: five parameter grain boundary characterization of olivine

NASA Astrophysics Data System (ADS)

Marquardt, K.; Rohrer, G. S.; Morales, L. F. G.; De Graef, M.; Farla, R. J.

2016-12-01

There is growing evidence that the presence of interfaces in rocks, including phase and grain boundaries influence macroscopic properties. To model resulting bulk rock properties and ultimately interpret geophysical signals, such as electrical conductivity, knowledge about the relative abundance of specific grain boundaries is needed. To date, neither the anisotropic frequency of appearance of specific grain boundaries nor its dependence on chemical composition is known for rock forming minerals. Here, we report detailed interface characterizations in olivine, the most abundant phase in the upper mantle. To obtain the area distribution of the geometrically varying interfaces, which is among the most fundamental information, we used electron backscatter diffraction (EBSD) to detect the orientations of over 3x104grains corresponding to more than 6000 mm length of grain boundary separating them. Subsequently we used a stereological approach to determine the grain boundary character distribution (GBCD), defined as the relative areas of grain boundaries of different types, distinguished by their five degrees of freedom (Rohrer et al. 2004). We discuss data collected from different olivine aggregates with chemical compositions ranging from Mg2SiO4 forsterite to Mg1.8Fe0.2SiO4 derived from different synthesis methods. We show that standard EBSD indexing as commonly used is sufficient for many applications, but when characterizing grain boundaries higher accuracy and precision is fundamental and provided by the new dictionary indexing approach, where clean up procedures, that can cause artifacts, are superfluous. The grain boundary planes show a preference for low index planes, which is in agreement with observations on other materials (e.g. MgO, TiO2, SrTiO3, MgAl2O4). We find that the principal crystallographic planes have the lowest energies resulting in crystal habits dominated by (001) planes, followed by (010) and (001) planes and that 90°/[001] (100)(010) are the most frequent grain boundaries, for pure forsterite aggregates. However in the absence of any impurities such as Al or Ca on the grain boundaries the (001) planes dominate the crystal habits. Rohrer G. S. et al. (2004) The distribution of internal interfaces in polycrystals. Zeitschrift für Met. 95, 197-214.

Improved toughness of refractory compounds. [with elimination of the grain boundary phase

NASA Technical Reports Server (NTRS)

Wright, T. R.; Niesz, D. E.

1974-01-01

The concept of grain-boundary-engineering through elimination of the grain-boundary silicate phase in silicon nitride was developed. The process involved removal of the silica from the nitride powder via a thermal treatment coupled with the use of nitride additives to compensate the remaining oxygen. Magnesium and aluminum nitrides are found to be the most effective additive for use as oxygen compensators. Strength decreases at elevated temperatures are not observed in the alumina containing material. The creep rate of a dual additive sialon composition was two orders of magnitude lower at 1400 C than commercial silicon nitride. A cursory analysis of the creep mechanism indicate that grain-boundary sliding is avoided through elimination of the grain-boundary silicate phase.

Origin of colossal dielectric permittivity of rutile Ti 0.9In 0.05Nb 0.05O 2: single crystal and polycrystalline

DOE PAGES

Song, Yongli; Wang, Xianjie; Sui, Yu; ...

2016-02-12

Here in this article, we investigated the dielectric properties of (In + Nb) co-doped rutile TiO 2 single crystal and polycrystalline ceramics. Both of them showed colossal, up to 10 4, dielectric permittivity at room temperature. The single crystal sample showed one dielectric relaxation process with a large dielectric loss. The voltage-dependence of dielectric permittivity and the impedance spectrum suggest that the high dielectric permittivity of single crystal originated from the surface barrier layer capacitor (SBLC). The impedance spectroscopy at different temperature confirmed that the (In+Nb) co-doped rutile TiO 2 polycrystalline ceramic had semiconductor grains and insulating grain boundaries, andmore » that the activation energies were calculated to be 0.052 eV and 0.35 eV for grain and grain boundary, respectively. The dielectric behavior and impedance spectrum of the polycrystalline ceramic sample indicated that the internal barrier layer capacitor (IBLC) mode made a major contribution to the high ceramic dielectric permittivity, instead of the electron-pinned defect-dipoles.« less

Origin of colossal dielectric permittivity of rutile Ti0.9In0.05Nb0.05O2: single crystal and polycrystalline

PubMed Central

Song, Yongli; Wang, Xianjie; Sui, Yu; Liu, Ziyi; Zhang, Yu; Zhan, Hongsheng; Song, Bingqian; Liu, Zhiguo; Lv, Zhe; Tao, Lei; Tang, Jinke

2016-01-01

In this paper, we investigated the dielectric properties of (In + Nb) co-doped rutile TiO2 single crystal and polycrystalline ceramics. Both of them showed colossal, up to 104, dielectric permittivity at room temperature. The single crystal sample showed one dielectric relaxation process with a large dielectric loss. The voltage-dependence of dielectric permittivity and the impedance spectrum suggest that the high dielectric permittivity of single crystal originated from the surface barrier layer capacitor (SBLC). The impedance spectroscopy at different temperature confirmed that the (In + Nb) co-doped rutile TiO2 polycrystalline ceramic had semiconductor grains and insulating grain boundaries, and that the activation energies were calculated to be 0.052 eV and 0.35 eV for grain and grain boundary, respectively. The dielectric behavior and impedance spectrum of the polycrystalline ceramic sample indicated that the internal barrier layer capacitor (IBLC) mode made a major contribution to the high ceramic dielectric permittivity, instead of the electron-pinned defect-dipoles. PMID:26869187

Origin of colossal dielectric permittivity of rutile Ti0.9In0.05Nb0.05O2: single crystal and polycrystalline

NASA Astrophysics Data System (ADS)

Song, Yongli; Wang, Xianjie; Sui, Yu; Liu, Ziyi; Zhang, Yu; Zhan, Hongsheng; Song, Bingqian; Liu, Zhiguo; Lv, Zhe; Tao, Lei; Tang, Jinke

2016-02-01

In this paper, we investigated the dielectric properties of (In + Nb) co-doped rutile TiO2 single crystal and polycrystalline ceramics. Both of them showed colossal, up to 104, dielectric permittivity at room temperature. The single crystal sample showed one dielectric relaxation process with a large dielectric loss. The voltage-dependence of dielectric permittivity and the impedance spectrum suggest that the high dielectric permittivity of single crystal originated from the surface barrier layer capacitor (SBLC). The impedance spectroscopy at different temperature confirmed that the (In + Nb) co-doped rutile TiO2 polycrystalline ceramic had semiconductor grains and insulating grain boundaries, and that the activation energies were calculated to be 0.052 eV and 0.35 eV for grain and grain boundary, respectively. The dielectric behavior and impedance spectrum of the polycrystalline ceramic sample indicated that the internal barrier layer capacitor (IBLC) mode made a major contribution to the high ceramic dielectric permittivity, instead of the electron-pinned defect-dipoles.

Origin of colossal dielectric permittivity of rutile Ti₀.₉In₀.₀₅Nb₀.₀₅O₂: single crystal and polycrystalline.

PubMed

Song, Yongli; Wang, Xianjie; Sui, Yu; Liu, Ziyi; Zhang, Yu; Zhan, Hongsheng; Song, Bingqian; Liu, Zhiguo; Lv, Zhe; Tao, Lei; Tang, Jinke

2016-02-12

In this paper, we investigated the dielectric properties of (In + Nb) co-doped rutile TiO2 single crystal and polycrystalline ceramics. Both of them showed colossal, up to 10(4), dielectric permittivity at room temperature. The single crystal sample showed one dielectric relaxation process with a large dielectric loss. The voltage-dependence of dielectric permittivity and the impedance spectrum suggest that the high dielectric permittivity of single crystal originated from the surface barrier layer capacitor (SBLC). The impedance spectroscopy at different temperature confirmed that the (In + Nb) co-doped rutile TiO2 polycrystalline ceramic had semiconductor grains and insulating grain boundaries, and that the activation energies were calculated to be 0.052 eV and 0.35 eV for grain and grain boundary, respectively. The dielectric behavior and impedance spectrum of the polycrystalline ceramic sample indicated that the internal barrier layer capacitor (IBLC) mode made a major contribution to the high ceramic dielectric permittivity, instead of the electron-pinned defect-dipoles.

Investigation of consolidation kinetics and microstructure evolution of Al alloys in direct metal laser sintering using phase field simulation

NASA Astrophysics Data System (ADS)

Bimal Satpathy, Bubloom; Nandy, Jyotirmoy; Sahoo, Seshadev

2018-03-01

Direct metal laser sintering is one of the very efficient processes which comes under the field of additive manufacturing and is capable of producing products of good mechanical and physical properties. The process parameters affect the physical and mechanical properties of the final products. Rapid solidification plays an important role in the consolidation kinetics as the powdered material sinters and forms a polycrystalline structure. In the recent times, the enormous use of computational modeling has helped in examining the utility of final products in a wide range of applications. In this study, a phase field model has been implemented to foresee the consolidation kinetics during the liquid state sintering. Temperature profiles have been used to study the densification behavior and neck growth which is caused by the surface diffusion of particles at initial stage. Later, importance of grain boundary and the volume diffusion during densification process is analyzed. It is also found that with rise in temperature, neck growth also increases rapidly due to the interaction of adjacent grains through grain boundary diffusion and stabilization of grain growth.

Enhancing the Bioactivity of Yttria-Stabilized Tetragonal Zirconia Ceramics via Grain-Boundary Activation.

PubMed

Ke, Jinhuan; He, Fupo; Ye, Jiandong

2017-05-17

Yttria-stabilized tetragonal zirconia (Y-TZP) has been proposed as a potential dental implant because of its good biocompatibility, excellent mechanical properties, and distinctive aesthetic effect. However, Y-TZP cannot form chemical bonds with bone tissue because of its biological inertness, which affects the reliability and long-term efficacy of Y-TZP implants. In this study, to improve the bioactivity of Y-TZP ceramics while maintaining their good mechanical performance, Y-TZP was modified by grain-boundary activation via the infiltration of a bioactive glass (BG) sol into the surface layers of Y-TZP ceramics under different negative pressures (atmospheric pressure, -0.05 kPa, and -0.1 kPa), followed by gelling and sintering. The in vitro bioactivity, mechanical properties, and cell behavior of the Y-TZP with improved bioactivity were systematically investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS), electron probe microanalysis (EPMA), and Raman spectroscopy. The results of the bioactivity test conducted by immersing Y-TZP in simulated body fluid (SBF) showed that a bonelike apatite layer was produced on the entire surface. The mechanical properties of the modified Y-TZP decreased as the negative pressure in the BG-infiltration process increased relative to those of the Y-TZP blank group. However, the samples infiltrated with the BG sol under -0.05 kPa and atmospheric pressure still retained good mechanical performance. The cell-culture results revealed that the bioactive surface modification of Y-TZP could promote cell adhesion and differentiation. The present work demonstrates that the bioactivity of Y-TZP can be enhanced by grain-boundary activation, and the bioactive Y-TZP is expected to be a potential candidate for use as a dental implant material.

Uranium vacancy mobility at the Σ5 symmetric tilt and Σ5 twist grain boundaries in UO₂

DOE PAGES

Uberuaga, Blas Pedro; Andersson, David A.

2015-10-01

Ionic transport at grain boundaries in oxides dictates a number of important phenomena, from ionic conductivity to sintering to creep. For nuclear fuels, it also influences fission gas bubble nucleation and growth. Here, using a combination of atomistic calculations and object kinetic Monte Carlo (okMC) simulations, we examine the kinetic pathways associated with uranium vacancies at two model grain boundaries in UO 2. The barriers for vacancy motion were calculated using the nudged elastic band method at all uranium sites at each grain boundary and were used as the basis of the okMC simulations. For both boundaries considered – amore » simple tilt and a simple twist boundary – the mobility of uranium vacancies is significantly higher than in the bulk. For the tilt boundary, there is clearly preferred migration along the tilt axis as opposed to in the perpendicular direction while, for the twist boundary, migration is essentially isotropic within the boundary plane. These results show that cation defect mobility in fluorite-structured materials is enhanced at certain types of grain boundaries and is dependent on the boundary structure with the tilt boundary exhibiting higher rates of migration than the twist boundary.« less

Oxidation of Alloy 600 and Alloy 690: Experimentally Accelerated Study in Hydrogenated Supercritical Water

NASA Astrophysics Data System (ADS)

Moss, Tyler; Cao, Guoping; Was, Gary S.

2017-04-01

The objective of this study is to determine whether the oxidation of Alloys 600 and 690 in supercritical water occurs by the same mechanism in subcritical water. Coupons of Alloys 690 and 600 were exposed to hydrogenated subcritical and supercritical water from 633 K to 673 K (360 °C to 400 °C) and the oxidation behavior was observed. By all measures of oxide character and behavior, the oxidation process is the same above and below the supercritical line. Similar oxide morphologies, structures, and chemistries were observed for each alloy across the critical point, indicating that the oxidation mechanism is the same in both subcritical and supercritical water. Oxidation results in a multi-layer oxide structure composed of particles of NiO and NiFe2O4 formed by precipitation on the outer surface and a chromium-rich inner oxide layer formed by diffusion of oxygen to the metal-oxide interface. The inner oxide on Alloy 600 is less chromium rich than that observed on Alloy 690 and is accompanied by preferential oxidation of grain boundaries. The inner oxide on Alloy 690 initially forms by internal oxidation before a protective layer of chromium-rich MO is formed with Cr2O3 at the metal-oxide interface. Grain boundaries in Alloy 690 act as fast diffusion paths for chromium that forms a protective Cr2O3 layer at the surface, preventing grain boundary oxidation from occurring.

Selective Internal Oxidation as a Mechanism for Intergranular Stress Corrosion Cracking of Ni-Cr-Fe Alloys

NASA Astrophysics Data System (ADS)

Capell, Brent M.; Was, Gary S.

2007-06-01

The mechanism of selective internal oxidation (SIO) for intergranular stress corrosion cracking (IGSCC) of nickel-base alloys has been investigated through a series of experiments using high-purity alloys and a steam environment to control the formation of NiO on the surface. Five alloys (Ni-9Fe, Ni-5Cr, Ni-5Cr-9Fe, Ni-16Cr-9Fe, and Ni-30Cr-9Fe) were used to investigate oxidation and intergranular cracking behavior for hydrogen-to-water vapor partial pressure ratios (PPRs) between 0.001 and 0.9. The Ni-9Fe, Ni-5Cr, and Ni-5Cr-9Fe alloys formed a uniform Ni(OH)2 film at PPRs less than 0.09, and the higher chromium alloys formed chromium-rich oxide films over the entire PPR range studied. Corrosion coupon results show that grain boundary oxides extended for significant depths (>150 nm) below the sample surface for all but the highest Cr containing alloy. Constant extension rate tensile (CERT) test results showed that intergranular cracking varied with PPR and cracking was more pronounced at a PPR value where nonprotective Ni(OH)2 was able to form and a link between the nonprotective Ni(OH)2 film and the formation of grain boundary oxides is suggested. The observation of grain boundary oxides in stressed and unstressed samples as well as the influence of alloy content on IG cracking and oxidation support SIO as a mechanism for IGSCC.

Pipe and grain boundary diffusion of He in UO 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Galvin, C. O.T.; Cooper, M. W. D.; Fossati, P. C. M.

Molecular dynamics simulations have been conducted to study the effects of dislocations and grain boundaries on He diffusion inmore » $$\\text{U}{{\\text{O}}_{2}}$$ . Calculations were carried out for the {100}, {110} and {111} $$\\langle 1\\,1\\,0\\rangle $$ edge dislocations, the screw $$\\langle 1\\,1\\,0\\rangle $$ dislocation and Σ5, Σ13, Σ19 and Σ25 tilt grain boundaries. He diffusivity as a function of distance from the dislocation core and grain boundaries was investigated for the temperature range 2300–3000 K. An enhancement in diffusivity was predicted within 20 Å of the dislocations or grain boundaries. Further investigation showed that He diffusion in the edge dislocations follows anisotropic behaviour along the dislocation core, suggesting that pipe diffusion occurs. Here, an Arrhenius plot of He diffusivity against the inverse of temperature was also presented and the activation energy calculated for each structure, as a function of distance from the dislocation or grain boundary.« less

Pipe and grain boundary diffusion of He in UO 2

DOE PAGES

Galvin, C. O.T.; Cooper, M. W. D.; Fossati, P. C. M.; ...

2016-10-12

Molecular dynamics simulations have been conducted to study the effects of dislocations and grain boundaries on He diffusion inmore » $$\\text{U}{{\\text{O}}_{2}}$$ . Calculations were carried out for the {100}, {110} and {111} $$\\langle 1\\,1\\,0\\rangle $$ edge dislocations, the screw $$\\langle 1\\,1\\,0\\rangle $$ dislocation and Σ5, Σ13, Σ19 and Σ25 tilt grain boundaries. He diffusivity as a function of distance from the dislocation core and grain boundaries was investigated for the temperature range 2300–3000 K. An enhancement in diffusivity was predicted within 20 Å of the dislocations or grain boundaries. Further investigation showed that He diffusion in the edge dislocations follows anisotropic behaviour along the dislocation core, suggesting that pipe diffusion occurs. Here, an Arrhenius plot of He diffusivity against the inverse of temperature was also presented and the activation energy calculated for each structure, as a function of distance from the dislocation or grain boundary.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Tingguang; Xia, Shuang, E-mail: xs@shu.edu.cn; Li, Hui

Grain boundary engineering was carried out on an aging-treated nickel based Alloy 690, which has precipitated carbides at grain boundaries. Electron backscatter diffraction technique was used to investigate the grain boundary networks. Results show that, compared with the solution-annealed samples, the aging-treated samples with pre-existing carbides at grain boundaries need longer duration or higher temperature during annealing after low-strain tensile deformation for forming high proportion of low-Σ coincidence site lattice grain boundaries (more than 75%). The reason is that the primary recrystallization is inhibited or retarded owing to that the pre-existing carbides are barriers to grain boundaries migration. - Highlights:more » • Study of GBE as function of pre-existing GB carbides, tensile strain and annealing • Recrystallization of GBE is inhibited or retarded by the pre-existing carbides. • Retained carbides after annealing show the original GB positions. • More than 80% of special GBs were formed after the modification of GBE processing. • Multiple twinning during recrystallization is the key process of GBE.« less

Reconstruction of 3d grain boundaries from rock thin sections, using polarised light

NASA Astrophysics Data System (ADS)

Markus Hammes, Daniel; Peternell, Mark

2016-04-01

Grain boundaries affect the physical and chemical properties of polycrystalline materials significantly by initiating reactions and collecting impurities (Birchenall, 1959), and play an essential role in recrystallization (Doherty et al. 1997). In particular, the shape and crystallographic orientation of grain boundaries reveal the deformation and annealing history of rocks (Kruhl and Peternell 2002, Kuntcheva et al. 2006). However, there is a lack of non-destructive and easy-to-use computer supported methods to determine grain boundary geometries in 3D. The only available instrument using optical light to measure grain boundary angles is still the polarising microscope with attached universal stage; operated manually and time-consuming in use. Here we present a new approach to determine 3d grain boundary orientations from 2D rock thin sections. The data is recorded by using an automatic fabric analyser microscope (Peternell et al., 2010). Due to its unique arrangement of 9 light directions the highest birefringence colour due to each light direction and crystal orientation (retardation) can be determined at each pixel in the field of view. Retardation profiles across grain boundaries enable the calculation of grain boundary angle and direction. The data for all positions separating the grains are combined and further processed. In combination with the lateral position of the grain boundary, acquired using the FAME software (Hammes and Peternell, in review), the data is used to reconstruct a 3d grain boundary model. The processing of data is almost fully automatic by using MATLAB®. Only minor manual input is required. The applicability was demonstrated on quartzite samples, but the method is not solely restricted on quartz grains and other birefringent polycrystalline materials could be used instead. References: Birchenall, C.E., 1959: Physical Metallurgy. McGraw-Hill, New York. Doherty, R.D., Hughes, D.A., Humphreys, F.J., Jonas, J.J., Juul Jensen, D., Kassner, M.E., King, W.E., McNelley, T.R., McQueen, H.J., Rollett, A.D., 1997: Current issues in recrystallization: a review. Materials Science and Engineering A 238, 219-274. Hammes, D.M., Peternell, M., in review. FAME: Software for analysing rock microstructures. Computers & Geoscience. Kruhl, J.H., Peternell, M., 2002. The equilibration of high-angle grain boundaries in dynamically recrystallized quartz: the effect of crystallography and temperature. Journal of Structural Geology 24, 1125-1137. Kuntcheva, B., Kruhl, J.H. & Kunze, K., 2006. Crystallographic orientation of high-angle grain boundaries in dynamically recrystallized quartz: First results. Tectonophysics 421, 331-346. Peternell, M., Hasalová, P., Wilson, J.L., Piaziolo, S., Schulmann, K., 2010. Evaluating quartz crystallographic preferred orientations and the role of deformation partitioning using EBSD and fabric analyser techniques. Journal of Structural Geology 32, 803-817.

Searching for Hysteresis in Models of Mantle Convection with Grain-Damage

NASA Astrophysics Data System (ADS)

Lamichhane, R.; Foley, B. J.

2017-12-01

The mode of surface tectonics on terrestrial planets is determined by whether mantle convective forces are capable of forming weak zones of localized deformation in the lithosphere, which act as plate boundaries. If plate boundaries can form then a plate tectonic mode develops, and if not convection will be in the stagnant lid regime. Episodic subduction or sluggish lid convection are also possible in between the nominal plate tectonic and stagnant lid regimes. Plate boundary formation is largely a function of the state of the mantle, e.g. mantle temperature or surface temperature, and how these conditions influence both mantle convection and the mantle rheology's propensity for forming weak, localized plate boundaries. However, a planet's tectonic mode also influences whether plate boundaries can form, as the driving forces for plate boundary formation (e.g. stress and viscous dissipation) are different in a plate tectonic versus stagnant lid regime. As a result, tectonic mode can display hysteresis, where convection under otherwise identical conditions can reach different final states as a result of the initial regime of convection. Previous work has explored this effect in pseudoplastic models, finding that it is more difficult to initiate plate tectonics starting from a stagnant lid state than it is to sustain plate tectonics when already in a mobile lid regime, because convective stresses in the lithosphere are lower in a stagnant lid regime than in a plate tectonic regime. However, whether and to what extent such hysteresis is displayed when alternative rheological models for lithospheric shear localization are used is unknown. In particular, grainsize reduction is commonly hypothesized to be a primary cause of shear localization and plate boundary formation. We use new models of mantle convection with grain-size evolution to determine how the initial mode of surface tectonics influences the final convective regime reached when convection reaches statistical steady-state. Scaling analysis is performed to quantify how subduction initiation from a stagnant lid differs from sustaining subduction in a mobile lid. The implications of our results for the evolution of the mode of surface tectonics on terrestrial planets will also be discussed.

Density functional calculation of activation energies for lattice and grain boundary diffusion in alumina

NASA Astrophysics Data System (ADS)

Lei, Yinkai; Gong, Yu; Duan, Zhiyao; Wang, Guofeng

2013-06-01

To acquire knowledge on the lattice and grain boundary diffusion processes in alumina, we have determined the activation energies of elementary O and Al diffusive jumps in the bulk crystal, Σ3(0001) grain boundaries, and Σ3(101¯0) grain boundaries of α-Al2O3 using the first-principles density functional theory method. Specifically, we calculated the activation energies for four elementary jumps of both O and Al lattice diffusion in alumina. It was predicted that the activation energy of O lattice diffusion varied from 3.58 to 5.03 eV, while the activation energy of Al lattice diffusion ranged from 1.80 to 3.17 eV. As compared with experimental measurements, the theoretical predictions of the activation energy for lattice diffusion were lower and thus implied that there might be other high-energy diffusive jumps in the experimental alumina samples. Moreover, our results suggested that the Al lattice diffusion was faster than the O lattice diffusion in alumina, in agreement with experiment observations. Furthermore, it was found from our calculations for α-Al2O3 that the activation energies of O and Al grain boundary diffusion in the high-energy Σ3(0001) grain boundaries were significantly lower than those of the lattice diffusion. In contrast, the activation energies of O and Al grain boundary diffusion in the low-energy Σ3(101¯0) grain boundaries could be even higher than those of the lattice diffusion.

TEM Study of Intergranular Fluid Distributions in Rocks at a Nanometer Scale

NASA Astrophysics Data System (ADS)

Hiraga, T.; Anderson, I. M.; Kohlstedt, D. L.

2002-12-01

The distribution of intergranular fluids in rocks plays an essential role in fluid migration and rock rheology. Structural and chemical analyses with sub-nanometer resolution is possible with transmission and scanning-transmission electron microscopy; therefore, it is possible to perform the fine-scale structural analyses required to determine the presence or absence of very thin fluid films along grain boundaries. For aqueous fluids in crustal rocks, Hiraga et al. (2001) observed a fluid morphology controlled by the relative values of the solid-solid and solid-fluid interfacial energies, which resulted in well-defined dihedral angles. Their high-resolution transmission electron microscopy (TEM) observations demonstrate that grain boundaries are tight even at a nanometer scale, consistent with the absence of aqueous fluid films. For partially molten ultra-mafic rocks, two conflicting conclusions have been reached: nanometer-thick melt films wet grain boundaries (Drury and Fitz Gerald 1996; De Kloe et al. 2000) versus essentially all grain boundaries are melt-free (Vaughan et al. 1982; Kohlstedt 1990). To resolve this conflict, Hiraga et al. (2002) examined grain boundaries in quenched partially molten peridotites. Their observations demonstrate the following: (i) Although a small fraction of the grains are separated by relatively thick (~1 μm) layers of melt, lattice fringe images obtained with a high-resolution TEM reveal that most of the remaining boundaries do not contain a thin amorphous phase. (ii) In addition, the composition of olivine-olivine grain boundaries was analyzed with a nano-beam analytical scanning TEM with a probe size of <2 nm. Although the grain boundaries contained no melt film, the concentration of Ca, Al and Ti were enhanced near the boundaries. The segregation of these elements to the grain boundaries formed enriched regions <7 nm wide. A similar pattern of chemical segregation was detected in subsolidus systems. Creep experiments on the partially molten rocks that were analyzed in this study reveal little weakening even at melt contents approaching 4 vol%, consistent with our observations of melt-free grain boundaries.

Austenite grain growth simulation considering the solute-drag effect and pinning effect.

PubMed

Fujiyama, Naoto; Nishibata, Toshinobu; Seki, Akira; Hirata, Hiroyuki; Kojima, Kazuhiro; Ogawa, Kazuhiro

2017-01-01

The pinning effect is useful for restraining austenite grain growth in low alloy steel and improving heat affected zone toughness in welded joints. We propose a new calculation model for predicting austenite grain growth behavior. The model is mainly comprised of two theories: the solute-drag effect and the pinning effect of TiN precipitates. The calculation of the solute-drag effect is based on the hypothesis that the width of each austenite grain boundary is constant and that the element content maintains equilibrium segregation at the austenite grain boundaries. We used Hillert's law under the assumption that the austenite grain boundary phase is a liquid so that we could estimate the equilibrium solute concentration at the austenite grain boundaries. The equilibrium solute concentration was calculated using the Thermo-Calc software. Pinning effect was estimated by Nishizawa's equation. The calculated austenite grain growth at 1473-1673 K showed excellent correspondence with the experimental results.

Role of grain and grain boundary on the electrical and thermal conductivity of Bi0.9Y0.1Fe0.9Mn0.1O3 ceramics

NASA Astrophysics Data System (ADS)

Pandey, Rabichandra; Panda, Chandrakanta; Kumar, Pawan; Pradhan, Lagen Kumar; Kar, Manoranjan

2017-05-01

Role of grain and grain boundary on electrical and thermal conductivity of Bi0.9Y0.1Fe0.9Mn0.1O3 ceramic was investigated systematically. Tartaric acid modified sol gel method was used to synthesize the compound. X-ray diffraction technique was used to confirm the formation of single phase orthorhombic (Pbnm) structure. Electrical properties of the sample were measured with a wide frequency range from 100Hz to 10MHz at different temperature from 40°C to 250°C. AC impedance studies indicate the presence of grain and grain boundary effect. The negative temperature coefficient of resistance (NTCR) behaviour of the compound has been confirmed by the cole-cole plot. DC electrical and thermal conductivities of the compound were explained on the basis of grain and grain boundaries.

Unraveling irradiation induced grain growth with in situ transmission electron microscopy and coordinated modeling

DOE PAGES

Bufford, D. C.; Abdeljawad, F. F.; Foiles, S. M.; ...

2015-11-09

Here, nanostructuring has been proposed as a method to enhance radiation tolerance, but many metallic systems are rejected due to significant concerns regarding long term grain boundary and interface stability. This work utilized recent advancements in transmission electron microscopy (TEM) to quantitatively characterize the grain size, texture, and individual grain boundary character in a nanocrystalline gold model system before and after in situ TEM ion irradiation with 10 MeV Si. The initial experimental measurements were fed into a mesoscale phase field model, which incorporates the role of irradiation-induced thermal events on boundary properties, to directly compare the observed and simulatedmore » grain growth with varied parameters. The observed microstructure evolution deviated subtly from previously reported normal grain growth in which some boundaries remained essentially static. In broader terms, the combined experimental and modeling techniques presented herein provide future avenues to enhance quantification and prediction of the thermal, mechanical, or radiation stability of grain boundaries in nanostructured crystalline systems.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Weiguo, E-mail: wang_weiguo@vip.163.com

High purity (99.99%) iron samples were cold rolled with a thickness reduction of 87% followed by a annealing at 620 °C for 15 and 45 min, then the grain boundary plane distributions were characterized by electron backscatter diffraction and a stereology and statistics based five parameter analysis. The results showed that the grain boundary planes were mainly distributed on (1 0 0) and such distribution was enhanced obviously when the holding time of annealing increased from 15 to 45 min during which an extensive grain growth and a dramatic texture evolution took place. Further analysis indicated such distribution was largelymore » due to the rotation of grain boundary planes of the [1 0 0] misoriented grains. Additionally, it was also observed that some random boundaries of [1 0 0] misoriented grains were changing from asymmetrical tilt into (1 0 0)/(− 1 0 0) twist when annealing proceeded from 15 to 45 min. Based on the present work and the results reported by other investigators, it was suggested that the chemistry appeared to be critical in determining the grain boundary plane distribution in iron based materials. - Highlights: •Grain boundary (GB) plane distribution (GBPD) in a high purity (99.99%) was studied. •GB planes are mainly distributed on (1 0 0) in the cold rolled and annealed samples. •Such distribution is largely due to the rotation of GB planes of [100] misoriented grains. •Some [1 0 0] asymmetrical tilt boundaries are evolving into twist ones during annealing.« less

Electromigration in Cu(Al) and Cu(Mn) damascene lines

NASA Astrophysics Data System (ADS)

Hu, C.-K.; Ohm, J.; Gignac, L. M.; Breslin, C. M.; Mittal, S.; Bonilla, G.; Edelstein, D.; Rosenberg, R.; Choi, S.; An, J. J.; Simon, A. H.; Angyal, M. S.; Clevenger, L.; Maniscalco, J.; Nogami, T.; Penny, C.; Kim, B. Y.

2012-05-01

The effects of impurities, Mn or Al, on interface and grain boundary electromigration (EM) in Cu damascene lines were investigated. The addition of Mn or Al solute caused a reduction in diffusivity at the Cu/dielectric cap interface and the EM activation energies for both Cu-alloys were found to increase by about 0.2 eV as compared to pure Cu. Mn mitigated and Al enhanced Cu grain boundary diffusion; however, no significant mitigation in Cu grain boundary diffusion was observed in low Mn concentration samples. The activation energies for Cu grain boundary diffusion were found to be 0.74 ± 0.05 eV and 0.77 ± 0.05 eV for 1.5 μm wide polycrystalline lines with pure Cu and Cu (0.5 at. % Mn) seeds, respectively. The effective charge number in Cu grain boundaries Z*GB was estimated from drift velocity and was found to be about -0.4. A significant enhancement in EM lifetimes for Cu(Al) or low Mn concentration bamboo-polycrystalline and near-bamboo grain structures was observed but not for polycrystalline-only alloy lines. These results indicated that the existence of bamboo grains in bamboo-polycrystalline lines played a critical role in slowing down the EM-induced void growth rate. The bamboo grains act as Cu diffusion blocking boundaries for grain boundary mass flow, thus generating a mechanical stress-induced back flow counterbalancing the EM force, which is the equality known as the "Blech short length effect."

Reversal in the Size Dependence of Grain Rotation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Xiaoling; Tamura, Nobumichi; Mi, Zhongying

The conventional belief, based on the Read-Shockley model for the grain rotation mechanism, has been that smaller grains rotate more under stress due to the motion of grain boundary dislocations. However, in our high-pressure synchrotron Laue x-ray microdiffraction experiments, 70 nm nickel particles are found to rotate more than any other grain size. We infer that the reversal in the size dependence of the grain rotation arises from the crossover between the grain boundary dislocation-mediated and grain interior dislocation-mediated deformation mechanisms. The dislocation activities in the grain interiors are evidenced by the deformation texture of nickel nanocrystals. This new findingmore » reshapes our view on the mechanism of grain rotation and helps us to better understand the plastic deformation of nanomaterials, particularly of the competing effects of grain boundary and grain interior dislocations.« less

Reversal in the Size Dependence of Grain Rotation

DOE PAGES

Zhou, Xiaoling; Tamura, Nobumichi; Mi, Zhongying; ...

2017-03-01

The conventional belief, based on the Read-Shockley model for the grain rotation mechanism, has been that smaller grains rotate more under stress due to the motion of grain boundary dislocations. However, in our high-pressure synchrotron Laue x-ray microdiffraction experiments, 70 nm nickel particles are found to rotate more than any other grain size. We infer that the reversal in the size dependence of the grain rotation arises from the crossover between the grain boundary dislocation-mediated and grain interior dislocation-mediated deformation mechanisms. The dislocation activities in the grain interiors are evidenced by the deformation texture of nickel nanocrystals. This new findingmore » reshapes our view on the mechanism of grain rotation and helps us to better understand the plastic deformation of nanomaterials, particularly of the competing effects of grain boundary and grain interior dislocations.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Merkle, K. L.; Csencsits, R.; Rynes, K. L.

In the absence of high-order aberrations, the lattice fringe technique should allow measurement of grain boundary rigid-body displacements to accuracies about an order of magnitude better than the point-to-point resolution of the transmission electron microscope. The three-fold astigmatism, however, introduces shifts of the lattice fringe pattern that depend on the orientation of the lattice relative to the direction of the three-fold astigmatism and thus produces an apparent shift between the two grains bordering the grain boundary. By image simulation of grain boundary model structures, the present paper explores the effect of these extraneous shifts on grain boundary volume expansion measurements.more » It is found that the shifts depend, among others, on zone axis direction and the magnitude of the lattice parameter. For many grain boundaries of interest, three-fold astigmatism correction to better than 100 nm appears necessary to achieve the desired accuracies.« less

Measuring grain boundary character distributions in Ni-base alloy 725 using high-energy diffraction microscopy

DOE PAGES

Bagri, Akbar; Hanson, John P.; Lind, J. P.; ...

2016-10-25

We use high-energy X-ray diffraction microscopy (HEDM) to characterize the microstructure of Ni-base alloy 725. HEDM is a non-destructive technique capable of providing three-dimensional reconstructions of grain shapes and orientations in polycrystals. The present analysis yields the grain size distribution in alloy 725 as well as the grain boundary character distribution (GBCD) as a function of lattice misorientation and boundary plane normal orientation. We find that the GBCD of Ni-base alloy 725 is similar to that previously determined in pure Ni and other fcc-base metals. We find an elevated density of Σ9 and Σ3 grain boundaries. We also observe amore » preponderance of grain boundaries along low-index planes, with those along (1 1 1) planes being the most common, even after Σ3 twins have been excluded from the analysis.« less

Defect and grain boundary scattering in tungsten: A combined theoretical and experimental study

NASA Astrophysics Data System (ADS)

Lanzillo, Nicholas A.; Dixit, Hemant; Milosevic, Erik; Niu, Chengyu; Carr, Adra V.; Oldiges, Phil; Raymond, Mark V.; Cho, Jin; Standaert, Theodorus E.; Kamineni, Vimal K.

2018-04-01

Several major electron scattering mechanisms in tungsten (W) are evaluated using a combination of first-principles density functional theory, a Non-Equilibrium Green's Function formalism, and thin film Kelvin 4-point sheet resistance measurements. The impact of grain boundary scattering is found to be roughly an order of magnitude larger than the impact of defect scattering. Ab initio simulations predict average grain boundary reflection coefficients for a number of twin grain boundaries to lie in the range r = 0.47 to r = 0.62, while experimental data can be fit to the empirical Mayadas-Schatzkes model with a comparable but slightly larger value of r = 0.69. The experimental and simulation data for grain boundary resistivity as a function of grain size show excellent agreement. These results provide crucial insights for understanding the impact of scaling of W-based contacts between active devices and back-end-of-line interconnects in next-generation semiconductor technology.

Limitations to the Measurement of Oxygen Concentrations by HRTEM Imposed by Surface Roughness

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lupini, Andrew R; Chisholm, Matthew F; van Benthem, Klaus

2005-01-01

In an article published in Microscopy and Microanalysis recently (Jia et al., 2004), it was claimed that aberration-corrected high resolution transmission electron microscopy (HRTEM) allows the quantitative measurement of oxygen concentrations in ceramic materials with atomic resolution. Similar claims have recently appeared elsewhere, based on images obtained through aberration correction (Jia et al., 2003; Jia & Urban, 2004) or very high voltages (Zhang et al., 2003). Seeing oxygen columns is a significant achievement of great importance (Spence, 2003) that will doubtlessly allow some exciting new science; however, other models could provide a better explanation for some of the experimental datamore » than variations in the oxygen concentration. Quantification of the oxygen concentrations was attempted by comparing experimental images with simulations in which the fractional occupancy in individual oxygen columns was reduced. The results were interpreted as representing nonstoichiometry within the bulk and at grain boundaries. This is plausible because previous studies have shown that grain boundaries can be nonstoichiometric (Kim et al., 2001), and it is indeed possible that oxygen vacancies are present at boundaries or in the bulk. However, is this the only possible interpretation? We show that for the thicknesses considered a better match to the images is obtained using a simple model of surface damage in which atoms are removed from the surface, which would usually be interpreted as surface damage or local thickness variation (from ion milling, for example).« less

Analysis of grain boundary phase devitrification of Y2O3- and Al2O3-doped Si3N4

NASA Technical Reports Server (NTRS)

Hench, L. L.; Vaidyanathan, P. N.

1983-01-01

The present study has the objective to show that a Fourier Transform IR (FTIR) spectrometer in a single-beam reflection mode can be used for direct comparison of fractured vs nonfractured Si3N4 surfaces. This can be done because the FTIR method permits a digital summation of nearly 1000 scans of the fracture surface. Commercial-grade Si3N4, Y2O3, and Al2O3 were used in the study. The samples were heat treated in a vacuum induction heating furnace at either 1000 C for 10 h or 1200 C for 10 h each. Use of Fourier transform IR reflection spectroscopic analysis and X-ray diffraction shows that 10 h at 1200 C is sufficient to devitrify the amorphous grain boundary phase of Si3N4 containing 15 percent Y2O3 + 2 percent Al2O3 densification aids.

Microstructural characterization and electron backscatter diffraction analysis across the welded interface of duplex stainless steel

NASA Astrophysics Data System (ADS)

Zhang, Zhiqiang; Jing, Hongyang; Xu, Lianyong; Han, Yongdian; Gao, Zhanqi; Zhao, Lei; Zhang, Jianli

2017-08-01

The microstructural evolution, orientation relationships, boundary characteristics, grain type, local deformation, and microhardness across the welded interface of duplex stainless steel (DSS) were investigated. The DSS welded joint consisted of four typical zones: base metal (BM), low-temperature heat-affected zone (LTHAZ), high-temperature heat-affected zone (HTHAZ), and weld metal (WM). The apparent microstructural changes in the HTHAZ and LTHAZ were secondary austenite and Cr2N precipitation. A modified cooperative precipitation mechanism of secondary austenite and Cr2N at the interface was proposed. Furthermore, the ferrite in both the HTHAZ and LTHAZ maintained the same distribution as the ferrite texture in the BM, while this ferrite texture disappeared completely in the WM. Different austenite grains in the different zones exhibited different orientation relationships with the ferrite matrix. Special grain boundaries were mainly distributed between the austenite grains, while the ferrite grains primarily contained random grain boundaries. Austenite twins constituted the largest proportion of the special boundaries. The special austenite grain boundaries in the BM and LTHAZ were higher in relative frequency than those in the HTHAZ and WM. The ferrite grains in the HTHAZ and WM mainly consisted of substructured grains. In the BM, the recrystallization degree of ferrite was significantly lower than that of austenite grains. The local deformations were mainly generated in the grain boundaries and within the deformed grains. The HTHAZ exhibited the highest hardness, while the BM had the lowest hardness. The LTHAZ had a lower hardness than the HTHAZ and higher hardness than the BM.

Low-Voltage High-Performance UV Photodetectors: An Interplay between Grain Boundaries and Debye Length.

PubMed

Bo, Renheng; Nasiri, Noushin; Chen, Hongjun; Caputo, Domenico; Fu, Lan; Tricoli, Antonio

2017-01-25

Accurate detection of UV light by wearable low-power devices has many important applications including environmental monitoring, space to space communication, and defense. Here, we report the structural engineering of ultraporous ZnO nanoparticle networks for fabrication of very low-voltage high-performance UV photodetectors. A record high photo- to dark-current ratio of 3.3 × 10 5 and detectivity of 3.2 × 10 12 Jones at an ultralow operation bias of 2 mV and low UV-light intensity of 86 μW·cm -2 are achieved by controlling the interplay between grain boundaries and surface depletion depth of ZnO nanoscale semiconductors. An optimal window of structural properties is determined by varying the particle size of ultraporous nanoparticle networks from 10 to 42 nm. We find that small electron-depleted nanoparticles (≤40 nm) are necessary to minimize the dark-current; however, the rise in photocurrent is tampered with decreasing particle size due to the increasing density of grain boundaries. These findings reveal that nanoparticles with a size close to twice their Debye length are required for high photo- to dark-current ratio and detectivity, while further decreasing their size decreases the photodetector performance.

Diffraction-based study of fatigue crack initiation and propagation in aerospace aluminum alloys

NASA Astrophysics Data System (ADS)

Gupta, Vipul K.

The crack initiation sites and microstructure-sensitive growth of small fatigue cracks are experimentally characterized in two precipitation-hardened aluminum alloys, 7075-T651 and 7050-T7451, stressed in ambient temperature moist-air (warm-humid) and -50°C dry N2 (cold-dry) environmental conditions. Backscattered electron imaging (BSE) and energy dispersive spectroscopy (EDS) of the fracture surfaces showed that Fe-Cu rich constituent particle clusters are the most common initiation sites within both alloys stressed in either environment. The crack growth within each alloy, on average, was observed to be slowed in the cold-dry environment than in the warm-humid environment, but only at longer crack lengths. Although no overwhelming effects of grain boundaries and grain orientations on small-crack growth were observed, crack growth data showed local fluctuations within individual grains. These observations are understood as crack propagation through the underlying substructure at the crack surface and frequent interaction with low/high-angle grain and subgrain boundaries, during cyclic loading, and, are further attributed to periodic changes in crack propagation path and multiple occurrences of crack-branching observed in the current study. SEM-based stereology in combination with electron backscattered diffraction (EBSD) established fatigue crack surface crystallography within the region from ˜1 to 50 mum of crack initiating particle clusters. Fatigue crack facets were parallel to a wide variety of crystallographic planes, with pole orientations distributed broadly across the irreducible stereographic triangle between the {001} and {101}-poles within both warm-humid and cold-dry environments. The results indicate environmentally affected fatigue cracking in both cases, given the similarity between the observed morphology and crystallography with that of a variety of aerospace aluminum alloys cracked in the presence of moist-air. There was no evidence of crystallographic {111} slip-plane cracking typical of the Stage I crack growth mode observed in single crystals and high purity polycrystals of face centered cubic metals, and which has presently been assumed for the present materials within fatigue crack initiation models. Rather, the facets tend to have near-Mode I spatial orientation, which is another indicator of the importance of environmentally affected fatigue damage. The results provide a physical basis to develop microstructurally-based next generation multi-stage fatigue (MSF) models that should include a new crack decohesion criteria based upon environmental fatigue cracking mechanisms. EBSD study of small-cracks in alloy 7050-T7451, stressed in warm-humid environment, showed that crack-path orientation changes and crack-branching occurred at both low/high-angle grain and subgrain boundaries. Single surface trace analysis suggests that the crack-path differs substantially from crystallographic slip-planes. EBSD-based observations of small-crack propagation through subgrain structure, either formed by cyclic plastic strain accumulation or pre-existing (typical of unrecrystallized grain structure in the present materials), suggest that subgrain structure plays a crucial role in small fatigue crack propagation. As mentioned earlier, local fluctuations in small-crack growth rates appear to be caused by frequent interaction with subgrain boundaries, and multiple occurrences of crack-branching and crack-path orientation changes at low/high-angle grain and subgrain boundaries. The aforementioned deviation from low-index {001}/{101}-planes and the occurrence of high-index cracking planes observed by EBSD/Stereology, in this study and others, are interpreted as trans-subgranular decohesion or inter-subgranular cracking, due to trapped hydrogen. In summary, the results provide a firmer experimental foundation for, and clearer understanding of, the mechanisms of environmental fatigue cracking of aluminum alloys, especially the role of inter-subgranular cracking, which had previously been advanced based upon fracture surface observations alone.

Cellular interface morphologies in directional solidification. II - The effect of grain boundaries

NASA Technical Reports Server (NTRS)

Ungar, Lyle H.; Brown, Robert A.

1984-01-01

A singular perturbation analysis valid for small grain-boundary slopes is used with the one-sided model for solidification to show that grain boundaries introduce imperfections into the symmetry of the developing cellular interfaces which rupture the junction between the family of planar shapes and the bifurcating cellular families. Undulating interfaces are shown to develop first near grain boundaries, and to evolve with decreasing temperature gradient either by a smooth transition from the almost planar family or by a sudden jump to moderate-amplitude cellular forms, depending on the growth rate.

Ceramic transactions - Materials processing and design: Grain-boundary-controlled properties of fine ceramics II. Volume 44

DOE Office of Scientific and Technical Information (OSTI.GOV)

Niihara, Koichi; Ishizaki, Kozo; Isotani, Mitsuo

This volume contains selected papers presented at a workshop by the Japan Fine Ceramics Center, `Materials Processing and Design Through Better Control of Grain Boundaries: Emphasizing Fine Ceramics II,` which was held March 17-19, 1994, in Koda-cho, Aichi, Japan. The focus of the workshop was the application of grain boundary phenomena to materials processing and design. The topics covered included electronic materials, evaluation methods, structural materials, and interfaces. Also included is an illuminating overview of the current status of work on grain boundary assisted materials processing and design, particularly for fine ceramics. The volume`s chapter titles are: Electron Microscopy, Evaluation,more » Grain Boundary Control and Design, Functional Ceramics, Composite Materials, Synthesis and Sintering, and Mechanical Properties.« less

An improved procedure for determining grain boundary diffusion coefficients from averaged concentration profiles

NASA Astrophysics Data System (ADS)

Gryaznov, D.; Fleig, J.; Maier, J.

2008-03-01

Whipple's solution of the problem of grain boundary diffusion and Le Claire's relation, which is often used to determine grain boundary diffusion coefficients, are examined for a broad range of ratios of grain boundary to bulk diffusivities Δ and diffusion times t. Different reasons leading to errors in determining the grain boundary diffusivity (DGB) when using Le Claire's relation are discussed. It is shown that nonlinearities of the diffusion profiles in lnCav-y6/5 plots and deviations from "Le Claire's constant" (-0.78) are the major error sources (Cav=averaged concentration, y =coordinate in diffusion direction). An improved relation (replacing Le Claire's constant) is suggested for analyzing diffusion profiles particularly suited for small diffusion lengths (short times) as often required in diffusion experiments on nanocrystalline materials.

Grain Boundary Engineering the Mechanical Properties of Allvac 718Plus(Trademark) Superalloy

NASA Technical Reports Server (NTRS)

Gabb, Timothy P.; Telesman, Jack; Garg, Anita; Lin, Peter; Provenzano, virgil; Heard, Robert; Miller, Herbert M.

2010-01-01

Grain Boundary Engineering can enhance the population of structurally-ordered "low S" Coincidence Site Lattice (CSL) grain boundaries in the microstructure. In some alloys, these "special" grain boundaries have been reported to improve overall resistance to corrosion, oxidation, and creep resistance. Such improvements could be quite beneficial for superalloys, especially in conditions which encourage damage and cracking at grain boundaries. Therefore, the effects of GBE processing on high-temperature mechanical properties of the cast and wrought superalloy Allvac 718Plus (Allvac ATI) were screened. Bar sections were subjected to varied GBE processing, and then consistently heat treated, machined, and tested at 650 C. Creep, tensile stress relaxation, and dwell fatigue crack growth tests were performed. The influences of GBE processing on microstructure, mechanical properties, and associated failure modes are discussed.

Dielectric and electric modulus study of PPy/TiO2/CNT/SLS composite with temperature

NASA Astrophysics Data System (ADS)

Tiwari, D. C.; Atri, Priyanka; Sharma, Rishi

2013-02-01

Here we report the preparation and electrical characterization of nanocomposite of PPy/TiO2/CNT/SLS synthesized by in situ oxidative polymerization of pyrrole in the presence of TiO2 nanofibers, CNT and surfactant sodium lauryl sulfate. The surface morphology and elemental analysis is studied by SEM and EDAX. Dielectric and modulas studies were carried out in frequency range of 1 KHz to 2 MHz which provides quantitative description of grain and grain boundary effect in nanocomposite material.

Phase transformation during surface ablation of cobalt-cemented tungsten carbide with pulsed UV laser

NASA Astrophysics Data System (ADS)

Li, T.; Lou, Q.; Dong, J.; Wei, Y.; Liu, J.

Surface ablation of cobalt-cemented tungsten carbide hard metal has been carried out in this work using a 308 nm, 20 ns XeCl excimer laser. Surface microphotography and XRD, as well as an electron probe have been used to investigate the transformation of phase and microstructure as a function of the pulse-number of laser shots at a laser fluence of 2.5 J/cm2. The experimental results show that the microstructure of cemented tungsten carbide is transformed from the original polygonal grains of size 3 μm to interlaced large, long grains with an increase in the number of laser shots up to 300, and finally to gross grains of size 10 μm with clear grain boundaries after 700 shots of laser irradiation. The crystalline structure of the irradiated area is partly transformed from the original WC to βWC1-x, then to αW2C and CW3, and finally to W crystal. It is suggested that the undulating `hill-valley' morphology may be the result of selective removal of cobalt binder from the surface layer of the hard metal. The formation of non-stoichiometric tungsten carbide may result from the escape of elemental carbon due to accumulated heating of the surface by pulsed laser irradiation.

Understanding the Effect of Grain Boundary Character on Dynamic Recrystallization in Stainless Steel 316L

NASA Astrophysics Data System (ADS)

Beck, Megan; Morse, Michael; Corolewski, Caleb; Fritchman, Koyuki; Stifter, Chris; Poole, Callum; Hurley, Michael; Frary, Megan

2017-08-01

Dynamic recrystallization (DRX) occurs during high-temperature deformation in metals and alloys with low to medium stacking fault energies. Previous simulations and experimental research have shown the effect of temperature and grain size on DRX behavior, but not the effect of the grain boundary character distribution. To investigate the effects of the distribution of grain boundary types, experimental testing was performed on stainless steel 316L specimens with different initial special boundary fractions (SBF). This work was completed in conjunction with computer simulations that used a modified Monte Carlo method which allowed for the addition of anisotropic grain boundary energies using orientation data from electron backscatter diffraction (EBSD). The correlation of the experimental and simulation work allows for a better understanding of how the input parameters in the simulations correspond to what occurs experimentally. Results from both simulations and experiments showed that a higher fraction of so-called "special" boundaries ( e.g., Σ3 twin boundaries) delayed the onset of recrystallization to larger strains and that it is energetically favorable for nuclei to form on triple junctions without these so-called "special" boundaries.

Oxidation-assisted graphene heteroepitaxy on copper foil.

PubMed

Reckinger, Nicolas; Tang, Xiaohui; Joucken, Frédéric; Lajaunie, Luc; Arenal, Raul; Dubois, Emmanuel; Hackens, Benoît; Henrard, Luc; Colomer, Jean-François

2016-11-10

We propose an innovative, easy-to-implement approach to synthesize aligned large-area single-crystalline graphene flakes by chemical vapor deposition on copper foil. This method doubly takes advantage of residual oxygen present in the gas phase. First, by slightly oxidizing the copper surface, we induce grain boundary pinning in copper and, in consequence, the freezing of the thermal recrystallization process. Subsequent reduction of copper under hydrogen suddenly unlocks the delayed reconstruction, favoring the growth of centimeter-sized copper (111) grains through the mechanism of abnormal grain growth. Second, the oxidation of the copper surface also drastically reduces the nucleation density of graphene. This oxidation/reduction sequence leads to the synthesis of aligned millimeter-sized monolayer graphene domains in epitaxial registry with copper (111). The as-grown graphene flakes are demonstrated to be both single-crystalline and of high quality.

Electrochemical polishing of thread fastener test specimens of nickel-chromium iron alloys

DOEpatents

Kephart, Alan R.

1991-01-01

An electrochemical polishing device and method for selective anodic dissolution of the surface of test specimens comprised, for example, of nickel-chromium-iron alloys, which provides for uniform dissolution at the localized sites to remove metal through the use of a coiled wire electrode (cathode) placed in the immediate proximity of the working, surface resulting in a polished and uniform grain boundary.

Creep of quartz by dislocation and grain boundary processes

NASA Astrophysics Data System (ADS)

Fukuda, J. I.; Holyoke, C. W., III; Kronenberg, A. K.

2015-12-01

Wet polycrystalline quartz aggregates deformed at temperatures T of 600°-900°C and strain rates of 10-4-10-6 s-1 at a confining pressure Pc of 1.5 GPa exhibit plasticity at low T, governed by dislocation glide and limited recovery, and grain size-sensitive creep at high T, governed by diffusion and sliding at grain boundaries. Quartz aggregates were HIP-synthesized, subjecting natural milky quartz powder to T=900°C and Pc=1.5 GPa, and grain sizes (2 to 25 mm) were varied by annealing at these conditions for up to 10 days. Infrared absorption spectra exhibit a broad OH band at 3400 cm-1 due to molecular water inclusions with a calculated OH content (~4000 ppm, H/106Si) that is unchanged by deformation. Rate-stepping experiments reveal different stress-strain rate functions at different temperatures and grain sizes, which correspond to differing stress-temperature sensitivities. At 600-700°C and grain sizes of 5-10 mm, flow law parameters compare favorably with those for basal plasticity and dislocation creep of wet quartzites (effective stress exponents n of 3 to 6 and activation enthalpy H* ~150 kJ/mol). Deformed samples show undulatory extinction, limited recrystallization, and c-axis maxima parallel to the shortening direction. Similarly fine-grained samples deformed at 800°-900°C exhibit flow parameters n=1.3-2.0 and H*=135-200 kJ/mol corresponding to grain size-sensitive Newtonian creep. Deformed samples show some undulatory extinction and grain sizes change by recrystallization; however, grain boundary deformation processes are indicated by the low value of n. Our experimental results for grain size-sensitive creep can be compared with models of grain boundary diffusion and grain boundary sliding using measured rates of silicon grain boundary diffusion. While many quartz mylonites show microstructural and textural evidence for dislocation creep, results for grain size-sensitive creep may apply to very fine-grained (<10 mm) quartz mylonites.

Multiscale simulation of xenon diffusion and grain boundary segregation in UO₂

DOE PAGES

Andersson, David A.; Tonks, Michael R.; Casillas, Luis; ...

2015-07-01

In light water reactor fuel, gaseous fission products segregate to grain boundaries, resulting in the nucleation and growth of large intergranular fission gas bubbles. The segregation rate is controlled by diffusion of fission gas atoms through the grains and interaction with the boundaries. Based on the mechanisms established from earlier density functional theory (DFT) and empirical potential calculations, diffusion models for xenon (Xe), uranium (U) vacancies and U interstitials in UO₂ have been derived for both intrinsic (no irradiation) and irradiation conditions. Segregation of Xe to grain boundaries is described by combining the bulk diffusion model with a model formore » the interaction between Xe atoms and three different grain boundaries in UO₂ (Σ5 tilt, Σ5 twist and a high angle random boundary), as derived from atomistic calculations. The present model does not attempt to capture nucleation or growth of fission gas bubbles at the grain boundaries. The point defect and Xe diffusion and segregation models are implemented in the MARMOT phase field code, which is used to calculate effective Xe and U diffusivities as well as to simulate Xe redistribution for a few simple microstructures.« less

A three-dimensional polyhedral unit model for grain boundary structure in fcc metals

NASA Astrophysics Data System (ADS)

Banadaki, Arash Dehghan; Patala, Srikanth

2017-03-01

One of the biggest challenges in developing truly bottom-up models for the performance of polycrystalline materials is the lack of robust quantitative structure-property relationships for interfaces. As a first step in analyzing such relationships, we present a polyhedral unit model to classify the geometrical nature of atomic packing along grain boundaries. While the atomic structure in disordered systems has been a topic of interest for many decades, geometrical analyses of grain boundaries has proven to be particularly challenging because of the wide range of structures that are possible depending on the underlying macroscopic crystallographic character. In this article, we propose an algorithm that can partition the atomic structure into a connected array of three-dimensional polyhedra, and thus, present a three-dimensional polyhedral unit model for grain boundaries. A point-pattern matching algorithm is also provided for quantifying the distortions of the observed grain boundary polyhedral units. The polyhedral unit model is robust enough to capture the structure of high-Σ, mixed character interfaces and, hence, provides a geometric tool for comparing grain boundary structures across the five-parameter crystallographic phase-space. Since the obtained polyhedral units circumscribe the voids present in the structure, such a description provides valuable information concerning segregation sites within the grain boundary. We anticipate that this technique will serve as a powerful tool in the analysis of grain boundary structure. The polyhedral unit model is also applicable to a wide array of material systems as the proposed algorithm is not limited by the underlying lattice structure.

Initial stage corrosion of nanocrystalline copper particles and thin films

NASA Astrophysics Data System (ADS)

Tao, Weimin

1997-12-01

Corrosion behavior is an important issue in nanocrystalline materials research and development. A very fine grain size is expected to have significant effects on the corrosion resistance of these novel materials. However, both the macroscopic corrosion properties and the corresponding structure evolution during corrosion have not been fully studied. Under such circumstances, conducting fundamental research in this area is important and necessary. In this study, high purity nanocrystalline and coarse-grained copper were selected as our sample material, sodium nitrite aqueous solution at room temperature and air at a high temperature were employed as corrosive environments. The weight loss testing and electrochemical methods were used to obtain the macroscopic corrosion properties, whereas the high resolution transmission electron microscope was employed for the structure analysis. The weight loss tests indicate that the corrosion rate of nanocrystalline copper is about 5 times higher than that of coarse-grained copper at the initial stage of corrosion. The electrochemical measurements show that the corrosion potential of the nanocrystalline copper has a 230 mV negative shift in comparison with that of the coarse-grained copper. The nanocrystalline copper also exhibits a significantly higher exchange current density than the coarse-grained copper. High resolution TEM revealed that the surface structure changes at the initial stage of corrosion. It was found that the first copper oxide layer formed on the surface of nanocrystalline copper thin film contains a large density of high angle grain boundaries, whereas that formed on the surface of coarse-grained copper shows highly oriented oxide nuclei and appears to show a strong tendency for forming low angle grain boundaries. A correlation between the macroscopic corrosion properties and the structure characteristics is proposed for the nanocrystalline copper based on the concept of the "apparent" exchange current density associated with mass transport of ions in the oxide layer. A hypothesis is developed that the high corrosion rate of the nanocrystalline copper is closely associated with the structure of the copper oxide layer. Therefore, a high "apparent" exchange current density for the nanocrystalline copper is associated with the high angle grain boundary structure in the initial oxide layer. Additional structure analysis was also carried out: (a) High resolution TEM imaging has provided a cross sectional view of the epitaxial interface between nanocrystalline copper and copper (I) oxide and explicitly discloses the presence of interface defects such as misfit dislocations. Based on this observation, a mechanism was proposed to explain the Cu/Cusb2O interface misfit accommodation. This appears to be the first time this interface has been directly examined. (b) A nanocrystalline analogue to a cross-section of Gwathmey's copper single crystal sphere was revealed by high resolution TEM imaging. A partially oxidized nanocrystalline copper particle is used to examine the variation of the Cu/Cusb2O orientation relationship with respect to changes in surface orientation. A new orientation relationship, Cu (011) //Cusb2O (11), ˜ Cu(011)//Cusb2O(111), was found for the oxidation of nanocrystalline copper.

The evolution of slip surface roughness during earthquake propagation in carbonate faults

NASA Astrophysics Data System (ADS)

Zhu, B.; De Paola, N.; Llewellin, E. W.; Holdsworth, R.

2014-12-01

Slip surface roughness is understood to control the dynamics of earthquake propagation. Quantifying the micro- and nano-scale roughness of slip surfaces can give insight into the grain-scale processes controlling the strength of faults during earthquake propagation. Friction experiments were performed on fine-grained calcite gouges, at speed 1 ms-1, normal stress 18 MPa, displacements 0.009-1.46 m, and room temperature and humidity. Results show a two stage-evolution (S1-2) of the fault strength, with an initial increase up to peak value 0.82 (S1), followed by a sudden decrease to a low, steady-state value 0.18 (S2). Samples retrieved at the end of S1 show the development of a cohesive slip zone (SZ), made of micron-scale, angular clasts formed by brittle fracturing and cataclasis. The SZ of samples deformed up to S2, is composed of nanograin aggregates which exhibit polygonal grain boundaries indicating high temperature grain boundary sliding creep deformation. In both cases, the SZ is bounded by a sharply defined slip surface. The 3-D geometry of seven experimental slip surfaces (40μm×40μm) has been reconstructed by digital processing of sets of 1800 images of SZ cross sections acquired at 20 nm intervals perpendicular to the slip direction, using a slicing (Focussed Ion Beam) and viewing (Field Emission Scanning Electron Microscope) technique. Spectrum power density analyses show that nano- and micron-scale slip surface roughness is anisotropic for both S1 and S2 slip surfaces. At the nano- and micron-scale, root mean square values decrease with length for S1 slip surfaces, but only slightly for S2 surfaces, and are anisotropic in the slip-normal and slip-parallel directions. The anisotropy is reduced at the nano-scale, although S2 slip surfaces are still smoother parallel to slip than normal to slip. Hurst exponents vary through scales, and are anisotropic in the directions parallel and normal to slip. Variable Hurst exponents indicate that slip surface roughness is scale-dependent with anisotropic, not self-affine behaviour at the micro/nano-scale, in contrast to the self-affine behaviour inferred at the mm to km scales. Dynamic weakening and creep deformation, observed during S2, coincide with an evolution towards less anisotropic and scale-dependent slip surface roughness at the nanoscale.

Defects-tolerant Co-Cr-Mo dental alloys prepared by selective laser melting.

PubMed

Qian, B; Saeidi, K; Kvetková, L; Lofaj, F; Xiao, C; Shen, Z

2015-12-01

CrCoMo alloy specimens were successfully fabricated using selective laser melting (SLM). The aim of this study was to carefully investigate microstructure of the SLM specimens in order to understand the influence of their structural features inter-grown on different length scales ranging from nano- to macro-levels on their mechanical properties. Two different sets of processing parameters developed for building the inner part (core) and the surface (skin) of dental prostheses were tested. Microstructures were characterized by SEM, EBSD and XRD analysis. The elemental distribution was assessed by EDS line profile analysis under TEM. The mechanical properties of the specimens were measured. The microstructures of both specimens were characterized showing formation of grains comprised of columnar sub-grains with Mo-enrichment at the sub-grain boundaries. Clusters of columnar sub-grains grew coherently along one common crystallographic direction forming much larger single crystal grains which are intercrossing in different directions forming an overall dendrite-like microstructure. Three types of microstructural defects were occasionally observed; small voids (<10 μm), fine cracks at grain boundaries (<10 μm) and cracks at weld line boundaries (>10 μm). Despite the presence of these defects, the yield and the ultimate tensile strength (UTS) were 870 and 430MPa and 1300MPa and 1160MPa, respectively, for the skin and core specimens which are higher than casted dental alloy. Although the formation of microstructural defects is hard to be avoided during the SLM process, the SLM CoCrMo alloys can achieve improved mechanical properties than their casted counterparts, implying they are "defect-tolerant". Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Mechanisms of Texture Development in Lead-Free Piezoelectric Ceramics with Perovskite Structure Made by the Templated Grain Growth Process

PubMed Central

Kimura, Toshio; Yi, Yuan; Sakurai, Fumito

2010-01-01

The mechanisms of texture development were examined for BaTiO3 and a (K,Na,Li)(Nb,Ta)O3 solid solution made by the templated grain growth method, and compared with the mechanism in Bi0.5(Na,K)0.5TiO3. The dominant mechanism was different in each material; grain boundary migration in BaTiO3, solid state spreading in Bi0.5(Na,K)0.5TiO3, and abnormal grain growth in the (K,Na,Li)(Nb,Ta)O3 solid solution. The factor determining the dominant mechanism is the degree of smoothness of surface structure at an atomic level. PMID:28883364

Symmetric Tilt Grain Boundaries of Synthetic Forsterite Bicrystals

NASA Astrophysics Data System (ADS)

Heinemann, S.; Wirth, R.; Dresen, G.

2002-12-01

{ indent1.5em skip0ex Structure and transport properties of grain boundaries in rocks are still poorly understood. For example, grain boundary diffusivity and mobility depend on orientation, and they are different for low and high angle grain boundaries. The transition from low to high angle grain boundaries in rock-forming minerals is not studied in detail, but a high angle grain boundary is commonly defined by a lattice misorientation of >10°-15°. To investigate the physical properties of olivine grain boundaries we produced a series of synthetic forsterite bicrystals with symmetric tilt grain boundaries by direct bonding [1,2]. For each bicrystal two oriented synthetic forsterite single crystals were joined at room temperature and annealed at 400°C for one week. All bicrystals were cut in two parts and one part was annealed further at 1650°C for 48h. The tilt axis of the boundary in the synthesized bicrystals is parallel to the a direction, and the tilt angles of the series range from 9° to 21°. Specimens were prepared for investigations in the transmission electron microscope (TEM) using focused ion beam (FIB) technique. High-resolution TEM investigations of symmetric tilt grain boundaries reveal dislocation arrays between undisturbed crystal regions in samples annealed at 400°C and 1650°C. This suggests that bonding of bicrystals occurred already below or at 400°C. The burgers vectors of the dislocations are parallel to c. Dislocation cores do not overlap up to a tilt angle of 21°. This indicates that for forsterite small angle grain boundaries exist up to tilt angles of 21°. The dislocation model of small angle grain boundaries can be applied and the observed dislocation spacings d are related to tilt angle θ and burgers vector length b by Franks formula [3]: d = b/(2sin(2/θ )) ~ b/θ . With tilt angles increasing from 9° to 21° the dislocation spacing decreased. Using Frank's equation and the observation that dislocations do not overlap at a misorientation of 21° allows to estimate the maximum radius of the dislocation cores, r0<1.4b.} {skip0ex \\small [1] Heinemann S et al. (2001) Phys Chem Minerals 28, 685 [2] Heinemann S et al. (2002) Beih Eur Mineral 14(1), 66 [3] Frank FC (1951) Pittsburgh Symposium on the Plastic Deformation of Solids. 150}

Deformation, recrystallization, strength, and fracture of press-forged ceramic crystals.

NASA Technical Reports Server (NTRS)

Rice, R. W.

1972-01-01

Sapphire and ruby were very difficult to press-forge because they deformed without cracking only in a limited temperature range before they melted. Spinel crystals were somewhat easier and MgO, CaO, and TiC crystals much easier to forge. The degree of recrystallization that occurred during forging (which was related to the ease and type of slip intersections) varied from essentially zero in Al2O3 to complete (i.e., random polycrystalline bodies were produced) in CaO. Forging of bi- and polycrystalline bodies produced incoherent bodies as a result of grain-boundary sliding. Strengths of the forged crystals were comparable to those of dense polycrystalline bodies of similar grain size. However, forged and recrystallized CaO crystals were ductile at lower temperatures than dense hot-pressed CaO. This behavior is attributed to reduced grain-boundary impurities and porosity. Fracture origins could be located, indicating that fracture in the CaO occurs internally as a result of surface work hardening caused by machining.-

Colloidal crystal grain boundary formation and motion

PubMed Central

Edwards, Tara D.; Yang, Yuguang; Beltran-Villegas, Daniel J.; Bevan, Michael A.

2014-01-01

The ability to assemble nano- and micro- sized colloidal components into highly ordered configurations is often cited as the basis for developing advanced materials. However, the dynamics of stochastic grain boundary formation and motion have not been quantified, which limits the ability to control and anneal polycrystallinity in colloidal based materials. Here we use optical microscopy, Brownian Dynamic simulations, and a new dynamic analysis to study grain boundary motion in quasi-2D colloidal bicrystals formed within inhomogeneous AC electric fields. We introduce “low-dimensional” models using reaction coordinates for condensation and global order that capture first passage times between critical configurations at each applied voltage. The resulting models reveal that equal sized domains at a maximum misorientation angle show relaxation dominated by friction limited grain boundary diffusion; and in contrast, asymmetrically sized domains with less misorientation display much faster grain boundary migration due to significant thermodynamic driving forces. By quantifying such dynamics vs. compression (voltage), kinetic bottlenecks associated with slow grain boundary relaxation are understood, which can be used to guide the temporal assembly of defect-free single domain colloidal crystals. PMID:25139760

Testing thermal gradient driving force for grain boundary migration using molecular dynamics simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bai, Xian-Ming; Zhang, Yongfeng; Tonks, Michael R.

2015-02-01

Strong thermal gradients in low-thermal-conductivity ceramics may drive extended defects, such as grain boundaries and voids, to migrate in preferential directions. In this work, molecular dynamics simulations are conducted to study thermal gradient driven grain boundary migration and to verify a previously proposed thermal gradient driving force equation, using uranium dioxide as a model system. It is found that a thermal gradient drives grain boundaries to migrate up the gradient and the migration velocity increases under a constant gradient owing to the increase in mobility with temperature. Different grain boundaries migrate at very different rates due to their different intrinsicmore » mobilities. The extracted mobilities from the thermal gradient driven simulations are compared with those calculated from two other well-established methods and good agreement between the three different methods is found, demonstrating that the theoretical equation of the thermal gradient driving force is valid, although a correction of one input parameter should be made. The discrepancy in the grain boundary mobilities between modeling and experiments is also discussed.« less

Linking Grain Boundary Microstructure to Stress Corrosion Cracking of Cold Rolled Alloy 690 in PWR Primary Water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bruemmer, Stephen M.; Olszta, Matthew J.; Toloczko, Mychailo B.

2012-10-01

Grain boundary microstructures and microchemistries are examined in cold-rolled alloy 690 tubing and plate materials and comparisons are made to intergranular stress corrosion cracking (IGSCC) behavior in PWR primary water. Chromium carbide precipitation is found to be a key aspect for materials in both the mill annealed and thermally treated conditions. Cold rolling to high levels of reduction was discovered to produce small IG voids and cracked carbides in alloys with a high density of grain boundary carbides. The degree of permanent grain boundary damage from cold rolling was found to depend directly on the initial IG carbide distribution. Formore » the same degree of cold rolling, alloys with few IG precipitates exhibited much less permanent damage. Although this difference in grain boundary damage appears to correlate with measured SCC growth rates, crack tip examinations reveal that cracked carbides appeared to blunt propagation of IGSCC cracks in many cases. Preliminary results suggest that the localized grain boundary strains and stresses produced during cold rolling promote IGSCC susceptibility and not the cracked carbides and voids.« less

Studies of electronic structure of ZnO grain boundary and its proximity by using spatially resolved electron energy loss spectroscopy

NASA Astrophysics Data System (ADS)

Ong, H. C.; Dai, J. Y.; Du, G. T.

2002-07-01

The low electron energy loss and complex dielectric functions of an arbitrary grain boundary and its proximity in ZnO thin films have been studied by using the spatially resolved electron energy loss spectroscopy. The critical point parameters have been determined by fitting the dielectric functions simultaneously with analytical line shape model. Gradual changes have been observed in the dielectric functions spectra. The critical points are found to redshift and then blueshift when the electron beam scanned across the grain boundary, which suggest the distinctive electronic structure not only of the grain boundary but also of the depletion region. In addition, comparison has been made between the experiment and the recent theoretical studies to account for the interband transitions that occur in the grain boundaries. Several features predicted by the theory are qualitatively found to be consistent with our results. The presence of dangling bonds instead of bond distortion is attributed to be the major cause of defects in the grain boundaries of ZnO.

Effect of Trace Levels of Si on Microstructure and Grain Boundary Segregation in DOP-26 Iridium Alloy

NASA Astrophysics Data System (ADS)

Pierce, Dean; Muralidharan, Govindarajan; Heatherly, Lee; Fox, Ethan

2018-03-01

The thermodynamics and kinetics of Silicon (Si) segregation to grain boundaries in Iridium alloy DOP-26 with added trace levels of Si of 6, 11, 29, and 36 wppm was studied by Auger Electron Spectroscopy. The four alloys were annealed at 1500 or 1535 °C for 19 or 76 hours followed by cooling at three different rates. Si enrichment at the grain boundaries (GB) increased with increasing bulk Si content, with the grain boundary Si enrichment factors ranging from 62 to 344, depending on the bulk Si content and the cooling rate. Grain boundary Si contents increased with decreasing cooling rate in all alloys, indicating that Si GB segregation is influenced by both thermodynamic and kinetic factors in the alloys and temperature ranges of the study. A Langmuir-McLean isotherm-based model was successfully used to predict the temperature dependence of GB Si segregation in DOP-26 alloys with Si additions and estimate the temperature independent free energy of Si segregation to grain boundaries in DOP-26.

Exploration of the mechanisms of temperature-dependent grain boundary mobility: Search for the common origin of ultrafast grain boundary motion

DOE PAGES

O’Brien, C. J.; Foiles, S. M.

2016-04-19

The temperature dependence of grain boundary mobility is complex, varied, and rarely fits ideal Arrhenius behavior. This work presents a series of case studies of planar grain boundaries in a model FCC system that were previously demonstrated to exhibit a variety of temperature-dependent mobility behaviors. It is demonstrated that characterization of the mobility versus temperature plots is not sufficient to predict the atomic motion mechanism of the grain boundaries. Herein, the temperature-dependent motion and atomistic motion mechanisms of planar grain boundaries are driven by a synthetic, orientation-dependent, driving force. The systems studied include CSL boundaries with Σ values of 5,more » 7, and 15, including both symmetric and asymmetric boundaries. These boundaries represent a range of temperature-dependent trends including thermally activated, antithermal, and roughening behaviors. Examining the atomic-level motion mechanisms of the thermally activated boundaries reveals that each involves a complex shuffle, and at least one atom that changes the plane it resides on. The motion mechanism of the antithermal boundary is qualitatively different and involves an in-plane coordinated shuffle that rotates atoms about a fixed atom lying on a point in the coincident site lattice. Furthermore, this provides a mechanistic reason for the observed high mobility, even at low temperatures, which is due to the low activation energy needed for such motion. However, it will be demonstrated that this mechanism is not universal, or even common, to other boundaries exhibiting non-thermally activated motion. This work concludes that no single atomic motion mechanism is sufficient to explain the existence of non-thermally activated boundary motion.« less

Grain-Size-Limited Mobility in Methylammonium Lead Iodide Perovskite Thin Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reid, Obadiah G.; Yang, Mengjin; Kopidakis, Nikos

2016-09-09

We report a systematic study of the gigahertz-frequency charge carrier mobility found in methylammonium lead iodide perovskite films as a function of average grain size using time-resolved microwave conductivity and a single processing chemistry. Our measurements are in good agreement with the Kubo formula for the AC mobility of charges confined within finite grains, suggesting (1) that the surface grains imaged via scanning electron microscopy are representative of the true electronic domain size and not substantially subdivided by twinning or other defects not visible by microscopy and (2) that the time scale of diffusive transport across grain boundaries is muchmore » slower than the period of the microwave field in this measurement (-100 ps). The intrinsic (infinite grain size) minimum mobility extracted form the model is 29 +/- 6 cm2 V-1 s-1 at the probe frequency (8.9 GHz).« less

Grain-boundary free energy in an assembly of elastic disks.

PubMed

Lusk, Mark T; Beale, Paul D

2004-02-01

Grain-boundary free energy is estimated as a function of misoriention for symmetric tilt boundaries in an assembly of nearly hard disks. Fluctuating cell theory is used to accomplish this since the most common techniques for calculating interfacial free energy cannot be applied to such assemblies. The results are analogous to those obtained using a Leonard-Jones potential, but in this case the interfacial energy is dominated by an entropic contribution. Disk assemblies colorized with free and specific volume elucidate differences between these two characteristics of boundary structure. Profiles are also provided of the Helmholtz and Gibbs free energies as a function of distance from the grain boundaries. Low angle grain boundaries are shown to follow the classical relationship between dislocation orientation/spacing and misorientation angle.

Austenite grain growth simulation considering the solute-drag effect and pinning effect

PubMed Central

Fujiyama, Naoto; Nishibata, Toshinobu; Seki, Akira; Hirata, Hiroyuki; Kojima, Kazuhiro; Ogawa, Kazuhiro

2017-01-01

Abstract The pinning effect is useful for restraining austenite grain growth in low alloy steel and improving heat affected zone toughness in welded joints. We propose a new calculation model for predicting austenite grain growth behavior. The model is mainly comprised of two theories: the solute-drag effect and the pinning effect of TiN precipitates. The calculation of the solute-drag effect is based on the hypothesis that the width of each austenite grain boundary is constant and that the element content maintains equilibrium segregation at the austenite grain boundaries. We used Hillert’s law under the assumption that the austenite grain boundary phase is a liquid so that we could estimate the equilibrium solute concentration at the austenite grain boundaries. The equilibrium solute concentration was calculated using the Thermo-Calc software. Pinning effect was estimated by Nishizawa’s equation. The calculated austenite grain growth at 1473–1673 K showed excellent correspondence with the experimental results. PMID:28179962

Transport properties of olivine grain boundaries from electrical conductivity experiments

NASA Astrophysics Data System (ADS)

Pommier, Anne; Kohlstedt, David L.; Hansen, Lars N.; Mackwell, Stephen; Tasaka, Miki; Heidelbach, Florian; Leinenweber, Kurt

2018-05-01

Grain boundary processes contribute significantly to electronic and ionic transports in materials within Earth's interior. We report a novel experimental study of grain boundary conductivity in highly strained olivine aggregates that demonstrates the importance of misorientation angle between adjacent grains on aggregate transport properties. We performed electrical conductivity measurements of melt-free polycrystalline olivine (Fo90) samples that had been previously deformed at 1200 °C and 0.3 GPa to shear strains up to γ = 7.3. The electrical conductivity and anisotropy were measured at 2.8 GPa over the temperature range 700-1400 °C. We observed that (1) the electrical conductivity of samples with a small grain size (3-6 µm) and strong crystallographic preferred orientation produced by dynamic recrystallization during large-strain shear deformation is a factor of 10 or more larger than that measured on coarse-grained samples, (2) the sample deformed to the highest strain is the most conductive even though it does not have the smallest grain size, and (3) conductivity is up to a factor of 4 larger in the direction of shear than normal to the shear plane. Based on these results combined with electrical conductivity data for coarse-grained, polycrystalline olivine and for single crystals, we propose that the electrical conductivity of our fine-grained samples is dominated by grain boundary paths. In addition, the electrical anisotropy results from preferential alignment of higher-conductivity grain boundaries associated with the development of a strong crystallographic preferred orientation of the grains.

Texture enhancement during grain growth of magnesium alloy AZ31B

DOE PAGES

Bhattacharyya, Jishnu J.; Agnew, S. R.; Muralidharan, G.

2015-01-03

In this paper, the microstructure and texture evolution during annealing of rolled Mg alloy AZ31B, at temperatures ranging from 260 to 450°C, is characterized, and a grain growth exponent of n=5, indicating inhibition of grain growth, is observed. Broadening of the normalized grain size distributions, which indicates abnormal grain growth, was observed at all temperatures investigated. It is shown, using a Zener-type analysis for pinning of grain boundaries by particles, that impurity-based particles are responsible for grain growth inhibition and abnormal grain growth. The strong basal texture which develops during rolling of the Mg alloy, resulting in an initial peakmore » intensity in the (0002) pole figure of nine multiples of a random distribution (MRD), increases to ~15 MRD during annealing at 400 and 450°C. Furthermore, a specific texture component {0001}(1120) is observed in the orientation distribution, which increases from 10 to 23 MRD at 400°C. It is hypothesized that the anisotropic grain boundary properties (i.e. low angle boundaries have low energy and mobility) are responsible for the texture strengthening. Additionally, electron backscattered diffraction reveals the recrystallized microstructure to contain a significant number of boundaries with ~30° misorientation about the <0001> direction, and this boundary type persists throughout most annealing treatments explored.« less

The relevance of grain dissection for grain size reduction in polar ice: insights from numerical models and ice core microstructure analysis

NASA Astrophysics Data System (ADS)

Steinbach, Florian; Kuiper, Ernst-Jan N.; Eichler, Jan; Bons, Paul D.; Drury, Martyn R.; Griera, Albert; Pennock, Gill M.; Weikusat, Ilka

2017-09-01

The flow of ice depends on the properties of the aggregate of individual ice crystals, such as grain size or lattice orientation distributions. Therefore, an understanding of the processes controlling ice micro-dynamics is needed to ultimately develop a physically based macroscopic ice flow law. We investigated the relevance of the process of grain dissection as a grain-size-modifying process in natural ice. For that purpose, we performed numerical multi-process microstructure modelling and analysed microstructure and crystallographic orientation maps from natural deep ice-core samples from the North Greenland Eemian Ice Drilling (NEEM) project. Full crystallographic orientations measured by electron backscatter diffraction (EBSD) have been used together with c-axis orientations using an optical technique (Fabric Analyser). Grain dissection is a feature of strain-induced grain boundary migration. During grain dissection, grain boundaries bulge into a neighbouring grain in an area of high dislocation energy and merge with the opposite grain boundary. This splits the high dislocation-energy grain into two parts, effectively decreasing the local grain size. Currently, grain size reduction in ice is thought to be achieved by either the progressive transformation from dislocation walls into new high-angle grain boundaries, called subgrain rotation or polygonisation, or bulging nucleation that is assisted by subgrain rotation. Both our time-resolved numerical modelling and NEEM ice core samples show that grain dissection is a common mechanism during ice deformation and can provide an efficient process to reduce grain sizes and counter-act dynamic grain-growth in addition to polygonisation or bulging nucleation. Thus, our results show that solely strain-induced boundary migration, in absence of subgrain rotation, can reduce grain sizes in polar ice, in particular if strain energy gradients are high. We describe the microstructural characteristics that can be used to identify grain dissection in natural microstructures.

Electromigration Reliability of Advanced Interconnects

NASA Astrophysics Data System (ADS)

Hu, C.-K.; Gignac, L. M.; Baker-O'Neal, B.; Liniger, E.; Yu, R.; Flaitz, P.; Stamper, A. K.

2007-10-01

Electromigration behavior in Cu damascene wires was studied for various metal line widths, thicknesses and grain sizes where the grain size was modulated by Cu linewidth and thickness, and by adjusting the wafer annealing process step after Cu electroplating and before Cu chemical mechanical polishing. Significantly different results were found between 0.2 μm and 65 nm CMOS node technologies. A larger variation of Cu grain size between the samples was achieved on 65 nm node which was due to the finer line width and thinner metal thickness. The Cu lifetime and mass flow in samples with bamboo, near bamboo, bamboo-polycrystalline mixture, and polycrystalline grain structures were measured. These factors allow one to accurately resolve the relative contribution between grain boundary and interface diffusions in the Cu nanowires. The electromigration mass flow estimated from the lifetime on the test line on a W via and physically stable liner was found to be linearly proportional to current density. The effects of Cu(Ti) alloy seeds and Cu surface pre-clean techniques before the dielectric cap depositions on Cu electromigration were also observed. A significantly improved Cu lifetime, at the expense of the Cu conductivity, was found. The electromigration activation energies for Cu in Cu(Ti) alloy, along Cu/amorphous a-SiCxNyHz interface and in Cu grain boundaries were found to be 1.3, 0.95 and 0.79+0.05 eV, respectively.

Experimental Characterization and Simulation of Slip Transfer at Grain Boundaries and Microstructurally-Sensitive Crack Propagation

NASA Technical Reports Server (NTRS)

Gupta, Vipul; Hochhalter, Jacob; Yamakov, Vesselin; Scott, Willard; Spear, Ashley; Smith, Stephen; Glaessgen, Edward

2013-01-01

A systematic study of crack tip interaction with grain boundaries is critical for improvement of multiscale modeling of microstructurally-sensitive fatigue crack propagation and for the computationally-assisted design of more durable materials. In this study, single, bi- and large-grain multi-crystal specimens of an aluminum-copper alloy are fabricated, characterized using electron backscattered diffraction (EBSD), and deformed under tensile loading and nano-indentation. 2D image correlation (IC) in an environmental scanning electron microscope (ESEM) is used to measure displacements near crack tips, grain boundaries and within grain interiors. The role of grain boundaries on slip transfer is examined using nano-indentation in combination with high-resolution EBSD. The use of detailed IC and EBSD-based experiments are discussed as they relate to crystal-plasticity finite element (CPFE) model calibration and validation.

Appling grain boundary engineering to Alloy 690 tube for enhancing intergranular corrosion resistance

NASA Astrophysics Data System (ADS)

Xia, Shuang; Li, Hui; Liu, Ting Guang; Zhou, Bang Xin

2011-09-01

The feasibility of applying the grain boundary engineering (GBE) processing to Alloy 690 tube manufacturing for improving the intergranular corrosion resistance was studied. Through small amount of deformation by cold drawing using a draw-bench on a production line and subsequent short time annealing at high temperature, the proportion of low Σ coincidence site lattice (CSL) grain boundaries of the Alloy 690 tube can be enhanced to about 75% which mainly were of Σ3 n ( n = 1, 2, 3, …) type. In this case, the grain boundary network (GBN) was featured by the formation of highly twinned large size grain-clusters produced by multiple twinning during recrystallization. All of the grains inside this kind of cluster had Σ3 n mutual misorientations, and hence all the boundaries inside the cluster were of Σ3 n type and formed many interconnected Σ3 n type triple junctions. The weight losses due to grain dropping during intergranular corrosion for the samples with the modified GBN were much less than that with conventional microstructure. Based on the characterization by scanning electron microscopy (SEM) and electron backscatter diffraction (EBSD) technique, it was shown that the highly twinned large size grain-cluster microstructure played a key role in enhancing the intergranular corrosion resistance: (1) the large grain-cluster can arrest the penetration of intergranular corrosion; (2) the large grain-cluster can protect the underlying microstructure.

Morphologies, microstructures, and mechanical properties of samples produced using laser metal deposition with 316 L stainless steel wire

NASA Astrophysics Data System (ADS)

Xu, Xiang; Mi, Gaoyang; Luo, Yuanqing; Jiang, Ping; Shao, Xinyu; Wang, Chunming

2017-07-01

Laser metal deposition (LMD) with a filler has been demonstrated to be an effective method for additive manufacturing because of its high material deposition efficiency, improved surface quality, reduced material wastage, and cleaner process environment without metal dust pollution. In this study, single beads and samples with ten layers were successfully deposited on a 316 L stainless steel surface under optimized conditions using a 4000 W continuous wave fibre laser and an arc welding machine. The results showed that satisfactory layered samples with a large deposition height and smooth side surface could be achieved under appropriate parameters. The uniform structures had fine cellular and network austenite grains with good metallurgical bonding between layers, showing an austenite solidification mode. Precipitated ferrite at the grain boundaries showed a subgrain structure with fine uniform grain size. A higher microhardness (205-226 HV) was detected in the middle of the deposition area, while the tensile strength of the 50 layer sample reached 669 MPa. In addition, ductile fracturing was proven by the emergence of obvious dimples at the fracture surface.

Scaling behavior of moisture-induced grain degradation in polycrystalline hybrid perovskite thin films

DOE PAGES

Wang, Qi; Chen, Bo; Liu, Ye; ...

2017-01-01

The stability of perovskite solar cells has shown a huge variation with respect to the film process and film morphology, while the underlining mechanism for the morphology-dependent degradation of the perovskite film has remained elusive. Herein, we report a scaling behavior of moisture-induced grain degradation in polycrystalline CH 3NH 3PbI 3 films. The degradation rates of CH 3NH 3PbI 3 films in moisture were shown to be sensitive to the grain sizes. The duration that was needed for different films to degrade by the same percent showed a linear relationship with the grain size, despite the fact that the filmsmore » were formed by five different deposition methods. This scaling behavior can be explained by the degradation along the in-plane direction, which is initiated at the grain boundary (GB). The GBs of CH 3NH 3PbI 3 films consist of an amorphous intergranular layer, which allows quick diffusion of moisture into the perovskite films. It was found that thermal annealing induced surface self-passivation plays a critical role in stabilizing the surfaces of thin films and single crystals by reducing the moisture-sensitive methylammonium ions at the surface. Finally, the determination of the scaling behavior of grain degradation highlights the importance of stabilizing the GBs to improve the stability of perovskite solar cells.« less

Scaling behavior of moisture-induced grain degradation in polycrystalline hybrid perovskite thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Qi; Chen, Bo; Liu, Ye

The stability of perovskite solar cells has shown a huge variation with respect to the film process and film morphology, while the underlining mechanism for the morphology-dependent degradation of the perovskite film has remained elusive. Herein, we report a scaling behavior of moisture-induced grain degradation in polycrystalline CH 3NH 3PbI 3 films. The degradation rates of CH 3NH 3PbI 3 films in moisture were shown to be sensitive to the grain sizes. The duration that was needed for different films to degrade by the same percent showed a linear relationship with the grain size, despite the fact that the filmsmore » were formed by five different deposition methods. This scaling behavior can be explained by the degradation along the in-plane direction, which is initiated at the grain boundary (GB). The GBs of CH 3NH 3PbI 3 films consist of an amorphous intergranular layer, which allows quick diffusion of moisture into the perovskite films. It was found that thermal annealing induced surface self-passivation plays a critical role in stabilizing the surfaces of thin films and single crystals by reducing the moisture-sensitive methylammonium ions at the surface. Finally, the determination of the scaling behavior of grain degradation highlights the importance of stabilizing the GBs to improve the stability of perovskite solar cells.« less

Study of Ferrite During Refinement of Prior Austenite Grains in Microalloyed Steel Continuous Casting

NASA Astrophysics Data System (ADS)

Liu, Jiang; Wen, Guanghua; Tang, Ping

2017-12-01

The formation of coarse prior austenite grain is a key factor to promote transverse crack, and the susceptibility to the transverse crack can be reduced by refining the austenite grain size. In the present study, the high-temperature confocal laser scanning microscope (CLSM) was used to simulate two types of double phase-transformation technologies. The distribution and morphology of ferrites under different cooling conditions were analyzed, and the effects of ferrite distribution and morphology on the double phase-transformation technologies were explored to obtain the suitable double phase-change technology for the continuous casting process. The results indicate that, under the thermal cycle TH0 [the specimens were cooled down to 913 K (640 °C) at a cooling rate of 5.0 K/s (5.0 °C/s)], the width of prior austenite grain boundaries was thick, and the dislocation density at grain boundaries was high. It had strong inhibition effect on crack propagation; under the thermal cycle TH1 [the specimens were cooled down to 1073 K (800 °C) at a cooling rate of 5.0 K/s (5.0 °C/s) and then to 913 K (640 °C) at a cooling rate of 1.0 K/s (1.0 °C/s)], the width of prior austenite grain boundary was thin, and the dislocation density at grain boundaries was low. It was beneficial to crack propagation. After the first phase change, the developed film-like ferrite along the austenite grain boundaries improved the nucleation conditions of new austenitic grains and removed the inhibition effect of the prior austenite grain boundaries on the austenite grain size.

The effect of grain boundary chemistry on Intergranular stress corrosion cracking of Ni-Cr-Fe alloys in 50 Pct NaOH at 140 °C

NASA Astrophysics Data System (ADS)

Sung, J. K.; Koch, J.; Angeliu, T.; Was, G. S.

1992-10-01

The role of chromium, carbon, chromium carbides, and phosphorus on the intergranular stress corrosion cracking (IGSCC) resistance of Ni-Cr-Fe alloys in 50 pct NaOH at 140 °C is studied using controlled-purity alloys. The effect of carbon is studied using heats in which the carbon level is varied between 0.002 and 0.063 wt pct while the Cr level is fixed at 16.8 wt pct. The effect of Cr is studied using alloys with Cr concentrations between 5 and 30 wt pct. The effect of grain boundary Cr and C together is studied by heat-treating the nominal alloy composition of Ni-16Cr-9Fe-0.035C, and the effect of P is studied using a high-purity, P-doped alloy and a carbon-containing, P-doped alloy. Constant extension rate tensile (CERT) results show that the crack depth increases with decreasing alloy Cr content and increasing alloy C content. Crack- ing severity also correlates inversely with thermal treatment time at 700 °C, during which the grain boundary Cr content rises and the grain boundary C content falls. Phosphorus is found to have a slightly beneficial effect on IG cracking susceptibility. Potentiodynamic polarization and potentiostatic current decay experiments confirm that Cr depletion or grain boundary C enhances the dissolution at the grain boundary. Results support a film rupture-anodic dissolution model in which Cr depletion or grain boundary C (independently or additively) enhances dissolution of nickel from the grain boundary region and leads to increased IG cracking.

Electrical transport across grain boundaries in graphene monolayers on SiC(0 0 0 \\bar{1} )

NASA Astrophysics Data System (ADS)

Zhou, Xiaodong; Ji, Shuai-Hua; Chockalingam, S. P.; Hannon, J. B.; Tromp, R. M.; Heinz, T. F.; Pasupathy, A. N.; Ross, F. M.

2018-07-01

We measure the role of structural defects, including grain boundaries and step edges, in determining the electrical transport characteristics of polycrystalline graphene monolayers synthesized on C-face SiC(0 0 0 ) by thermal decomposition. A combination of multi-probe scanning tunneling microscopy/potentiometry and low-energy electron microscopy allows the transport properties of individual grain boundaries to be correlated with their misorientation and atomic-level structure, without any device fabrication. We find that different types of grain boundary show dramatically different transport properties, and that boundaries can change structure and resistivity along their length. Boundary regions made up of dislocation superlattices separated by continuous graphene exhibit relatively low resistivity which is comparable to the resistivity of the graphene sheet itself. Other grain boundaries display trench structures with a resistivity 1–2 orders of magnitude greater and sufficient to dominate transport through the polycrystalline sheet. We also measure the transport properties of step edges and monolayer-bilayer boundaries on C-face graphene and compare them to Si-face graphene. Such measurements offer a guideline for optimizing graphene growth on SiC to improve its electronic properties.

The origin of current blocking in interfacial conduction in Sr-doped lanthanum gallates

NASA Astrophysics Data System (ADS)

Park, Hee Jung

2018-02-01

The grain boundary transport of lanthanum gallate has been studied with various doping concentrations, and the origins of blocking on the grain boundary are compared. La1-xSrxGaO3 samples (x = 0.005, 0.01, 0.05 and 0.1) have been prepared and their bulk (grain) and grain boundary resistances been experimentally measured as a function of temperature (T: 200-550 °C) and oxygen partial pressure (Po2) using ac-impedance measurements. In addition, Hebb-Wagner polarization measurements have been conducted to investigate the electrical conductivity of minor charge carriers in the lanthanum gallates. The grain boundary resistance in the low-doped materials (x = 0.005 and 0.01) increases with increasing Po2 while in the highly-doped materials (x = 0.05, 0.1) it hardly depended on Po2. At lower concentrations conduction is mixed and at higher concentrations is found to be predominantly ionic conductivity. The space charge model successfully describes the mixed conduction at the grain boundary at low-doping, but does not explain the predominant ionic conductivity at high-doping. The origin of blocking at high-doping is explained by the crystallographic asymmetry of the grain boundary with respect to the bulk and/or Sr-segregation.

The deformation record of olivine in mylonitic peridotites from the Finero Complex, Ivrea Zone: Separate deformation cycles during exhumation

NASA Astrophysics Data System (ADS)

Matysiak, Agnes K.; Trepmann, Claudia A.

2015-12-01

Mylonitic peridotites from the Finero complex are investigated to detect characteristic olivine microfabrics that can resolve separate deformation cycles at different metamorphic conditions. The heterogeneous olivine microstructures are characterized by deformed porphyroclasts surrounded by varying amounts of recrystallized grains. A well-developed but only locally preserved foam structure is present in recrystallized grain aggregates. This indicates an early stage of dynamic recrystallization and subsequent recovery and recrystallization at quasi-static stress conditions, where the strain energy was reduced such that a reduction in surface energy controlled grain boundary migration. Ultramylonites record a renewed stage of localized deformation and recrystallization by a second generation of recrystallized grains that do not show a foam structure. This second generation of recrystallized grains as well as sutured grain and kink band boundaries of porphyroclasts indicate that these microstructures developed during a stage of localized deformation after development of the foam structure. The heterogeneity of the microfabrics is interpreted to represent several (at least two) cycles of localized deformation separated by a marked hiatus with quasi-static recrystallization and recovery and eventually grain growth. The second deformation cycle did not only result in reactivation of preexisting shear zones but instead also locally affected the host rock that was not deformed in the first stage. Such stress cycles can result from sudden increases in differential stress imposed by seismic events, i.e., high stress-loading rates, during exhumation of the Finero complex.

Microstructure effects on the recrystallization of low-symmetry alpha-uranium

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCabe, Rodney James; Richards, Andrew Walter; Coughlin, Daniel Robert

2015-10-01

We employ electron backscatter diffraction (EBSD) to investigate microstructural evolution of uranium during recrystallization. To understand the relationship between microstructure and recrystallization, we use measures of intra-granular misorientation within grains and near grain boundaries in both deformed (non-recrystallized) uranium and recrystallizing uranium. The data show that the level of intra-granular misorientation depends on crystallographic orientation. However, contrary to expectation, this relationship does not significantly affect the recrystallization texture. Rather, the analysis suggests that recrystallization nucleation occurs along high angle grain boundaries in the deformed microstructure. Specifically, we show that the nucleation of recrystallized grains correlates well with the spatially heterogeneousmore » distribution of high angle boundaries. Due to the inhomogeneous distribution of high angle boundaries, the recrystallized microstructure after long times exhibits clustered distributions of small and large grains. Twin boundaries do not appear to act as recrystallization nucleation sites.« less

Softening due to Grain Boundary Cavity Formation and its Competition with Hardening in Helium Implanted Nanocrystalline Tungsten

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cunningham, W. Streit; Gentile, Jonathan M.; El-Atwani, Osman

The unique ability of grain boundaries to act as effective sinks for radiation damage plays a significant role in nanocrystalline materials due to their large interfacial area per unit volume. Leveraging this mechanism in the design of tungsten as a plasma-facing material provides a potential pathway for enhancing its radiation tolerance under fusion-relevant conditions. In this study, we explore the impact of defect microstructures on the mechanical behavior of helium ion implanted nanocrystalline tungsten through nanoindentation. Softening was apparent across all implantation temperatures and attributed to bubble/cavity loaded grain boundaries suppressing the activation barrier for the onset of plasticity viamore » grain boundary mediated dislocation nucleation. An increase in fluence placed cavity induced grain boundary softening in competition with hardening from intragranular defect loop damage, thus signaling a new transition in the mechanical behavior of helium implanted nanocrystalline tungsten.« less

Softening due to Grain Boundary Cavity Formation and its Competition with Hardening in Helium Implanted Nanocrystalline Tungsten

DOE PAGES

Cunningham, W. Streit; Gentile, Jonathan M.; El-Atwani, Osman; ...

2018-02-13

The unique ability of grain boundaries to act as effective sinks for radiation damage plays a significant role in nanocrystalline materials due to their large interfacial area per unit volume. Leveraging this mechanism in the design of tungsten as a plasma-facing material provides a potential pathway for enhancing its radiation tolerance under fusion-relevant conditions. In this study, we explore the impact of defect microstructures on the mechanical behavior of helium ion implanted nanocrystalline tungsten through nanoindentation. Softening was apparent across all implantation temperatures and attributed to bubble/cavity loaded grain boundaries suppressing the activation barrier for the onset of plasticity viamore » grain boundary mediated dislocation nucleation. An increase in fluence placed cavity induced grain boundary softening in competition with hardening from intragranular defect loop damage, thus signaling a new transition in the mechanical behavior of helium implanted nanocrystalline tungsten.« less

A grain boundary damage model for delamination

NASA Astrophysics Data System (ADS)

Messner, M. C.; Beaudoin, A. J.; Dodds, R. H.

2015-07-01

Intergranular failure in metallic materials represents a multiscale damage mechanism: some feature of the material microstructure triggers the separation of grain boundaries on the microscale, but the intergranular fractures develop into long cracks on the macroscale. This work develops a multiscale model of grain boundary damage for modeling intergranular delamination—a failure of one particular family of grain boundaries sharing a common normal direction. The key feature of the model is a physically-consistent and mesh independent, multiscale scheme that homogenizes damage at many grain boundaries on the microscale into a single damage parameter on the macroscale to characterize material failure across a plane. The specific application of the damage framework developed here considers delamination failure in modern Al-Li alloys. However, the framework may be readily applied to other metals or composites and to other non-delamination interface geometries—for example, multiple populations of material interfaces with different geometric characteristics.

Influence of Alloying upon Grain-Boundary Creep

NASA Technical Reports Server (NTRS)

Rhines, F N; Bond, W E; Kissel, M A

1957-01-01

Grain-boundary displacement, occurring in bicrystals during creep at elevated temperature (350 degrees c), has been measured as a function of the copper content (0.1 to 3 percent) in a series of aluminum-rich aluminum-copper solid-solution alloys. The minimums in stress and temperature, below which grain-boundary motion does not occur, increase regularly with the copper content as would be expected if recovery is necessary for movement. Otherwise, the effects, if any, of the copper solute upon grain-boundary displacement and its rate are too small for identification by the experimental technique employed. It was shown, additionally, that grain-boundary displacement appears regular and proceeds at a constant rate if observed parallel to the stress axis, whereas the motion is seen to occur in a sequence of surges and the rate to diminish with time if the observations are made perpendicular to the stress axis.

Experimental study on the effects of fixed boundaries in channelized free surface dry granular flows

NASA Astrophysics Data System (ADS)

Sarno, Luca; Carleo, Luigi; Nicolina Papa, Maria

2017-04-01

The dynamics of granular mixtures, involved in geophysical flows like avalanches and debris flows, is far from being completely understood. Several features of their motion, such as rheological stratification, non-local and boundary effects, still represent open problems. Experimental investigations at laboratory scale are an important tool that can provide insights about the dynamics of gravity driven granular flows. The measuring techniques should be non-invasive in order to measure undisturbed flows. In this work we present an experimental campaign devoted to the measurement of the velocity profiles of free surface steady granular flows in an open channel. To achieve this goal the flows were recorded by two cameras and velocity profiles were obtained by image analysis. The employed granular medium consists of acetal-polymeric beads with a mean diameter of 3mm and an estimated internal friction angle of 27°. All the experiments have been performed in a 2m-long plexiglas flume with a rectangular cross-section and a slope angle of 30°. The upper part of the channel was used as a reservoir where the material was loaded before each run and then let flow down through an adjustable gate. Several mass flow rates were investigated. Three different basal surfaces were employed so as to observe slip and non-slip boundary conditions: a smooth Bakelite surface, a roughened surface, obtained by gluing a layer of grains on the bed surface and a sandpaper surface with characteristic length of the roughness equal to 425 µm. The flume is equipped with two high-speed cameras, one placed aside the channel and the other one perpendicular to the channel bed, as to get both side-wall and free surface velocity profiles. The particle image velocimetry open-source code, PIVlab, is employed for estimating the flow velocities. All the free surface velocity profiles show an approximately parabolic shape with a maximum at the cross-section midpoint and a minimum at the side-walls, due to the wall friction. Different kinds of side-wall velocity profiles are observed. As regards the smooth basal surface, a slip velocity at the bed is observed. The profiles are Bagnold-type near the free surface and become linear as the depth increases. On the glued-grain basal surface the flow velocity at the bed is null and all the velocity profiles show a rheological stratification with a lower exponential tail and an upper linear profile. Grain rolling is observed at the sandpaper bed, instead. With the increase of flow depths, the velocity profiles gradually shift from the ones observed on the smooth bed to the ones observed on the glued-grain bed. In order to further understand the constitutive behaviour of granular mixtures, it is useful to perform simultaneous measurements of flow velocity and volume fraction. In this perspective, a new series of experiments is actually undergoing for the measurement of the volume fraction.

Strain Amount Dependent Grain Size and Orientation Developments during Hot Compression of a Polycrystalline Nickel Based Superalloy

PubMed Central

He, Guoai; Tan, Liming; Liu, Feng; Huang, Lan; Huang, Zaiwang; Jiang, Liang

2017-01-01

Controlling grain size in polycrystalline nickel base superalloy is vital for obtaining required mechanical properties. Typically, a uniform and fine grain size is required throughout forging process to realize the superplastic deformation. Strain amount occupied a dominant position in manipulating the dynamic recrystallization (DRX) process and regulating the grain size of the alloy during hot forging. In this article, the high-throughput double cone specimen was introduced to yield wide-range strain in a single sample. Continuous variations of effective strain ranging from 0.23 to 1.65 across the whole sample were achieved after reaching a height reduction of 70%. Grain size is measured to be decreased from the edge to the center of specimen with increase of effective strain. Small misorientation tended to generate near the grain boundaries, which was manifested as piled-up dislocation in micromechanics. After the dislocation density reached a critical value, DRX progress would be initiated at higher deformation region, leading to the refinement of grain size. During this process, the transformations from low angle grain boundaries (LAGBs) to high angle grain boundaries (HAGBs) and from subgrains to DRX grains are found to occur. After the accomplishment of DRX progress, the neonatal grains are presented as having similar orientation inside the grain boundary. PMID:28772514

Continuous modeling of a grain boundary in MgO and its disclination induced grain-boundary migration mechanism

NASA Astrophysics Data System (ADS)

Cordier, P.; Sun, X.; Taupin, V.; Fressengeas, C.

2016-12-01

Grain boundaries (GBs) are thin material layers where the lattice rotates from one orientation to the next one within a few nanometers. Because they treat these layers as infinitely thin interfaces, large-scale polycrystalline representations fail to describe their structure. Conversely, atomistic representations provide a detailed description of the GBs, but their character remains discrete and not prone to coarse-graining procedures. Continuum descriptions based on kinematic and crystal defect fields defined at interatomic scale are appealing because they can provide smooth and thorough descriptions of GBs, recovering in some sense the atomistic description and potentially serving as a basis for coarse-grained polycrystalline representations. In this work, a crossover between atomistic description and continuous representation of a MgO tilt boundary in polycrystals is set-up to model the periodic arrays of structural units by using dislocation and disclination dipole arrays along GBs. The strain, rotation, curvature, disclination and dislocation density fields are determined in the boundary area by using the discrete atomic positions generated by molecular dynamics simulations. Then, this continuous disclination/dislocation model is used as part of the initial conditions in elasto-plastic continuum mechanics simulations to investigate the shear-coupled boundary migration of tilt boundaries. The present study leads to better understanding of the structure and mechanical architecture of grain boundaries.

Microstructure evolution in the fusion zone of laser-welded Mg–Gd–Y–Zr alloy during solution and aging treatment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Lyuyuan

The microstructure evolution in the fusion zone of laser-welded Mg-Gd-Y-Zr alloy during solution and aging treatment is investigated. The morphology of the Mg{sub 24}(Gd,Y){sub 5} in the divorced eutectic at the grain boundary transforms from a continuous network to disconnected and fragmentized islands and then to spheroidal particles before complete dissolution during the solution treatment at 430 °C. During the subsequent aging treatment at 225 °C, the precipitation sequence in the fusion zone follows the order of supersaturated solid solution (SSSS) → βʺ(D0{sub 19}) → βʹ(cbco) → β{sub 1}(fcc) → β(fcc). High-density precipitates are present at the original grain boundariesmore » of the fusion zone from the welded structure but there are less precipitates in the interior of the original grains. The grain growth during the solution treatment at 430 °C comprises the slowly increasing stage, rapidly increasing stage, and stable stage. The network-distributed Mg{sub 24}(Gd,Y){sub 5} impedes migration of the grain boundaries, restricts grain growth in the first slowly increasing stage, and segregation of zirconium near the grain boundaries also affects migration of the grain boundaries. - Highlights: •Different quantities of precipitates are present at different location of grain. •The network-distributed Mg{sub 24}(Gd,Y){sub 5} restricts grain growth. •Segregation of Zr affects migration of grain boundaries.« less

Characterization of etch pits found on a large-grain bulk niobium superconducting radio-frequency resonant cavity

DOE PAGES

Zhao, Xin; Ciovati, G.; Bieler, T. R.

2010-12-15

The performance of superconducting radio-frequency (SRF) resonant cavities made of bulk niobium is limited by nonlinear localized effects. Surface analysis of regions of higher power dissipation is thus of intense interest. Such areas (referred to as “hotspots”) were identified in a large-grain single-cell cavity that had been buffered-chemical polished and dissected for examination by high resolution electron microscopy, electron backscattered diffraction microscopy (EBSD), and optical microscopy. Pits with clearly discernible crystal facets were observed in both “hotspot” and “coldspot” specimens. The pits were found in-grain, at bicrystal boundaries, and on tricrystal junctions. They are interpreted as etch pits induced bymore » crystal defects (e.g. dislocations). All coldspots examined had a qualitatively lower density of etch pits or relatively smooth tricrystal boundary junctions. EBSD mapping revealed the crystal orientation surrounding the pits. Locations with high pit density are correlated with higher mean values of the local average misorientation angle distributions, indicating a higher geometrically necessary dislocation content. In addition, a survey of the samples by energy dispersive x-ray analysis did not show any significant contamination of the samples’ surface. In conclusion, the local magnetic field enhancement produced by the sharp-edge features observed on the samples is not sufficient to explain the observed degradation of the cavity quality factor, which starts at peak surface magnetic field as low as 20 mT.« less

Electron Scattering at Surfaces of Epitaxial Metal Layers

NASA Astrophysics Data System (ADS)

Chawla, Jasmeet Singh

In the field of electron transport in metal films and wires, the 'size effect' refers to the increase in the resistivity of the films and wires as their critical dimensions (thickness of film, width and height of wires) approach or become less than the electron mean free path lambda, which is, for example, 39 nm for bulk copper at room temperature. This size-effect is currently of great concern to the semiconductor industry because the continued downscaling of feature sizes has already lead to Cu interconnect wires in this size effect regime, with a reported 2.5 times higher resistivity for 40 nm wide Cu wires than for bulk Cu. Silver is a possible alternate material for interconnect wires and titanium nitride is proposed as a gate metal in novel field-effect-transistors. Therefore, it is important to develop an understanding of how the growth, the surface morphology, and the microstructure of ultrathin (few nanometers) Cu, Ag and TiN layers affect their electrical properties. This dissertation aims to advance the scientific knowledge of electron scattering at surfaces (external surfaces and grain boundaries), that are, the primary reasons for the size-effect in metal conductors. The effect of surface and grain boundary scattering on the resistivity of Cu thin films and nanowires is separately quantified using (i) in situ transport measurements on single-crystal, atomically smooth Cu(001) layers, (ii) textured polycrystalline Cu(111) layers and patterned wires with independently varying grain size, thickness and line width, and (iii) in situ grown interfaces including Cu-Ta, Cu-MgO, Cu-vacuum and Cu-oxygen. In addition, the electron surface scattering is also measured in situ for single-crystal Ag(001), (111) twinned epitaxial Ag(001), and single-crystal TiN(001) layers. Cu(001), Ag(001), and TiN(001) layers with a minimum continuous thickness of 4, 3.5 and 1.8 nm, respectively, are grown by ultra-high vacuum magnetron sputter deposition on MgO(001) substrates with and without thin epitaxial TiN(001) wetting layers and are studied for structure, crystalline quality, surface morphology, density and composition by a combination of x-ray diffraction theta-2theta scans, o-rocking curves, pole figures, reciprocal space mapping, Rutherford backscattering, x-ray reflectometry and transmission electron microscopy. The TiN(001) surface suppresses Cu and Ag dewetting, yielding lower defect density, no twinning, and smaller surface roughness than if grown on MgO(001). Textured polycrystalline Cu(111) layers 25-50-nm-thick are deposited on a stack of 7.5-nm-Ta on SiO2/Si(001), and subsequent in situ annealing at 350°C followed by sputter etching in Ar plasma yields Cu layers with independently variable thickness and grain size. Cu nanowires, 75 to 350 nm wide, are fabricated from Cu layers with different average grain size using a subtractive patterning process. In situ electron transport measurements at room temperature in vacuum and at 77 K in liquid nitrogen for single-crystal Cu and Ag layers is consistent with the Fuchs-Sondheimer (FS) model and indicates specular scattering at the metal-vacuum boundary with an average specularity parameter p = 0.8 and 0.6, respectively. In contrast, layers measured ex situ show diffuse surface scattering due to sub-monolayer oxidation. Also, addition of Ta atoms on Cu(001) surface perturbs the smooth interface potential and results in completely diffuse scattering at the Cu-Ta interface, and in turn, a higher resistivity of single-crystal Cu layers. In situ exposure of Cu(001) layers to O2 between 10 -3 and 105 Pa-s results in a sequential increase, decrease and increase of the electrical resistance which is attributed to specular surface scattering for clean Cu(001) and for surfaces with a complete adsorbed monolayer, but diffuse scattering at partial coverage and after chemical oxidation. Electron transport measurements for polycrystalline Cu layers and wires show a 10-15% and 7-9% decrease in resistivity, respectively, when increasing the average lateral grain size by a factor of 1.8. The maximum resistivity decrease that can be achieved by increasing the grain size of polycrystalline Cu layers with an average grain size approximately ˜2.5x the layer thickness is 20-26%.

Premelting, fluctuations, and coarse-graining of water-ice interfaces.

PubMed

Limmer, David T; Chandler, David

2014-11-14

Using statistical field theory supplemented with molecular dynamics simulations, we consider premelting on the surface of ice as a generic consequence of broken hydrogen bonds at the boundary between the condensed and gaseous phases. A procedure for coarse-graining molecular configurations onto a continuous scalar order parameter field is discussed, which provides a convenient representation of the interface between locally crystal-like and locally liquid-like regions. A number of interfacial properties are straightforwardly evaluated using this procedure such as the average premelting thickness and surface tension. The temperature and system size dependence of the premelting layer thickness calculated in this way confirms the characteristic logarithmic growth expected for the scalar field theory that the system is mapped onto through coarse-graining, though remains finite due to long-ranged interactions. Finally, from explicit simulations the existence of a premelting layer is shown to be insensitive to bulk lattice geometry, exposed crystal face, and curvature.

Premelting, fluctuations, and coarse-graining of water-ice interfaces

NASA Astrophysics Data System (ADS)

Limmer, David T.; Chandler, David

2014-11-01

Using statistical field theory supplemented with molecular dynamics simulations, we consider premelting on the surface of ice as a generic consequence of broken hydrogen bonds at the boundary between the condensed and gaseous phases. A procedure for coarse-graining molecular configurations onto a continuous scalar order parameter field is discussed, which provides a convenient representation of the interface between locally crystal-like and locally liquid-like regions. A number of interfacial properties are straightforwardly evaluated using this procedure such as the average premelting thickness and surface tension. The temperature and system size dependence of the premelting layer thickness calculated in this way confirms the characteristic logarithmic growth expected for the scalar field theory that the system is mapped onto through coarse-graining, though remains finite due to long-ranged interactions. Finally, from explicit simulations the existence of a premelting layer is shown to be insensitive to bulk lattice geometry, exposed crystal face, and curvature.

Atomistic simulation of Al-graphene thin film growth on polycrystalline Al substrate

NASA Astrophysics Data System (ADS)

Zhang, Lan; Zhu, Yongchao; Li, Na; Rong, Yan; Xia, Huimin; Ma, Huizhong

2018-03-01

The growth of Al-Graphene composite coatings on polycrystalline Al substrate was investigated by using classical molecular dynamics (MD) simulations. Unlike the diffusion behaviors on single crystal surface, most of adatoms were easily bound by the steps on polycrystalline Al surface, owing to the local accelerated energy. Both Ehrlich-Schwoebel (ES) barriers and the steering effect backed up the volmer-weber growth mode, which was consistent with the dynamic growth process observed in the deposit. The morphology of composite coatings was significantly affected by graphene flakes. Enrichment of graphene flakes gave rise to an increase of the local thickness, and graphene flakes only existed in Al grain boundaries. The size of Al grains in the composite coating visibly decreased when compared with that in the pure Al coating. This grain refinement and the mechanical property can be reinforced by the increase of graphene flakes.

Effect of surfactant and mineralizer on the dielectric properties of zirconia nanocrsytals

NASA Astrophysics Data System (ADS)

Maheswari, A. Uma; Mohan, Sreedevi R.; Sivakumar, M.

2018-01-01

The combined effect of surfactants (PVP/CTAB) and alkaline mineralizers (NaOH/NH4OH) on dielectric properties of zirconia nanocrystals is analyzed. It is found that, the stabilization of zirconia tetramers by surfactants and the rate of hydroxyl ions released by alkaline mineralizers have significant impact on the dielectric properties of nanocrystals. The PVP capped tetramers form highly conducting grains with insulating boundaries, whereas the grains of CTAB capped tetramers are highly insulating with conducting grain boundaries, as revealed by Nyquist plots. Consequently, the space charge polarization would be quite large in highly conducting grains resulting in higher dielectric constant values at lower frequencies. The higher dielectric constant of PVP capped nanocrystals is due to greater tetragonal coordination of 3d5/2 and 3d3/2 electrons of Zr4+ ions than that of CTAB capped nanocrystals. Further, the surface oxygen vacancies of PVP samples are higher, resulting in a high space charge polarization. The ESR signal corresponding to F+ centers appears stronger for PVP/NH4OH nanocrystals. Moreover, the larger ESR line width of PVP/NH4OH nanocrystals corresponding to more oxygen vacancies is in accordance with the inference attained from the XPS analysis.

Comparison of microstructure of superplastically deformed synthetic materials and ultramylonite: Coalescence of secondary mineral grains via grain boundary sliding

NASA Astrophysics Data System (ADS)

Hiraga, T.; Miyazaki, T.; Tasaka, M.; Yoshida, H.

2011-12-01

Using very fine-grained aggregates of forsterite containing ~10vol% secondary mineral phase such as periclase and enstatite, we have been able to demonstrate their superplascity, that is, achievement of more than a few 100 % tensile strain (Hiraga et al. 2010). Superplastic deformation is commonly considered to proceed via grain boundary sliding (GBS) which results in grain switching in the samples. Hiraga et al. (2010) succeeded in detecting the operation of GBS from observing the coalescence of grains of secondary phase in superplastically deformed samples. The secondary phase pins the motion of grain boundaries of the primary phase; however, the reduction of the number of the grains of secondary phase due to their coalescence allows grain growth of the primary phase. We analyzed the relationships between grain size of the primary and secondary phases, between strain and grain size, and between strain and the number of coalesced grains in the superplastically deformed samples. The results supports participation of all the grains of the primary phase in grain switching process indicating that the grain boundary sliding accommodates almost entire strain during the deformation. Mechanical properties of these materials such as their stress and grain size exponents of 1-2 do not conflict this conclusion. We applied the relationships obtained from analyzing superplastic materials to the microstructure of the natural samples, which has been considered to have deformed via grain boundary sliding, that is, ultramylonite. The microstructure of greenschist-grade ultramylonite reported by Fliervoet et al. (1997) was analyzed. Distributions of the mineral phases (i.e., quartz, plagioclase, K-feldspar and biotite) show distinct coalescence of the same mineral phases in the direction almost perpendicular to the foliation of the rock. The number of coalesced grains indicates that the strain that rock experienced is > 2. [reference] Hiraga et al. (2010) Nature 468, 1091-1094; Fliervoet et al. (1997) Journal of Structural Geology 19, 1495-1520

A generalized self-consistent polycrystal model for the yield strength of nanocrystalline materials

NASA Astrophysics Data System (ADS)

Jiang, B.; Weng, G. J.

2004-05-01

Inspired by recent molecular dynamic simulations of nanocrystalline solids, a generalized self-consistent polycrystal model is proposed to study the transition of yield strength of polycrystalline metals as the grain size decreases from the traditional coarse grain to the nanometer scale. These atomic simulations revealed that a significant portion of atoms resides in the grain boundaries and the plastic flow of the grain-boundary region is responsible for the unique characteristics displayed by such materials. The proposed model takes each oriented grain and its immediate grain boundary to form a pair, which in turn is embedded in the infinite effective medium with a property representing the orientational average of all these pairs. We make use of the linear comparison composite to determine the nonlinear behavior of the nanocrystalline polycrystal through the concept of secant moduli. To this end an auxiliary problem of Christensen and Lo (J. Mech. Phys. Solids 27 (1979) 315) superimposed on the eigenstrain field of Luo and Weng (Mech. Mater. 6 (1987) 347) is first considered, and then the nonlinear elastoplastic polycrystal problem is addressed. The plastic flow of each grain is calculated from its crystallographic slips, but the plastic behavior of the grain-boundary phase is modeled as that of an amorphous material. The calculated yield stress for Cu is found to follow the classic Hall-Petch relation initially, but as the gain size decreases it begins to depart from it. The yield strength eventually attains a maximum at a critical grain size and then the Hall-Petch slope turns negative in the nano-range. It is also found that, when the Hall-Petch relation is observed, the plastic behavior of the polycrystal is governed by crystallographic slips in the grains, but when the slope is negative it is governed by the grain boundaries. During the transition both grains and grain boundaries contribute competitively.

Effect of small perturbations on the evolution of polycrystalline structure during plastic deformation

NASA Astrophysics Data System (ADS)

Korznikova, E. A.; Baimova, Yu. A.; Kistanov, A. A.; Dmitriev, S. V.; Korznikov, A. V.

2014-09-01

The method of molecular dynamics has been used to study the influence of initial perturbations on the evolution of grain boundaries during the shear plastic deformation of a two-dimensional polycrystalline material with nanoscale grains. It has been shown that short-term thermalization-induced small perturbations result in noticeable differences in grain boundaries configurations at the deformation of 0.05 and the polycrystal completely loses its initial grain boundary structure at the deformation of 0.4.

Characterization of structural and electrostatic complexity in pentacene thin films by scanning probe microscopy

NASA Astrophysics Data System (ADS)

Puntambekar, Kanan Prakash

The advancement of organic electronics for applications in solar energy conversion, printed circuitry, displays, and solid-state lighting depends upon optimization of structure and properties for a variety of organic semiconductor interfaces. Organic semiconductor/insulator (O/I) and organic-metal (O/M) interfaces, in particular, are critical to the operation of organic thin film transistors (OTFTs) currently being developed for printed flexible electronics. Scanning probe microscopy (SPM) is a powerful tool to isolate and characterize the bottlenecks to charge transport at these interfaces. This thesis establishes a direct correlation between the structural disorder and electrical complexity at these interfaces, using various SPM based methods and discusses the implications of such complexity on device performance. To examine the O/M interfaces, surface potentials of operating pentacene TFTs with two different contact geometries (bottom or top) were mapped by Kelvin probe force microscopy (KFM). The surface potential distribution was used to isolate the potential drops at the source and drain contacts. Simultaneously obtained topography and surface potential maps elucidated the correlation between the morphology and contact resistance at the O/M interface; the bottom contact TFTs were observed to be contact limited at large gate voltages, while the top contact TFTs were not contact limited. A direct correlation between structural defects and electric potential variations at the pentacene and silicon dioxide, a common insulator, is demonstrated. Lateral force microscopy (LFM) generates striking images of the polycrystalline microstructure of a monolayer thick pentacene film, allowing clear visualization of the grain boundary network. Further more, surface potential wells localized at the grain boundaries were observed by KFM, suggesting that the grain boundaries may serve as charge carrier (hole) traps. Line dislocations were also revealed in the second monolayer by chemical etching and SPM and produce strong variations in the surface potential that must affect the interfacial charge conductance. Structural disorder at the O/I and O/M interfaces degrades both injection and transport of charge, and therefore needs to be minimized. Thus both visualization and correlation of structural and electrical complexity at these interfaces have important implications for understanding electrical transport in OTFTs and for defining strategies to improve device performance.

Fatigue crack initiation and microcrack propagation in X7091 type aluminum P/M alloys

NASA Astrophysics Data System (ADS)

Hirose, S.; Fine, M. E.

1983-06-01

Fatigu crack initiation in extruded X7091 RSP-P/M aluminum type alloys o°Curs at grain boundaries at both low and high stresses. By a process of elimination this grain boundary embrittlement was attributed to Al2O3 particles formed mainly during atomization and segregated to some grain boundaries. It is not due to the small grain size, to Co2Al9, to η precipitates at grain boundaries, nor to a precipitate free zone. Thermomechanical processing after extrusion of X7091 with 0.8 pct Co was done by Alcoa to produce large recrystallized grains. This resulted in initiation of fatigue cracks at slip bands, and the resistance to initiation of fatigue cracks at low stresses was much greater. Microcrack growth is, however, much faster in the thermomechanically treated samples, as well as in ingot alloys, than in extruded and aged X7091.

Grain size constraints on twin expansion in hexagonal close packed crystals

DOE PAGES

Kumar, Mariyappan Arul; Beyerlein, Irene Jane; Tome, Carlos N.

2016-10-20

Deformation twins are stress-induced transformed domains of lamellar shape that form when polycrystalline hexagonal close packed metals, like Mg, are strained. Several studies have reported that the propensity of deformation twinning reduces as grain size decreases. Here, we use a 3D crystal plasticity based micromechanics model to calculate the effect of grain size on the driving forces responsible for expanding twin lamellae. The calculations reveal that constraints from the neighboring grain where the grain boundary and twin lamella meet induce a stress reversal in the twin lamella. A pronounced grain size effect arises as reductions in grain size cause thesemore » stress-reversal fields from twin/grain boundary junctions to affect twin growth. We further show that the severity of this neighboring grain constraint depends on the crystallographic orientation and plastic response of the neighboring grain. We show that these stress-reversal fields from twin/grain boundary junctions will affect twin growth, below a critical parent grain size. Finally, these results reveal an unconventional yet influential role that grain size and grain neighbors can play on deformation twinning.« less

Role of Relaxation on the Giant Permittivity and Electrical Properties of CaCu3Ti4O12 Ceramics

NASA Astrophysics Data System (ADS)

Zhao, Xuetong; Ren, Lulu; Liao, Ruijin; Li, Jianying; Yang, Lijun; Wang, Feipeng

2016-06-01

CaCu3Ti4O12 (CCTO) ceramics were synthesized under various sintering conditions to investigate the role of relaxation on permittivity and electrical properties. Two relaxation processes that respectively related to grain and to domain boundary at a temperature as low as 223 K were fitted according to the Cole-Cole theory. The results indicate that both relaxations largely account for the giant permittivity of CCTO ceramics. Moreover, the relaxation behaviors of grain and of the grain boundary can be processed via impedance plots that vary from 113 K to 473 K. It is shown that longer sintering duration leads to lower resistance of grain and of grain boundary: e.g., from 3200 Ω to 810 Ω and 1.76 MΩ to 0.48 MΩ, respectively. The activation energy related to grain-boundary relaxation drops from 1.14 eV to 0.80 eV, while the value of grain stays unchanged at about 0.11 eV. The Schottky barrier of the CCTO sample decreases from 0.65 eV to 0.57 eV. It is also proposed that the nonlinearity of current-voltage property for CCTO ceramics may be strongly related to the relaxation processes of grain boundaries.

Generation of plate tectonics with two-phase grain-damage and pinning: Source-sink model and toroidal flow

NASA Astrophysics Data System (ADS)

Bercovici, David; Ricard, Yanick

2013-03-01

The grain-damage and pinning mechanism of Bercovici and Ricard (2012) for lithospheric shear-localization is employed in two-dimensional flow calculations to test its ability to generate toroidal (strike-slip) motion and influence plate evolution. This mechanism posits that damage to the interface between phases in a polycrystalline material like peridotite (composed primarily of olivine and pyroxene) increases the number of small Zener pinning surfaces, which then constrain mineral grains to ever smaller sizes, regardless of creep mechanism. This effect allows a self-softening feedback in which damage and grain-reduction can co-exist with a grain-size dependent diffusion creep rheology; moreover, grain growth and weak-zone healing are greatly impeded by Zener pinning thereby leading to long-lived relic weak zones. The fluid dynamical calculations employ source-sink driven flow as a proxy for convective poloidal flow (upwelling/downwelling and divergent/convergent motion), and the coupling of this flow with non-linear rheological mechanisms excites toroidal or strike-slip motion. The numerical experiments show that pure dislocation-creep rheology, and grain-damage without Zener pinning (as occurs in a single-phase assemblages) permit only weak localization and toroidal flow; however, the full grain-damage with pinning readily allows focussed localization and intense, plate-like toroidal motion and strike-slip deformation. Rapid plate motion changes are also tested with abrupt rotations of the source-sink field after a plate-like configuration is developed; the post-rotation flow and material property fields retain memory of the original configuration for extensive periods, leading to suboptimally aligned plate boundaries (e.g., strike-slip margins non-parallel to plate motion), oblique subduction, and highly localized, weak and long lived acute plate-boundary junctions such as at what is observed at the Aleutian-Kurile intersection. The grain-damage and pinning theory therefore readily satisfies key plate-tectonic metrics of localized toroidal motion and plate-boundary inheritance, and thus provides a predictive theory for the generation of plate tectonics on Earth and other planets.

Subthreshold characteristics of pentacene field-effect transistors influenced by grain boundaries

NASA Astrophysics Data System (ADS)

Park, Jaehoon; Jeong, Ye-Sul; Park, Kun-Sik; Do, Lee-Mi; Bae, Jin-Hyuk; Sun Choi, Jong; Pearson, Christopher; Petty, Michael

2012-05-01

Grain boundaries in polycrystalline pentacene films significantly affect the electrical characteristics of pentacene field-effect transistors (FETs). Upon reversal of the gate voltage sweep direction, pentacene FETs exhibited hysteretic behaviours in the subthreshold region, which was more pronounced for the FET having smaller pentacene grains. No shift in the flat-band voltage of the metal-insulator-semiconductor capacitor elucidates that the observed hysteresis was mainly caused by the influence of localized trap states existing at pentacene grain boundaries. From the results of continuous on/off switching operation of the pentacene FETs, hole depletion during the off period is found to be limited by pentacene grain boundaries. It is suggested that the polycrystalline nature of a pentacene film plays an important role on the dynamic characteristics of pentacene FETs.

Investigation of Parent Austenite Grains from Martensite Structure Using EBSD in a Wear Resistant Steel

PubMed Central

Gyhlesten Back, Jessica; Engberg, Göran

2017-01-01

Crystallographic reconstruction of parent austenite grain boundaries from the martensitic microstructure in a wear resistant steel was carried out using electron backscattered diffraction (EBSD). The present study mainly aims to investigate the parent austenite grains from the martensitic structure in an as-rolled (reference) steel sample and samples obtained by quenching at different cooling rates with corresponding dilatometry. Subsequently, this study is to correlate the nearest cooling rate by the dilatometer which yields a similar orientation relationship and substructure as the reference sample. The Kurdjumov-Sachs orientation relationship was used to reconstruct the parent austenite grain boundaries from the martensite boundaries in both reference and dilatometric samples using EBSD crystallographic data. The parent austenite grain boundaries were successfully evaluated from the EBSD data and the corresponding grain sizes were measured. The parent austenite grain boundaries of the reference sample match the sample quenched at 100 °C/s (CR100). Also the martensite substructures and crystallographic textures are similar in these two samples. The results from hardness measurements show that the reference sample exhibits higher hardness than the CR100 sample due to the presence of carbides in the reference sample. PMID:28772813

Investigation of Parent Austenite Grains from Martensite Structure Using EBSD in a Wear Resistant Steel.

PubMed

Gyhlesten Back, Jessica; Engberg, Göran

2017-04-26

Crystallographic reconstruction of parent austenite grain boundaries from the martensitic microstructure in a wear resistant steel was carried out using electron backscattered diffraction (EBSD). The present study mainly aims to investigate the parent austenite grains from the martensitic structure in an as-rolled (reference) steel sample and samples obtained by quenching at different cooling rates with corresponding dilatometry. Subsequently, this study is to correlate the nearest cooling rate by the dilatometer which yields a similar orientation relationship and substructure as the reference sample. The Kurdjumov-Sachs orientation relationship was used to reconstruct the parent austenite grain boundaries from the martensite boundaries in both reference and dilatometric samples using EBSD crystallographic data. The parent austenite grain boundaries were successfully evaluated from the EBSD data and the corresponding grain sizes were measured. The parent austenite grain boundaries of the reference sample match the sample quenched at 100 °C/s (CR100). Also the martensite substructures and crystallographic textures are similar in these two samples. The results from hardness measurements show that the reference sample exhibits higher hardness than the CR100 sample due to the presence of carbides in the reference sample.

Origin of high carrier mobility and low residual stress in RF superimposed DC sputtered Al doped ZnO thin film for next generation flexible devices

NASA Astrophysics Data System (ADS)

Kumar, Naveen; Dubey, Ashish; Bahrami, Behzad; Venkatesan, S.; Qiao, Qiquan; Kumar, Mukesh

2018-04-01

In this work, the energy and flux of high energetic ions were controlled by RF superimposed DC sputtering process to increase the grain size and suppress grain boundary potential with minimum residual stress in Al doped ZnO (AZO) thin film. AZO thin films were deposited at different RF/(RF + DC) ratios by keeping total power same and were investigated for their electrical, optical, structural and nanoscale grain boundaries potential. All AZO thin film showed high crystallinity and orientation along (002) with peak shift as RF/(RF + DC) ratio increased from 0.0, pure DC, to 1.0, pure RF. This peak shift was correlated with high residual stress in as-grown thin film. AZO thin film grown at mixed RF/(RF + DC) of 0.75 showed high electron mobility, low residual stress and large crystallite size in comparison to other AZO thin films. The nanoscale grain boundary potential was mapped using Kelvin Probe Force Microscopy in all AZO thin film and it was observed that carrier mobility is controlled not only by grains size but also by grain boundary potential. The XPS analysis confirms the variation in oxygen vacancies and zinc interstitials which explain the origin of low grain boundaries potential and high carrier mobility in AZO thin film deposited at 0.75 RF/(RF + DC) ratio. This study proposes a new way to control the grain size and grain boundary potential to further tune the optoelectronic-mechanical properties of AZO thin films for next generation flexible and optoelectronic devices.

Grain Boundary Sliding in Deforming Wehrlite: Rheology and Microstructure

NASA Astrophysics Data System (ADS)

Zhao, N.; Hirth, G.; Cooper, R. F.; Kruckenberg, S. C.

2016-12-01

Elastic anisotropy of Earth's upper mantle used to be attributed exclusively to dislocation creep. However, recent experimental results suggest that crystallographic preferred orientation (CPO) in olivine, which contributes to elastic anisotropy, could also form during grain boundary sliding [e.g., 1-3]. Nevertheless, the fundamental problem of how CPO forms during grain boundary sliding is not fully understood. Our current efforts examine the grain-size-sensitive flow of wehrlite, to characterize the influence of the second phase (clinopyroxene) both on olivine CPO formation as well as the propensity of grain boundary sliding and accumulated strain to effect solid-state phase separation (i.e., metamorphic layering). Creep tests on fine-grain-size (2-5 µm) olivine and clinopyroxene aggregates (T =1100-1200ºC; P = 1.5 GPa; γ=3-7) have been conducted. These reveal strong type-B fabric for olivine. Characterization of effects of grain size, temperature and applied strain rate reveal the grain size dependence, stress exponent and activation energy of the flow kinetics of wehrlite. The stress exponent, which is similar to stress exponent for harzburgite reported by Sundberg & Cooper [1], and grain-size dependence suggest that the dominant deformation mechanism in our experiments may be grain boundary sliding. A large stress drop in early segments of experiments suggest an evolution of microstructure. The Fourier transform of backscatter images demonstrates that there exists a direction of foliation, defined by Ol-Cpx heterophase boundaries, which may be the key to understand the development of CPO formation. [1] Sundberg, M. & Cooper, R. F., J. Geophys. Res., 2008. [2] Miyazaki, T., Sueyoshi, K., and Hiraga, T., Nature, 2013. [3] Tielke, J. A., L. N. Hansen, M. Tasaka, C. Meyers, M. E. Zimmerman, and D. L. Kohlstedt, J. Geophys. Res., 2016.