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At least 1,477 records · Page 82

Strain-rate dependent deformation mechanisms in single-layered Cu, Mo, and multilayer Cu/Mo thin films

Here, strain-rate sensitivity and rate-dependent hardness, over a range of 10 -2 to 10 2 s -1 , of sputter-deposited single-layered Cu, Mo, and 5 nm Cu/ 5 nm Mo, and 100 nm Cu/ 100 nm Mo multilayer films with a total film thickness of 5 μm were measured using nanoindentation. The plastic zone underneath the nanoindents was characterized via cross-sectional transmission electron microscopy (XTEM). The multilayer films exhibited enhanced hardness but slightly reduced strain-rate sensitivity with decreasing layer thickness from 100 nm to 5 nm. Only the 5 nm Cu/ 5 nm Mo multilayer film exhibited shear bands underneath the nanoindents, and the size of the shear bands increased with increasing strain rate. In contrast, the 100 nm Cu/ 100 nm Mo multilayer film exhibited material pile-up around the indents and significant nanotwinning within Cu grains. The effect of strain rate and layer thickness on the hardness and strain rate sensitivity of the multilayer thin films is interpreted using a modified confined layer slip (CLS) model. The reduced rate sensitivity at 5 nm as compared to 100 nm correlates with abundant growth nanotwins in the Cu grains in 100 nm and formation of shear bands in 5 nm multilayers. In single layer films, a substructure with a high density of dislocations was observed consistent with the plastic strain gradient in the indent plastic zone. No evidence of deformation twins was noted in any of the samples.

36 MATERIALS SCIENCE↗

Study of growth twins produced through heat treatment of fine-grained magnesium

This study investigated the microstructural features of magnesium after the fine-grained magnesium sample was heat treated at 400 °C for 2 h. Both fine-grained and heat-treated magnesium samples were observed using the electron backscatter diffraction technique in scanning electron microscopy. The results show that the grains were substantially coarsened, the local strain and the local misorientation was significantly reduced, and a large number of twins were observed in the heat-treated magnesium sample. The misorientation angle analysis determined that the twins were oriented about 86.3° away from the orientation of their corresponding matrices, and the twins were the variants of $\{1 0 \bar{1} 2\}$ tensile twins. The relative orientation analysis also identified that the fast growth directions of the twins were closely along the $<2 \bar{1} \bar{1} 0>$ or $<1 0 \bar{1} 0>$ directions in the basal plane. The twins can merge or impinge onto each other. Most boundaries between the twins have the misorientation angle of about 7.4°.

36 MATERIALS SCIENCE↗

Dislocation-density evolution and pileups in bicrystalline systems

Here, a dislocation-density crystalline plasticity (DCP) framework based on total and partial dislocation densities interactions was used to investigate the behavior of Cu/Pb bicrystals with a focus on GB effects. The modeling predictions were validated with bicrystal compression micropillar experiments. A key new aspect of the modeling approach is to account for partial dislocation-densities. A GB formulation that is directly linked to GB energies was used to monitor GB transmission and blockages, such that pileups can be monitored and predicted at the GB interfaces for misorientations. The predictions indicate that pileups can form due to fully and partially blocked slip-rates and perfect and partial dislocation-densities. As the nominal strain increases from five to fifteen percent, dislocation-densities and pileups significantly increase by almost an order of magnitude. The proposed validated approach provides a microstructural scale predictive framework that accounts for a myriad of defects related to the interactions of partial and perfect dislocation densities that interact at highly misoriented GBs; it is these interactions that are critical to the formation and evolution of dislocation-density pileups that can lead to physically limiting stress accumulations in bicrystals.

36 MATERIALS SCIENCE↗

Nanotwin stability in alloyed copper under ambient and cryo-temperature dependent deformation states

Nanometer size grains, solid solution strengthening, low temperatures, and a high density of nanotwins can provide significant strengthening to a material. Nevertheless, under loading the microstructure may evolve altering the effect of grain size, twin density, etc. on this strengthening. In some cases, these effects can be coupled as in detwinning, which is a mechanism for cryogenic grain growth. Here, in this work, a series of copper nanotwinned columnar grains are solid solution alloyed with aluminum and subject to ambient and cryogenic (–196 °C) environments during mechanical indentation, with the influence of alloying on the detwinning evolution studied. Under indentation, at a lower aluminum solute content (2 at.%), the columnar grains bent corresponding to a loss of twins. At a higher aluminum solute content (8 at.%), the grains shear and retain the nanotwins. Atomistic-scale simulations reveal an increase in the incoherent twin boundary velocity with decreasing temperature, but this boundary velocity is reduced with increasing alloy solute content. The coupling of solid solution strengthening and nanotwin stabilization is then used to explain the microstructural stability as a function of indentation at different temperature conditions.

36 MATERIALS SCIENCE↗

Energy and mechanical properties predictions in Fe-Ni binary system by ab initio calculations

Here, the fcc random solid solutions in Fe-Ni binary system were investigated using ab initio calculations. Density functional theory (DFT) was applied along with supercells generated by the Special Quasi-Random Structure (SQS) method to predict the enthalpy of mixing and magnetic and elastic properties. The results were compared with relevant experimental and computational data produced by other groups. The effect of SQS supercell size and relaxation procedure on the predicted properties of the alloys were also studied. Our calculations show that 16-atoms SQS model provides adequate approach to the mixing energy of the alloy. However, calculation of mechanical properties requires larger supercell. Excellent agreement between experimental and calculated elastic properties was found in fcc region of Fe-Ni system.

36 MATERIALS SCIENCE↗

Density functional thermodynamic description of spin, phonon and displacement degrees of freedom in antiferromagnetic-to-paramagnetic phase transition in YNiO 3

This work herein demonstrates a direct density functional description of the finite-temperature thermodynamic properties of solids exhibiting phase transitions through positional and spin symmetry breaking degrees of freedom. A classic example addressed here is the rare-earth (R) nickelates RNiO 3 where the ground state is characterized by crystallographic and magnetic (e.g., antiferromagnetic) long-range order (LRO), whereas the higher temperature paramagnetic phase manifests a range of local spin and positional symmetry breaking motifs with short-range order (SRO). Unlike time-dependent simulations of spin and positional degrees of freedom, in the present work, phases are described via a superposition of static configurations constructed by populating a periodic base lattice supercell allowing for the formation of energy lowing distribution of positional and spin local motifs. The thermal populations of the configurations in such a superposition phase are obtained from the energy-minimized Density Functional Theory (DFT)-calculated partition functions at different temperatures. This approach offers flexible inclusion of different physical contributions to the free energy, such as elastic, electronic and phonon free energies, all obtained from the same underlying DFT total energy calculations of periodic structures. The thermodynamic and magnetic properties of both LRO and SRO crystallographic and spin phases, including antiferromagnetic (AFM) to paramagnetic (PM) Néel phase transition in YNiO3 are studied. Including spin and phonon contributions, we find a DFT-calculated Néel temperature to be 144 K in satisfactory agreement with the experimental value of 145 K; whereas omitting the phonon contribution, one obtains a Néel temperature of 81 K. We present phonon contributions to the DFT-calculated temperature-dependent SRO, heat capacities, and the polymorphous distribution of nonzero local magnetic moments in the PM phase. This approach thus extends to finite temperatures the symmetry-broken DFT description of both the AFM and PM phases, demonstrating that a thermodynamic superposition approach based on symmetry broken configurations evaluated by a mean-field like DFT is sufficient to obtain a consistent description of the thermal physics of the AFM, PM phases and their interconversion in 3d oxides illustrated by YNiO 3 .

36 MATERIALS SCIENCE↗

Effect of Sn oxides on the thermal conductivity of polycrystalline SnSe

SnSe is a promising thermoelectric material, with intrinsically low lattice thermal conductivity, κL. Surprisingly, in several reports, polycrystalline samples are found to have a higher thermal conductivity than single crystals. This disparity has been attributed to trace amounts of thermally conductive Sn oxides at the grain boundaries of polycrystalline samples. The same culprit was recently proposed to explain the reduction of κL in purified, oxide-free, SnSe polycrystals. Here, we test this hypothesis by: (i) tuning the type of oxide in SnSe by exploiting thermodynamic stability regions, since Sn-rich or Sn-poor compositions favour the formation of SnO or SnO 2 , respectively; and (ii) varying the quantity of SnO 2 by intentionally oxidizing SnSe powder before consolidation, to obtain samples with quantifiable amounts - up to 15% - of SnO 2 . We find that the κL of SnSe is impervious to changes in the type or the amount of Sn oxide present in the samples. Our results show that a simple “rule of mixtures” cannot be used to estimate the effect of grain boundary oxides on the thermal conductivity of SnSe. These results call for an improved understanding of the intriguing thermal transport mechanisms in SnSe and numerous other systems where a two-phase transport is presumed.

36 MATERIALS SCIENCE↗

Insights on the extraordinary tolerance to alcohols of Fe-N-C cathode catalysts in highly performing direct alcohol fuel cells

Direct alcohol fuel cells (DAFCs) represent the best alternative to batteries for portable and auxiliary power units application due to the high energy density of short chain alcohols. Currently, the utilization of the best platinum group metal (PGM) cathode catalysts is limited, not only by a high cost and scarce resources, but also by the inefficient oxygen reduction reaction (ORR) when permeated alcohols adsorb on the catalytic active sites. In this work, a highly active Fe-N-C catalyst derived from the pyrolysis of nicarbazin (a nitrogen charge transfer organic salt) and an iron precursor has been investigated to get insights on the extraordinary tolerance to the presence of alcohols (methanol and ethanol) of such a PGM-free catalyst. Density functional theory (DFT) calculations demonstrate for the first time that Fe-N 4 and Fe-N 2 C 2 active sites preferentially adsorb oxygen with much higher energy than methanol, ethanol and products of partial ethanol oxidation (0.73–1.16 eV stronger adsorption), while nitrogen-carbon related sites (pyridinic and graphitic nitrogen) are much less selective towards ORR. Half-cell electrochemical characterization showed that the Fe-N-C catalyst overcomes Pt ORR activity in acidic medium with methanol or ethanol concentrations as low as 0.01 M. The feasibility of DAFCs operation based on high methanol (up to 17 M) and ethanol (up to 5 M) concentration thanks to the utilization of Fe-N-C cathode catalyst is demonstrated. Lastly, a new strategy is proposed for DAFCs where using Pt only at the anode and Fe-N-C at the cathode allows extending the device energy density compared to PGM-based catalysts at both electrodes.

30 DIRECT ENERGY CONVERSION↗

The multi-purpose three-axis spectrometer (TAS) MIRA at FRM II

The cold-neutron three-axis spectrometer MIRA is an instrument optimized for low-energy excitations. Its excellent intrinsic $Q$-resolution makes it ideal for studying incommensurate magnetic systems (elastic and inelastic). MIRA is at the forefront of using advanced neutron focusing optics such as elliptic guides, which enable the investigation of small samples under extreme conditions. Another advantage of MIRA is the modular assembly allowing for instrumental adaption to the needs of the experiment within a few hours. The development of new methods such as the spin-echo technique MIEZE is another important application at MIRA. Finally, scientific topics include the investigation of complex inter-metallic alloys and spectroscopy on incommensurate magnetic structures.

36 MATERIALS SCIENCE↗

Phase-breaking effect on polaron transport in organic conjugated polymers

Despite intense investigations and many accepted viewpoints on theory and experiment, the coherent and incoherent carrier transport in organic semiconductors remains an unsettled topic due to the strong electron-phonon coupling. Based on the tight-binding Su-Schrieffer-Heeger (SSH) model combined with a non-adiabatic dynamics method, we study the effect of phase-breaking on polaron transport by introducing a group of phase-breaking factors into π-electron wave-functions in organic conjugated polymers. Two approaches are applied: the modification of the transfer integral and the phase-breaking addition to the wave-function. Within the former, it is found that a single site phase-breaking can trap a polaron. However, with a larger regular phase-breaking a polaron becomes more delocalized and lighter. Additionally, a group of disordered phase-breaking factors can make the polaron disperse in transport process. Within the latter approach, we show that the phase-breaking can render the delocalized state in valence band discrete and the state in the gap more localized. Consequently, the phase-breaking frequency and intensity can reduce the stability of a polaron. Furthermore, the phase-breaking in organic systems is the main factor that degrades the coherent transport and destroys the carrier stability.

36 MATERIALS SCIENCE↗

OLEDs on planarized light outcoupling-enhancing structures in plastic

Light extraction from OLEDs remains a challenge. While consumer demand for OLEDs in display technology continues to grow as prices decline, commercial use of OLEDs in solid state lighting (SSL) applications is lagging due to low light extraction, which results in low efficiency. Previous studies have been directed toward increasing the light extraction factor η out , but cost effective approaches that will enable high throughput and potential upscaling, as well as elucidation of the extraction process, are still lagging. One promising approach is the use of buried light extraction enhancing patterns that are planarized with a high refractive index (RI) layer. When adding substrate mode extracting means, the highest external quantum efficiencies (EQEs) were achieved using a complex approach of planarized vacuum nano holes. Here we present η out -enhancing planarized extraction structures (PES) in plastic. While plastic substrates currently present long-term stability issues and other drawbacks, as we show, they provide a tool for simple, inexpensive, and rapid generation of various enhancing structures that importantly can be transferred to the preferred rigid and flexible glass substrates. Moreover, plastic substrates are attractive for biomedical applications. The successful structures we present are easily scalable periodic corrugations, e.g., with pitch a ~ 4.25 µm and pitch/depth ratio a/h ~2.4 planarized by a layer of RI ~1.9, resulting in maximal EQEs exceeding 60% for a green OLED and 48.5% for a white OLED. Comparable increased EQEs were achieved for structures with a ~ 15 and 16 µm, and a/h ~ 2.1 and 4, respectively. Enhanced extraction was also observed with a very simply fabricated quasiperiodic nanohole array, and surprisingly, with a random shallow design. The latter is at variance with simulations based on diffraction only. Results are discussed in terms of a, h, and structural parameters together with scattering matrix simulations to assess the effect of various PES parameters and the nanoparticle-embedded planarizing layer on η out . The experiments and simulations indicate contributions of diffraction, reflection, and scattering to EQE enhancement.

36 MATERIALS SCIENCE↗

Monte Carlo simulations for understanding the transport properties of metallic nanowires

We report the conductance calculation of metallic nanowires of different metals under the application of a tensile force. The elongation induced by the tensile force was simulated by means of the canonical Monte Carlo method combined with the embedded atom method to compute the energy of the system. We studied nanowires composed of Ag, Au, Pt and Cu. The conductance was calculated by means of the Landauer formula and the non-equilibrium Green function formalism. As previously verified experimentally and using other simulation techniques, the conductance is quantized. In addition to this, we have found that there is a strong correlation between the magnitude of the conductance and the width of the nanowire at its thinnest point. Conductance histograms were analyzed for all the different metals.

36 MATERIALS SCIENCE↗

Electrons matter in ferromagnetic criticality

When elemental iron is cooled from high temperatures, magnetic moments carried by its d-electrons begin a continuous transition to a state of parallel aligned moments below its Curie temperature TC of about 1040 K. As established in the mid-1900s, the statistical physics of this second order phase transition is universal, independent of the ordering temperature, material structure and chemical composition as well as the character of moment-bearing electrons. Finally, the thermodynamics of the phase transition is determined solely by symmetries of the transition’s order parameter – magnetization in the case of a ferromagnet.

36 MATERIALS SCIENCE↗

Radiation induced detwinning in nanotwinned Cu

Superior radiation tolerance has been experimentally examined in nanotwinned metals. The stability of nanotwinned structure under radiation is the key factor for advancing the application of nanotwinned metals for nuclear reactors. We thus performed in situ radiation tests for nanotwinned Cu with various twin thicknesses inside a transmission electron microscope. We found that there is a critical twin thickness (10 nm), below which, radiation induced detwinning is primarily accomplished through migration of incoherent twin boundaries. Lastly, detwinning is faster for thinner twins in this range, while thicker twins are more stable.

36 MATERIALS SCIENCE↗

Nanoscale chemistry and ion segregation in zirconia-based ceramic at grain boundaries by atom probe tomography

In this work nanoscale features that are of importance in the stability of yttria-stabilized tetragonal zirconia (Y-TZP) are quantified through atom probe tomography. In-depth analysis of grain boundary chemistry revealed preferential segregation of lighter and smaller ions towards specific grain boundaries. The relationship between elemental segregation and the local atomistic structure is investigated at the sub-nanometer level to gain insights on nanoscale features associated with the tetragonal-monoclinic phase transformation in Y-TZP through grain boundary characterization. Furthermore, principal component analysis was implemented to reveal any potential biases from varied field evaporation across stabilizer-rich grain boundaries. The observed variations in ion density across different grains suggested a variation in field which was attributed to potential variations in grain crystal orientation. In order to reveal the subtle depletion of oxygen atoms within grain boundaries a new methodology to map oxygen vacancies is proposed, utilizing the relative neighborhood chemistry of individual yttrium atoms.

36 MATERIALS SCIENCE↗

Unveiling damage mechanisms of chromium-coated zirconium-based fuel claddings at LWR operating temperature by in-situ digital image correlation

Here, we investigate the coupled thermomechanical fracture mechanisms of coated nuclear fuel claddings at Light Water Reactor (LWR) operating temperatures. These coated claddings are a highly attractive, near-term solution, which addresses the demands for accident-tolerant fuel systems and provide greater oxidation resistance. However, the fracture mechanisms of these coatings, which may create channels for oxidation ingression, must be fully understood prior to implementation. Thus, high-temperature expanding plug experiments were conducted on coated cladding specimens at a temperature of 315 °C, consistent with the operating environment of LWRs. Furthermore, in-situ thermomechanical deformation was measured with stereo digital image correlation during heating and mechanical testing to separately resolve contributions of thermal and mechanical strain. Digital image correlation, supported by acoustic emissions (AE) detection, was also leveraged to track cracking activity during loading. Coating fracture was found to initiate at total hoop strains of 0.34%. The thermal deformation of the coated claddings was investigated via finite element simulations, revealing a bidirectional stress-state within the coating with axial and circumferential strains of 0.026 and 0.031%. This bidirectional stress-state was attributed with the generation of off-axis fracture pattern within the coating as identified via post-experiment scanning electron microscopy. Thus, this study unveiled critical, coupled thermomechanical mechanisms governing the coating fracture of coated claddings at LWR temperatures.

36 MATERIALS SCIENCE↗