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At least 793 records · Page 44

Advanced Methodology and Preliminary Measurements of Molecular and Mechanical Properties of Heart Valves under Dynamic Strain

Mammalian heart valves are soft tissue assemblies with multi-scale material properties. This is because they are constructs comprising both muscle and non-contractile extracellular matrix proteins (such as collagens and proteoglycans) and transition regions where one form of tissue structure becomes another, significantly different form. The leaflets of the mitral and tricuspid valves are connected to chordae tendinae which, in turn, bind through papillary muscles to the cardiac wall of the ventricle. The transition regions between these tissue subsets are complex and diffuse. Their material composition and mechanical properties have not been previously described with both micro and nanoscopic data recorded simultaneously, as reported here. Annotating the mechanical characteristics of these tissue transitions will be of great value in developing novel implants, improving the state of the surgical simulators and advancing robot-assisted surgery. We present here developments in multi-scale methodology that produce data that can relate mechanical properties to molecular structure using scanning X-ray diffraction. We correlate these data to corresponding tissue level (macro and microscopic) stress and strain, with particular emphasis on the transition regions and present analyses to indicate points of possible failure in these tissues.

valve failure↗

Fast Multilevel Solvers for a Class of Discrete Fourth Order Parabolic Problems

In this paper, we study fast iterative solvers for the solution of fourth order parabolic equations discretized by mixed finite element methods. We propose to use consistent mass matrix in the discretization and use lumped mass matrix to construct efficient preconditioners. We provide eigenvalue analysis for the preconditioned system and estimate the convergence rate of the preconditioned GMRes method. Furthermore, we show that these preconditioners only need to be solved inexactly by optimal multigrid algorithms. Our numerical examples indicate that the proposed preconditioners are very efficient and robust with respect to both discretization parameters and diffusion coefficients. We also investigate the performance of multigrid algorithms with either collective smoothers or distributive smoothers when solving the preconditioner systems.

97 MATHEMATICS AND COMPUTING↗

The j and k dependencies of the line coupling and line mixing effects: Theoretical studies of the relaxation matrices of N 2 -broadened CH 3 D

Line coupling and line mixing effects in parallel and perpendicular bands of CH 3 D perturbed by N 2 have been studied. The work focuses on exhibiting the j and k dependencies of these two processes. The calculations were based on a previously reported anisotropic intermolecular potential including both the long-range multipole, induction, and dispersion forces and a short-range atom-atom model. Throughout this work, it is shown that components with L 1 = 3 of the atom-atom model are dominant contributions to the diffusion operator. As a consequence, in comparison with other molecular systems such as the CH 3 Cl-N 2 and CH 3 I-N 2 , theoretically predicted line coupling and line mixing effects exhibit completely new j and k dependencies. In general, the theoretically calculated halfwidths and intra-doublets’ off-diagonal elements of the relaxation matrix are in reasonable agreement with measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Performance and Durability of Advanced Environmental Barrier Coating Systems

This paper summarizes recent NASA environmental barrier coating (EBC) material advances for protecting the SiC/SiC Ceramic Matrix Composites (CMCs) for meeting next generation turbine engine performance requirements. We particularly present an advanced multicomponent rare earth silicate EBCs with HfO2-Si bond coat system, the temperature capability, environmental stability, and thermomechanical durability, advanced laboratory testing toward subelement demonstrations. Fundamental coating properties of the coating system will also be discussed, with the emphasis on the coating diffusion barrier performance and Calcium Magnesium Alumino-Silicate (CMAS) resistance.

Zhu, Dongming↗

The J and K Dependencies of the Line Coupling and Line Mixing Effects: Theoretical Studies of the Relaxation Matrices of N 2 -Broadened Ch 3 D

Line coupling and line mixing effects in parallel and perpendicular bands of CH 3 D perturbed by N 2 have been studied. The work focuses on exhibiting the j and k dependencies of these two processes. The calculations were based on a previously reported anisotropic intermolecular potential including both the long-range multipole, induction, and dispersion forces and a short-range atom-atom model. It is shown that components with L 1 = 3 of the atom-atom model are dominant contributions to the diffusion operator. As a consequence, in comparison with other molecular systems such as the CH 3 Cl-N 2 and CH 3 I-N 2 , theoretically predicted line coupling and line mixing effects exhibit completely new j and k dependencies. In general, the theoretically calculated halfwidths and intra-doublets’ off-diagonal elements of the relaxation matrix are in reasonable agreement with measurements.

Methane-d↗

Elements distribution and deformation features of a 4.5% Re nickel-based single crystal superalloy during creep at high temperature

Highlights: • Atom probe is used to investigate the element concentration changes in γ and γ' phase during creep. • Mo, W and Re diffuse from γ' to γ phase and enrich in γ/γ' interface during high temperature creep. • Super-dislocations in γ' phase may cross-slip from {111} to {100} plane due to the elements diffusions. • Dislocations shearing into γ' phase may decompose into K-W locks plus APB due to the refractory elements enrichment. - Abstract: By means of creep property measurement, microstructure observation and atom probe tomography, the elements distribution and deformation features of a 4.5% Re nickel-based single crystal superalloy during creep are investigated. Results show that after fully heat treated, the elements Al and Ta are mainly distributed in γ′ phase of alloy. After the alloy is crept up to fracture at 1100 °C/137 MPa, the change of the elements distributing in γ and γ′ phases occurs, wherein, the concentration decrement of the elements Al and Cr in γ′ and γ phases is attributed to their oxidation which may consume the ones. Moreover, some of the atoms Re, W and Mo dissolving in γ′ phase are repelled into γ matrix to reduce its internal energy. And the peak concentration of the atoms Re and W appears in the γ phase near the transition region, the atoms Re, W in the peak region cause the lattice distortion to increase the resistance of dislocations motion, which may improve the creep resistance of alloy. In the later stage of creep, dislocations shearing into the rafted γ′ phase may cross-slip from {111} to {100} plane to form the configuration of K-W locks, which may restrain the slipping of dislocations to improve the creep resistance of alloy. Wherein, the atom Re with lower diffusion coefficient may delay the dislocations in K-W locks for slipping and cross-slipping, which is thought to be the main reason of the K-W locks keeping in 4.5%Re alloy during creep at 1100 °C.

36 MATERIALS SCIENCE↗

Higher order methods for convection-diffusion problems

This paper applies C1 cubic Hermite polynomials embedded in an orthogonal collocation scheme to the spatial discretization of the unsteady nonlinear Burgers equation as a model of the equations of fluid mechanics. The temporal discretization is carried out by means of either a noniterative finite difference or an iterative finite difference procedure. Results of this method are compared with those of a second-order finite difference scheme and a splined-cubic Taylor's series scheme. Stability limits are derived and the matrix structure of the several schemes are compared.

Murphy, J. D.↗

Analytic derivative couplings and first-principles exciton/phonon coupling constants for an ab initio Frenkel-Davydov exciton model: Theory, implementation, and application to compute triplet exciton mobility parameters for crystalline tetracene

Recently, we introduced an ab initio version of the Frenkel-Davydov exciton model for computing excited-state properties of molecular crystals and aggregates. Within this model, supersystem excited states are approximated as linear combinations of excitations localized on molecular sites, and the electronic Hamiltonian is constructed and diagonalized in a direct-product basis of non-orthogonal configuration state functions computed for isolated fragments. In this work, we derive and implement analytic derivative couplings for this model, including nuclear derivatives of the natural transition orbital and symmetric orthogonalization transformations that are part of the approximation. Nuclear derivatives of the exciton Hamiltonian’s matrix elements, required in order to compute the nonadiabatic couplings, are equivalent to the “Holstein” and “Peierls” exciton/phonon couplings that are widely discussed in the context of model Hamiltonians for energy and charge transport in organic photovoltaics. As an example, we compute the couplings that modulate triplet exciton transport in crystalline tetracene, which is relevant in the context of carrier diffusion following singlet exciton fission.

74 ATOMIC AND MOLECULAR PHYSICS↗

Understanding irradiation growth through atomistic simulations: Defect diffusion and clustering in α-zirconium and the influence of alloying elements - 2016-0093

Irradiation-induced structural changes of α-zirconium alloys and in particular the effect of iron were investigated by molecular dynamics simulations using embedded atom potentials derived from first-principles calculations. The simulations revealed that at temperatures between 500 and 600 K self-interstitial atoms (SIAs) diffuse rapidly in a cooperative movement, preferably parallel to basal planes (a directions; ), forming nano-clusters with an extension in and . Vacancies diffuse more slowly than SIAs and remain isolated for a longer period of time. Nano-clusters associated with SIAs cause a pronounced overall expansion in a directions, as well as local strains. Under compressive strain in the c direction, vacancy diffusivity increases in the c direction. In contrast, the diffusivity of SIAs increases in the c direction under a tensile strain in the c direction. SIA nano-clusters are highly mobile within basal planes. Vacancy clusters grow by merging, leading to a contraction in the a direction, compensating for the expansion caused by SIA nano-clusters and possibly contributing to the plateau in growth after the initial rapid expansion. At the onset of breakaway growth, possibly due to stress buildup, the vacancy nano-clusters can condense into c loops, thereby diminishing the compensation effect. The alloying elements iron, nickel, chromium, and niobium liberated from secondary phase particles under irradiation or already in solution are attracted to vacancies and SIAs and are found inside vacancy and SIA loops. The interaction of alloying elements with defect clusters is discussed, with a particular focus on iron. Iron has been found to promote cluster formation in zirconium, and the structures of zirconium-iron clusters have been analyzed. Tin is repelled by SIA clusters and only weakly attracted by vacancies. Niobium impedes the diffusion of SIAs (and therefore may increase annihilation rates with nearby vacancies) and does not destabilize vacancy or SIA clusters. Ab initio calculations of the dimensional and elastic coefficients of the intermetallic phases occurring in secondary phase particles, such as Zr{sub 2}Fe and Zr{sub 3}Fe, are presented, allowing an assessment of local strains in a zirconium matrix. Thus, novel results from extended molecular dynamics simulations provide new insights and contribute to a deeper understanding of the complex mechanisms causing irradiation-induced dimensional changes and the breakaway growth of zirconium alloys. (authors)

36 MATERIALS SCIENCE↗

Microstructure and hardness evolution induced by annealing of ion irradiated LiTaO 3

We report the evolution of the microstructure and mechanical properties of low-energy heavy-ion-irradiated LiTaO 3 crystals annealed at various temperatures was investigated by transmission electron microscopy (TEM) observations and nanoindentation tests to extend the applications of irradiated LiTaO 3 crystals. Before annealing, randomly distributed voids formed in an approximately 200 nm thick region at the end of the ion irradiation range, which was attributed to preferential absorption of interstitials by the amorphous-crystalline interface. After annealing, a new directional diffusion path of defects was identified, resulting in a void string. Furthermore, void string diffusion to the free surface was also found during the annealing temperature increase process, which offers a potential application in designing custom sized-thickness exfoliation at the nanoscale. Meanwhile, two competing processes were identified during the annealing process: epitaxial recrystallization from the amorphous-crystalline interface and grain nucleation process in the amorphous region, which formed phases different from the matrix crystal structure, resulting in an interaction between them. Furthermore, the hardness of irradiated samples was also found to be affected by the annealing process; in particular, a hardness decrease induced by the interstitial Fe ions in the recrystallized region was also confirmed, which can improve the processability of samples for further application.

36 MATERIALS SCIENCE↗

RRR and thermal conductivity of Ag and Ag0.2wt%Mg alloy in Ag/Bi-2212 wires

The residual resistivity ratio (RRR) and thermal conductivity of metal matrix in metal/superconductor composite wires are important parameters for designing superconducting magnets. However, the resistivity of silver in reacted Ag/Bi-2212 wires has yet to be determined over temperature range from 4.2 K to 80 K because Bi-2212 filaments have a critical transition temperature Tc of ~ 80 K, and because it is unknown whether the RRR of Ag/Bi-2212 degrades with Cu diffusing from Bi-2212 filaments into silver sheathes at elevated temperatures and to what degree it varies with heat treatment. We measured the resistivity of stand-alone Ag and AgMg (Ag-0.2wt%Mg) wires as well as the resistivity of Ag and Ag- 0.2wt%Mg in the state-of-the-art Ag/Bi-2212 round wires reacted in 1 bar oxygen at 890 °C for 1, 8, 24 and 48 hours and quickly cooled to room temperature. The heat treatment was designed to reduce the critical current Ic of Bi-2212 wires to nearly zero while allowing Cu loss to fully manifest itself. We determined that pure silver exhibits a RRR of ~ 220 while the oxide-dispersion strengthened AgMg exhibits a RRR of ~ 5 in stand-alone samples. A surprising result is that the RRR of silver in the composite round wires doesn’t degrade with extended time at 890 °C for up to 48 hours. This surprising result may be explained by our observation that the Cu that diffuses into the silver tends to form Cu2O precipitates in oxidizing atmosphere, instead of forming Ag-Cu solution alloy. We also measured the thermal conductivity and the magneto-resistivity of pure Ag and Ag-0.2 wt%Mg from 4.2 K to 300 K in magnetic fields up to 14.8 T and summarized them using a Kohler plot.

43 PARTICLE ACCELERATORS↗

Quasi‐Solid‐State Dye‐Sensitized Solar Cells Containing a Charged Thermoplastic Elastomeric Gel Electrolyte and Hydrophilic/phobic Photosensitizers

As the threat of global climate change due to combustion emissions becomes increasingly alarming, the search for clean and sustainable alternative energy is of paramount importance. With this objective in mind, harnessing solar energy is particularly attractive due to ongoing improvements in silicon‐, perovskite‐, and organic‐based solar cells. Of these, dye‐sensitized solar cells (DSSCs) constitute a promising technology due to their relatively low cost, moderate conversion efficiency, and robust mechanical properties. An important breakthrough in the development of DSSCs is the use of polymer gel electrolytes. In this work, we employ amphi­philic thermoplastic elastomers (TPEs) in the form of sulfonated block ionomer (SBI) homologs for this purpose. Since the midblock of each charged copolymer is hydrophilic, the resultant microphase‐separated nanostructures consist of continuous ionic channels that facilitate electron diffusion. A unique characteristic of the SBI archetype studied here is that the morphology can be solvent‐templated. We exploit this feature by introducing either hydrophilic or hydrophobic photosensitizers into the DSSCs. When the SBI exhibits a primarily lamellar morphology, a hydrophilic dye yields the highest efficiency (7.0%), whereas the opposite is observed when the nanostructure consists of a solvent‐templated nonpolar matrix. Photosensi­tizer tunability is augmented by the intrinsic mechanical and adhesive properties of a TPE.

Al‐Mohsin, Heba A.↗

Ab Initio Design of High-Entropy Thermal/ Environmental Barrier Coatings

Next generation thermal/environmental barrier coatings (TEBC) require carefully balancing various properties including phase stability, thermal conductivity, coefficient of thermal expansion (CTE), mechanical properties, and resistance against hot corrosion and water vapor recession. This work mainly focuses on rapid design of cost-effective high entropy rare-earth disilicates and aluminum garnets to protect SiC-based ceramic matrix composites and nickel-based superalloys in the hot section of gas turbine engines using density functional theory methods. Our calculations identify several low-cost high entropy TEBC exhibiting ultralow thermal conductivity at 1500 K and desirable CTE while maintaining good mechanical properties, including Er1/2Y3/4Yb3/4Si2O7, Gd1/4Er1/4Y3/4Yb3/4Si2O7, Eu1/4Er1/4Y3/4Yb3/4Si2O7, and (Y1/4Gd1/4Er1/4Yb1/4)3Al5O12. This work also aims to gain fundamental understanding of oxygen diffusion in model disilicates. Minimizing oxidizer (such as water vapor and oxygen) permeability through the EBC layer can significantly decrease the growth rate of thermally grown oxide and extend the service life of the coating system. Oxygen diffusion mechanisms including formation energy of defects under varying oxygen conditions and defect migration energy barriers will be presented.

coefficient of thermal expansion↗

The HANDE-QMC Project: Open-Source Stochastic Quantum Chemistry from the Ground State Up

Building on the success of Quantum Monte Carlo techniques such as diffusion Monte Carlo, alternative stochastic approaches to solve electronic structure problems have emerged over the past decade. The full configuration interaction quantum Monte Carlo (FCIQMC) method allows one to systematically approach the exact solution of such problems, for cases where very high accuracy is desired. The introduction of FCIQMC has subsequently led to the development of coupled cluster Monte Carlo (CCMC) and density matrix quantum Monte Carlo (DMQMC), allowing stochastic sampling of the coupled cluster wave function and the exact thermal density matrix, respectively. In this Article, we describe the HANDE-QMC code, an open-source implementation of FCIQMC, CCMC and DMQMC, including initiator and semistochastic adaptations. We describe our code and demonstrate its use on three example systems; a molecule (nitric oxide), a model solid (the uniform electron gas), and a real solid (diamond). An illustrative tutorial is also included.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tuning nanoparticle size for enhanced functionality in perovskite thin films deposited by metal organic deposition

Because of pressing global environmental challenges, focus has been placed on materials for efficient energy use, and this has triggered the search for nanostructural modification methods to improve performance. Achieving a high density of tunable-sized second-phase nanoparticles while ensuring the matrix remains intact is a long-sought goal. In this paper, we present an effective, scalable method to achieve this goal using metal organic deposition in a perovskite system REBa 2 Cu 3 O 7 (rare earth (RE)) that enhances the superconducting properties to surpass that of previous achievements. We present two industrially compatible routes to tune the nanoparticle size by controlling diffusion during the nanoparticle formation stage by selecting the second-phase material and modulating the precursor composition spatially. Combining these routes leads to an extremely high density (8 × 10 22 m -3 ) of small nanoparticles (7 nm) that increase critical currents and reduce detrimental effects of thermal fluctuations at all magnetic field strengths and temperatures. This method can be directly applied to other perovskite materials where nanoparticle addition is beneficial.

36 MATERIALS SCIENCE↗

Lithium superoxide encapsulated in a benzoquinone anion matrix

Lithium peroxide is the crucial storage material in lithium–air batteries. Understanding the redox properties of this salt is paramount toward improving the performance of this class of batteries. Lithium peroxide, upon exposure to p –benzoquinone (p–C 6 H 4 O 2 ) vapor, develops a deep blue color. This blue powder can be formally described as [Li 2 O 2 ] 0.3 • [LiO 2 ] 0.7 • {Li[p–C 6 H 4 O 2 ]} 0.7 , though spectroscopic characterization indicates a more nuanced structural speciation. Infrared, Raman, electron paramagnetic resonance, diffuse-reflectance ultraviolet-visible and X-ray absorption spectroscopy reveal that the lithium salt of the benzoquinone radical anion forms on the surface of the lithium peroxide, indicating the occurrence of electron and lithium ion transfer in the solid state. As a result, obligate lithium superoxide is formed and encapsulated in a shell of Li[p–C 6 H 4 O 2 ] with a core of Li 2 O 2 . Lithium superoxide has been proposed as a critical intermediate in the charge/discharge cycle of Li–air batteries, but has yet to be isolated, owing to instability. The results reported herein provide a snapshot of lithium peroxide/superoxide chemistry in the solid state with redox mediation.

25 ENERGY STORAGE↗

Phase evolution in the ferroelectric relaxor Ba ( Ti 1 - x , Zr x ) O 3 from atomistic simulations

We develop and/or use a combination of first-principles density functional theory and first-principles-based effective Hamiltonian approaches to investigate phase evolution in Ba(Ti 1–x ,Zr x )O 3 ferroelectric relaxor. Our simulations reveal two competing effects, which are associated with substitution of Ti with Zr and primarily responsible for the unusual phase evolution and the properties of this family of solid solutions. They are the negative chemical pressure that Zr exerts on the BaTiO 3 matrix and the ferroelectric “inactivity” of Zr itself. While the former has a stabilizing effect on ferroelectricity, the latter disrupts the ferroelectric cooperation. These competing effects are responsible for the so-called pinched phase transition, where the three phases of parent BaTiO 3 merge together, and the loss of ferroelectricity at the onset of relaxor behavior. Here, the origin of the controversial diffuse phase transition is attributed to the coexistence of the three ferroelectric phases. In the region of the diffuse phase transition, we detect polar nanoregions, which often exhibit unusual nanopillar geometry.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Simultaneous numerical representation of soil microsite production and consumption of carbon dioxide, methane, and nitrous oxide using probability distribution functions

Production and consumption of nitrous oxide (N 2 O), methane (CH 4 ), and carbon dioxide (CO 2 ) are affected by complex interactions of temperature, moisture, and substrate supply, which are further complicated by spatial heterogeneity of the soil matrix. This microsite heterogeneity is often invoked to explain non-normal distributions of greenhouse gas (GHG) fluxes, also known as hot spots and hot moments. To advance numerical simulation of these belowground processes, we expanded the Dual Arrhenius and Michaelis-Menten (DAMM) model, to apply it consistently for all three GHGs with respect to the biophysical processes of production, consumption, and diffusion within the soil, including the contrasting effects of oxygen (O 2 ) as substrate or inhibitor for each process. High-frequency chamber-based measurements of all three GHGs at the Howland Forest (ME, USA) were used to parameterize the model using a multiple constraint approach. The area under a soil chamber is partitioned according to a bivariate lognormal probability distribution function (PDF) of carbon (C) and water content across a range of microsites, which leads to a PDF of heterotrophic respiration and O 2 consumption among microsites. Linking microsite consumption of O 2 with a diffusion model generates a broad range of microsite concentrations of O 2 , which then determines the PDF of microsites that produce or consume CH 4 and N 2 O, such that a range of microsites occurs with both positive and negative signs for net CH 4 and N 2 O flux. Results demonstrate that it is numerically feasible for microsites of N 2 O reduction and CH 4 oxidation to co-occur under a single chamber, thus explaining occasional measurement of simultaneous uptake of both gases. Simultaneous simulation of all three GHGs in a parsimonious modeling framework is challenging, however it increases confidence that agreement between simulations and measurements is based on skillful numerical representation of processes across a heterogeneous environment.

59 BASIC BIOLOGICAL SCIENCES↗