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At least 73 records · Page 4

Hydrogen storage properties of magnesium nanotrees investigated by a quartz crystal microbalance system

We report on enhanced low temperature hydrogen storage properties of magnesium “nanotrees” fabricated by glancing angle deposition (GLAD) method. The arrays of nanotrees and conventional thin films of elemental Mg have been deposited directly onto gold coated unpolished quartz crystal substrates. Mg nanotrees were about 15 μm in height, 10 μm by 1 μm in lateral size, and were composed of “nanoleaves” of about 20 nm in thickness, 2 μm length, and 1 μm width. Hydrogen absorption and desorption properties of Mg nanotrees and thin films were investigated using a quartz crystal microbalance (QCM) testing system that is capable of measuring weight changes with a nanogram sensitivity. QCM absorption tests were performed at temperatures 100, 200, and 300 °C under 30 bars of H 2 pressure. Measurements revealed that Mg nanotrees can absorb hydrogen at significantly higher weight percentage (wt%) and faster rates compared to conventional Mg films under similar conditions. Hydrogen storage of Mg thin film was observed to be at 0.02, 0.30 and 3.91 wt% (weight percentage), while it reached to 1.26, 3.75, and 5.86 wt% for nanotrees at temperatures 100, 200, and 300 °C, respectively, after 150 min. In addition, the results of desorption experiments show that Mg nanotrees can start to release hydrogen at temperatures as low as 100 °C at a rate of 0.11 wt% (vs. 0.01 wt% for thin film at the same temperature) with desorption rates reaching to 1.05 wt% at 200 °C (0.26 wt% for thin film) and 2.57 wt% at 300 °C (1.45 wt% for thin film), which are considerably lower desorption temperatures compared to previously reported values for bulk Mg (>300 °C). The enhancement in hydrogen absorption and desorption properties of Mg nanotrees is believed to originate from their thin and isolated nanoleaves that also have an improved oxidation resistance property.

08 HYDROGEN↗

Convection analysis on various crystal growth systems

Specific work done during an indicated contract period was reviewed. An extensive survey of crystal growth literature and related topics was accomplished during this time. Specific attention was given to those areas dealing with the effects of transport phenomena on crystal growth. Critical evaluations of growth techniques were made. Techniques studied included closed tube vapor growth, open reactor vapor growth, melt growth and solution growth.

Source record↗

Crystallization Physics in Biomacromolecular Systems

The crystals are built of molecules of protein, nucleic acid and their complexes, like viruses, approx. 5x10(exp 3)+ 3x10(exp 6) Da in weight and 2 + 20 nm in effective diameter. This size strongly exceeds action range of molecular forces and makes a big difference with inorganic crystals. Intermolecular contacts form patches on the biomacromolecular surface. Each patch may occupy only a small percent of the whole surface and vary from polymorph to polymorph of the same protein. Thus, under different conditions (pH, solution chemistry, temperature, any area on the macromolecular surface may form a contact. The crystal Young moduli, E approx. equals 0.1 + 0.5 GPa are more than 10 times lower than that of inorganics and the biomolecules themselves. Water within biocrystals (30-70%) is unable to flow unless typical deformation time is longer than approx. 10(exp -5)s. This explains the discrepancy between light scattering and static measurements of E. Nucleation and Growth requires typically concentrations exceeding the equilibrium ones up to 100 times - because of the new size scale results in 10 - 10(exp 3) times lower kinetic coefficients than that needed for inorganic solution growth. All phenomena observed in the latter occur with protein crystallization and are even better studied by AFM. Crystals are typically facetted. Among unexpected findings of general significance are - net molecular exchange flux at kinks is much lower than that expected from supersaturation, steps with low (< approx. 10(exp -2)) kink density at steps follow Gibbs-Thomson law only at very low supersaturations, step segment growth rate may be independent of step energy. Crystal perfection is a must of biocrystallization to achieve the major goal to find 3-D atomic structure of biomacromolecules by x-ray diffraction. Poor diffraction resolution (> 3Angstrom) makes crystallization a bottleneck for structural biology. All defects typical of small molecule crystals are found in biocrystals, but the defects responsible for poor resolution are not identified. Conformational changes are one of them. Biocrystallization in microgravity reportedly results in 20% cases of better crystals. The mechanism of how lack of convection can do this is still not clear. Lower supersaturation, self-purification &om preferentially trapped homologous impurities and step bunching are viable hypotheses.

Chernov, A. A.↗

Automated prediction of lattice parameters from X-ray powder diffraction patterns

A key step in the analysis of powder X-ray diffraction (PXRD) data is the accurate determination of unit-cell lattice parameters. This step often requires significant human intervention and is a bottleneck that hinders efforts towards automated analysis. This work develops a series of one-dimensional convolutional neural networks (1D-CNNs) trained to provide lattice parameter estimates for each crystal system. A mean absolute percentage error of approximately 10% is achieved for each crystal system, which corresponds to a 100- to 1000-fold reduction in lattice parameter search space volume. The models learn from nearly one million crystal structures contained within the Inorganic Crystal Structure Database and the Cambridge Structural Database and, due to the nature of these two complimentary databases, the models generalize well across chemistries. A key component of this work is a systematic analysis of the effect of different realistic experimental non-idealities on model performance. It is found that the addition of impurity phases, baseline noise and peak broadening present the greatest challenges to learning, while zero-offset error and random intensity modulations have little effect. However, appropriate data modification schemes can be used to bolster model performance and yield reasonable predictions, even for data which simulate realistic experimental non-idealities. In order to obtain accurate results, a new approach is introduced which uses the initial machine learning estimates with existing iterative whole-pattern refinement schemes to tackle automated unit-cell solution.

42 ENGINEERING↗

Residual Gases in Crystal Growth Systems: Their Origin, Magnitude, and Dependence on the Processing Conditions

Residual gases present in closed ampoules may affect different crystal growth processes. Their presence may affect techniques requiring low pressures and affect the crystal quality in different ways. For that reason a good understanding and control of formation of residual gases may be important for an optimum design and meaningful interpretation of crystal growth experiments. Our extensive experimental and theoretical study includes degassing of silica glass and generation of gases from various source materials. Different materials processing conditions, like outgassing under vacuum, annealing in hydrogen, resublimation, different material preparation procedures, multiple annealings, different processing times, and others were applied and their effect on the amount and composition of gas were analyzed. The experimental results were interpreted based on theoretical calculations on diffusion in silica glass and source materials and thermochemistry of the system. Procedures for a reduction of the amount of gas are also discussed.

Palosz, W.↗

Investigating deformation and mesoscale void creation in HMX based composites using tomography based grain scale FEM

The microstructure of plastic bonded explosives (PBXs) significantly affects their macroscale mechanical characteristics. Imaging and modeling of the mesoscale constituents allows for a detailed examination of the deformation of mechanically loaded PBXs. In this study, a pair of explosive HMX crystals were bound with an HTPB based polymer binder and imaged using micro Computed Tomography ($µ$CT). Delamination of the polymer binder from the crystals was induced via macro-scale application of a tensile load. Cohesive parameters for simulation of the crystal/binder interface were determined by comparing numerical and experimental results of the delamination of this bi-crystal system. Simulations showed macro-scale plastic behavior is accommodated through both crystal-binder delamination and plastic deformation of the binder itself. Imaging and simulation of this bi-crystal system demonstrated the complex interplay of material constitutive behavior and grain-scale geometry. Successful parameterization of this relatively simple mechanical system is a step toward a better understanding void nucleation in similarly composed polycrystalline composites.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

A Crystal-Diffraction System Prototype for Measuring Neutron’s Charge: Thermal Protection Test and Vibration Measurements

A prototype system design for ultra-high-precision neutron spectrometry using diffraction in perfect crystals is described. Results of experimental verification of the temperature stability inside the setup are presented. Results of vibration spectrum measurements in working zone of the PF1b beam of ILL reactor (Grenoble, France), where the prototype setup will be arranged for experimental testing, are considered.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Computing dispersive, polarizable, and electrostatic shifts of excitation energy in supramolecular systems: PTCDI crystal

The gas-to-crystal-shift denotes the shift of electronic excitation energies, i.e., the difference between ground and excited state energies, for a molecule transferred from the gas to the bulk phase. The contributions to the gas-to-crystal-shift comprise electrostatic as well as inductive polarization and dispersive energy shifts of the molecular excitation energies due to interaction with environmental molecules. For the example of 3,4,9,10-perylene-tetracarboxylic-diimide (PTCDI) bulk, the contributions to the gas-to-crystal shift are investigated. In the present work, electrostatic interaction is calculated via Coulomb interaction of partial charges while inductive and dispersive interactions are obtained using respective sum over states expressions. The coupling of higher transition densities for the first 4500 excited states of PTCDI was computed using transition partial charges based on an atomistic model of PTCDI bulk obtained from molecular dynamics simulations. As a result it is concluded that for the investigated model system of a PTCDI crystal, the gas to crystal shift is dominated by dispersive interaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cluster self-organization of inorganic crystal-forming systems: Templated nanocluster precursors and self-assembly of framework MT structures of A/B,Zr silicates (A = Na, K; B = Ca, Sr)

The basic concepts that are used to describe crystallization as a phenomenon of the hierarchical (cluster) self-organization of a chemical system are considered. The templation of theoretically possible nan-ocluster precursors composed of M octahedra and T tetrahedra by atoms of (A) alkaline and (B) alkaline earth metals is considered for the first time. A relationship between the A/B,M,T composition of templated nanocluster precursors with the composition of A/B,M silicates is established. The model that is developed is used to search for nanocluster precursors in framework MT structures of A/B,Zr silicates. Computer methods (TOPOS 4.0 program package) were used to perform complete 3D reconstruction of the self-assembly of all (four) structural types of A/B,Zr silicates (A = Na, K; B = Ca, Sr) with frameworks of the MT{sub 2}O{sub 7} type: nan-ocluster precursor S{sub 3}{sup 0}-primary chain S{sub 3}{sup 1}-microlayer S{sub 3}{sup 2}-microframework S{sub 3}{sup 3}. The invariant type of mono-cyclic nanocluster precursor M{sub 2}T{sub 4} (with the point symmetries 1-bar and 2), stabilized by one or two template cations (A and B), is determined. Bifurcations of the paths of evolution at the S{sub 3}{sup 1} level (structural branching point) are established for the self-assembly of the following frameworks: MT-1 in CaZrSi{sub 2}O{sub 7} (gittinsite, C2), MT-2 in SrZrSi{sub 2}O{sub 7} (P2{sub 1}/c); MT-3 in Na{sub 2}ZrSi{sub 2}O{sub 7} (parakeldyshite,), K{sub 2}ZrSi{sub 2}O{sub 7} (khibinskite, P2{sub 1}/b), and K{sub 2}ZrGe{sub 2}O{sub 7} (C2/c); and MT-4 in Na{sub 2}ZrSi{sub 2}O{sub 7} (H{sub 2}O)(C2/c), Na{sub 3}ScSi{sub 2}O{sub 7} (Pbnm), and K{sub 3}ScSi{sub 2}O{sub 7} (P6{sub 3}/mmc).

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Helfrich-Hurault elastic instabilities driven by geometrical frustration

Here, the Helfrich-Hurault (HH) elastic instability is a well-known mechanism behind patterns that form as a result of strain upon liquid crystal systems with periodic ground states. In the HH model, layered structures undulate and buckle in response to local, geometric incompatibilities in order to maintain the preferred layer spacing. Classic HH systems include cholesteric liquid crystals under electromagnetic field distortions and smectic liquid crystals under mechanical strains, where both materials are confined between rigid substrates. However, richer phenomena are observed when undulation instabilities occur in the presence of deformable interfaces and variable boundary conditions. Understanding how the HH instability is affected by deformable surfaces is imperative for applying the instability to a broader range of materials. In this review, the HH mechanism is reexamined and special focus is given to how the boundary conditions influence the response of lamellar systems to geometrical frustration. Lamellar liquid crystals confined within a spherical shell geometry are used as the model system. Made possible by the relatively recent advances in microfluidics within the past 15 years, liquid crystal shells are composed entirely of fluid interfaces and have boundary conditions that can be dynamically controlled at will. Past and recent work that exemplifies how topological constraints, molecular anchoring conditions, and boundary curvature can trigger the HH mechanism in liquid crystals with periodic ground states is examined. The review ends by identifying similar phenomena across a wide variety of materials, both biological and synthetic. The fact that the HH mechanism is a generic and often overlooked response of periodic materials to geometrical frustration is highlighted.

42 ENGINEERING↗

Scalable fabrication of coupled NV center - photonic crystal cavity systems by self-aligned N ion implantation

Towards building large-scale integrated photonic systems for quantum information processing, spatial and spectral alignment of single quantum systems to photonic nanocavities is required. In this paper, we demonstrate spatially targeted implantation of nitrogen vacancy (NV) centers into the mode maximum of 2-d diamond photonic crystal cavities with quality factors up to 8000, achieving an average of 1.1 ± 0.2 NVs per cavity. Nearly all NV-cavity systems have significant emission intensity enhancement, reaching a cavity-fed spectrally selective intensity enhancement, F int , of up to 93. Although spatial NV-cavity overlap is nearly guaranteed within about 40 nm, spectral tuning of the NV’s zero-phonon-line (ZPL) is still necessary after fabrication. To demonstrate spectral control, we temperature tune a cavity into an NV ZPL, yielding F ZPL int ~5 at cryogenic temperatures.

36 MATERIALS SCIENCE↗

Phase formation in the Li{sub 2}MoO{sub 4}-K{sub 2}MoO{sub 4}-In{sub 2}(MoO{sub 4}){sub 3} system and crystal structures of new compounds K{sub 3}InMo{sub 4}O{sub 15} and LiK{sub 2}In(MoO{sub 4}){sub 3}

XRD study of solid-phase interaction in the Li{sub 2}MoO{sub 4}-K{sub 2}MoO{sub 4}-In{sub 2}(MoO{sub 4}){sub 3} system was performed. The boundary K{sub 2}MoO{sub 4}-In{sub 2}(MoO{sub 4}){sub 3} system is an non-quasibinary join of the K{sub 2}O-In{sub 2}O{sub 3}-MoO{sub 3} system where a new polymolybdate K{sub 3}InMo{sub 4}O{sub 15} isotypic to K{sub 3}FeMo{sub 4}O{sub 15} was found. In the structure (a=33.2905(8), b=5.8610(1), c=15.8967(4) A, {beta}=90.725(1) Degree-Sign , sp. gr. C2/c, Z=8, R(F)=0.0407), InO{sub 6} octahedra, Mo{sub 2}O{sub 7} diortho groups and MoO{sub 4} tetrahedra form infinite ribbons {l_brace}[In(MoO{sub 4}){sub 2}(Mo{sub 2}O{sub 7})]{sup 3-}{r_brace}{sub {infinity}} along the b-axis. Between the chains, 8- to 10-coordinate potassium cations are located. A subsolidus phase diagram of the Li{sub 2}MoO{sub 4}-K{sub 2}MoO{sub 4}-In{sub 2}(MoO{sub 4}){sub 3} system was constructed and a novel triple molybdate LiK{sub 2}In(MoO{sub 4}){sub 3} was revealed. Its crystal structure (a=7.0087(2), b=9.2269(3), c=10.1289(3) A, {beta}=107.401(1) Degree-Sign , sp. gr. P2{sub 1}, Z=2, R(F)=0.0280) contains an open framework of vertex-shared MoO{sub 4} tetrahedra, InO{sub 6} octahedra and LiO{sub 5} tetragonal pyramids with nine- and seven-coordinate potassium ions in the framework channels. - Graphical abstract: Exploring the Li{sub 2}MoO{sub 4}-K{sub 2}MoO{sub 4}-In{sub 2}(MoO{sub 4}){sub 3} system showed its partial non-quasibinarity and revealed new compounds K{sub 3}InMo{sub 4}O{sub 15} (isotypic to K{sub 3}FeMo{sub 4}O{sub 15}) and LiK{sub 2}In(MoO{sub 4}){sub 3} which were structurally studied. An open framework of the latter is formed by vertex-shared MoO{sub 4} tetrahedra, InO{sub 6} octahedra and LiO{sub 5} tetragonal pyramids. Highlights: Black-Right-Pointing-Pointer Subsolidus phase relations in the Li{sub 2}MoO{sub 4}-K{sub 2}MoO{sub 4}-In{sub 2}(MoO{sub 4}){sub 3} system were explored. Black-Right-Pointing-Pointer The K{sub 2}MoO{sub 4}-In{sub 2}(MoO{sub 4}){sub 3} system is a non-quasibinary join of the K{sub 2}O-In{sub 2}O{sub 3}-MoO{sub 3} system. Black-Right-Pointing-Pointer New compounds K{sub 3}InMo{sub 4}O{sub 15} and LiK{sub 2}In(MoO{sub 4}){sub 3} were obtained and structurally studied. Black-Right-Pointing-Pointer K{sub 3}InMo{sub 4}O{sub 15} is isotypic to K{sub 3}FeMo{sub 4}O{sub 15} and carries bands of InO{sub 6}, MoO{sub 4} and Mo{sub 2}O{sub 7} units. Black-Right-Pointing-Pointer An open framework of LiK{sub 2}In(MoO{sub 4}){sub 3} is formed by polyhedra MoO{sub 4}, InO{sub 6} and LiO{sub 5}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tailored multivariate analysis for modulated enhanced diffraction

Modulated enhanced diffraction (MED) is a technique allowing the dynamic structural characterization of crystalline materials subjected to an external stimulus, which is particularly suited for in situ and operando structural investigations at synchrotron sources. Contributions from the (active) part of the crystal system that varies synchronously with the stimulus can be extracted by an offline analysis, which can only be applied in the case of periodic stimuli and linear system responses. In this paper a new decomposition approach based on multivariate analysis is proposed. The standard principal component analysis (PCA) is adapted to treat MED data: specific figures of merit based on their scores and loadings are found, and the directions of the principal components obtained by PCA are modified to maximize such figures of merit. As a result, a general method to decompose MED data, called optimum constrained components rotation (OCCR), is developed, which produces very precise results on simulated data, even in the case of nonperiodic stimuli and/or nonlinear responses. The multivariate analysis approach is able to supply in one shot both the diffraction pattern related to the active atoms (through the OCCR loadings) and the time dependence of the system response (through the OCCR scores). When applied to real data, OCCR was able to supply only the latter information, as the former was hindered by changes in abundances of different crystal phases, which occurred besides structural variations in the specific case considered. To develop a decomposition procedure able to cope with this combined effect represents the next challenge in MED analysis.

Caliandro, Rocco↗

Phase formation in the Li{sub 2}MoO{sub 4}–Rb{sub 2}MoO{sub 4}–Fe{sub 2}(MoO{sub 4}){sub 3} system and crystal structure of a novel triple molybdate LiRb{sub 2}Fe(MoO{sub 4}){sub 3}

X-ray investigation of solid state interaction of the components in the Li{sub 2}MoO{sub 4}–Rb{sub 2}MoO{sub 4}–Fe{sub 2}(MoO{sub 4}){sub 3} system was carried out, and a subsolidus phase diagram of the said system was constructed. The subsystem Rb{sub 2}MoO{sub 4}–LiRbMoO{sub 4}–RbFe(MoO{sub 4}){sub 2} was shown to be non-quasiternary. Formation of a novel triple molybdate LiRb{sub 2}Fe(MoO{sub 4}){sub 3} was established, conditions of solid state synthesis and crystallization of the compound were found. Its crystal structure (orthorhombic, space group Pnma, Z=4, a=24.3956(6), b=5.8306(1), c=8.4368(2) Å) represents a new structure type and includes infinite two-row ribbons ([Fe(MoO{sub 4}){sub 3}]{sup 3−}){sub ∞} parallel to the b axis and composed of FeO{sub 6} octahedra, terminal Mo(3)O{sub 4} tetrahedra, and bridge Mo(1)O{sub 4} and Mo(2)O{sub 4} tetrahedra connecting two or three FeO{sub 6} octahedra. The ribbons are connected to form 3D framework via corner-sharing LiO{sub 4} tetrahedra. Rubidium cations are 11- and 13-coordinated and located in cavities of this heterogeneous polyhedral framework. - Graphical abstract: Exploring the Li{sub 2}MoO{sub 4}–Rb{sub 2}MoO{sub 4}–Fe{sub 2}(MoO{sub 4}){sub 3} system showed its partial non-quasiternarity and revealed a new compound LiRb{sub 2}Fe(MoO{sub 4}){sub 3} which was structurally studied. - Highlights: • The Li{sub 2}MoO{sub 4}–Rb{sub 2}MoO{sub 4}–Fe{sub 2}(MoO{sub 4}){sub 3} system study revealed a new compound LiRb{sub 2}Fe(MoO{sub 4}){sub 3}. • Its structure of a new type includes ribbons of FeO{sub 6} octahedra and MoO{sub 4} tetrahedra. • The ribbons are connected into a 3D framework via corner-sharing LiO{sub 4} tetrahedra.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mild Hydrothermal Crystal Growth of Two Luminescing Uranyl Phosphates Exhibiting an Autunite-Type Sheet Structure

Two new layered uranyl phosphate compounds, K(UO 2 )PO 4 (H 2 O) 3 and Na(UO 2 )PO 4 (H 2 O) 1.52 , crystallizing in an autunite-type sheet structure, were successfully synthesized as both single-crystals and polycrystalline powders under mild hydrothermal conditions. The compound K(UO 2 )PO 4 (H 2 O) 3 crystallizes in the tetragonal crystal system with the space group P4/ncc, exhibiting lattice parameters of a = b = 6.99320(7) Å and c = 17.8389(3) Å. Similarly, Na(UO 2 )PO 4 (H 2 O) 1.52 also crystallizes in the tetragonal crystal system, however, in the space group P4/nmm and exhibits lattice parameters of a = b = 6.9787 Å and c = 8.6303(17) Å. Both compounds adopt layered structures, a characteristic feature of uranyl phosphates, and exhibit intense green fluorescence typical for uranyl-containing materials. As a result, the infrared spectroscopy, photoluminescence, and scintillation properties of these compounds were investigated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modeling shock-induced void collapse in single-crystal Ta systems at the mesoscales

Understanding the role of microstructural heterogeneities on the shock wave propagation and defect evolution behavior is essential to predicting the dynamic response of metals. Heterogeneities, such as voids, provide challenges to understanding the wave propagation behavior as the shock-void interaction can collapse the void and result in large plastic strains and significant heating (hot spot formation) in the metal. Accurate modeling of this phenomenon requires predicting the void collapse mechanisms and the related heat generation and dissipation mechanisms (hotspot formation) that determine the microstructure evolution. While molecular dynamics (MD) simulations can model the void collapse behavior, the time/length scale capabilities pose a challenge to connect with continuum models or the experimental scales. Here, this study presents the capability of the newly developed quasi-coarse-grained dynamics (QCGD) method that extends the MD simulations to larger system sizes and longer times to model this phenomenon. This study uses QCGD simulations to investigate the mechanisms of shock wave interactions with pre-existing voids in single-crystal Ta microstructures for variations in shock pressures, void size, and loading orientations. For a given orientation, the plasticity contributions and rates of void collapse are observed to vary with shock pressures and void size. The larger void sizes and higher pressures result in increased temperatures (hot spots) and faster void collapse rates and unravel the variations in the plasticity contributions. In addition, QCGD simulations investigate the post-collapse microstructure evolution as a release wave travels through the hot spot region. The simulations reveal that the reduction in temperatures due to heat dissipation initiates the dynamic recrystallization behavior in the hotspot regions.

36 MATERIALS SCIENCE↗

Drop deployment system for crystal growth apparatus

A crystal growth apparatus is presented. It utilizes a vapor diffusion method for growing protein crystals, and particularly such an apparatus wherein a ball mixer is used to mix the fluids that form a drop within which crystals are grown. Particular novelty of this invention lies in utilizing a ball mixer to completely mix the precipitate and protein solutions prior to forming the drop. Additional novelty lies in details of construction of the vials, the fluid deployment system, and the fluid storage system of the preferred embodiment.

Rhodes, Percy↗