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At least 271 records · Page 15

Cr3+ doped ZnGa2O4 far-red emission phosphor-in-glass: Toward high-power and color-stable plant growth LEDs with responds to all of phytochrome

Highlights: • A high-power and color-stable far-red emission phosphor-convertor LEDs is proposed. • The Cr{sup 3+} ion as the center of luminescence not only increase choice in plant lighting but also provides far-red light. • The ZGO:Cr{sup 3+}-PiG shows a quantum efficiency of ∼52.8%. • The high-power plant growth LEDs was fabricated, triggering providing broad spectral range for plant growth LEDs. - Abstract: In present work, a series of luminescent glass ceramic plates were prepared via phosphor-in-glass (PiG) technology, in which included the phosphor of ZnGa{sub 2}O{sub 4}:Cr{sup 3+} (ZGO:Cr{sup 3+}) and glass host with composition of 30SiO{sub 2}-30ZnO-22B{sub 2}O{sub 3}-12BaO-6Al{sub 2}O{sub 3} as matrix. The structure of ZnGa{sub 2}O{sub 4}:Cr{sup 3+}-based PiG (ZGO:Cr{sup 3+}-PiG) samples are characterized by powder X-ray diffraction, scanning electron microscope, and energy dispersive spectrometer mapping. These phosphors are found to be embedded in glass matrix without interfacial reaction. In addition, the ZGO:Cr{sup 3+}-PiG sample shows a quantum efficiency of ∼52.8% and its fluorescence intensity maintains 68.2% when temperature reaching 150 °C. Finally, high-power and color-stable far-red emission plant growth LEDs was fabricated by ZGO:Cr{sup 3+}-PiG and 400 nm near-UV LED chip, which spectra matches well the absorption of plant's photosynthetic pigments. More importantly, it responds to all of phytochrome, triggering providing broad spectral range for plant growth LEDs.

36 MATERIALS SCIENCE↗

Properties of Cerium Hydroxides from Matrix Infrared Spectra and Electronic Structure Calculations

Reactions of laser ablated cerium atoms with hydrogen peroxide or hydrogen and oxygen mixtures diluted in argon and condensed at 4 K produced the Ce(OH) 3 and Ce(OH) 2 molecules and Ce(OH) 2 + cation as major products. Additional minor products were identified as the Ce(OH) 4 , HCeO, and OCeOH molecules. These new species were identified from their matrix infrared spectra with D 2 O 2 , D 2 , and 18 O 2 isotopic substitution and correlating observed frequencies with values calculated by density functional theory. We find that the amounts of Ce(OH) 3 and of the Ce(OH) 2 + cation increase on UV ($λ$ > 220 nm) photolysis, while Ce(OH) 2 , Ce(OH) 4 , and HCeO are photosensitive. The observed major species for Ce are in the +III or +II oxidation state, and the minor product, Ce(OH) 4 , is in the +IV oxidation state. The calculations for the vibrational frequencies with the B3LYP functional agree well with the experiment. The NBO analysis shows significant backbonding to the metal 4f and 5d orbitals for the closed shell species. Most open shell species have the excess spin in the 4f with paired spin in the 5d due to backbonding. The heats of formation of the observed species were derived from the available data from experiment and the calculated reaction energies. The major products in this study are different from similar reactions for Th where the tetrahydroxide was the major species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Plant Cell Growth and Cell Wall Enlargement

Irreversible cell enlargement begins with cell wall loosening which induces wall stress relaxation, leading to cell water uptake and cell enlargement. Growing cell walls consist of a cohesive network of cellulose microfibrils embedded in hydrophilic pectins and cellulose-binding hemicelluloses. Models of the growing cell wall are provisional hypotheses about how these wall polymers interact to make a strong yet extensible wall. Recent results clarify how wall strength, plasticity and elasticity depend mostly on the stretching, straightening and sliding of cellulose microfibril networks in the wall. Passive sliding of cellulose microfibrils is facilitated by nonenzymic proteins named expansins while various enzymes modify pectins and hemicelluloses, altering their interactions with each other and with cellulose. Growth cessation is correlated with reduced expression of genes that promote wall loosening as well as changes in the direction of cellulose deposition and the structure of matrix polysaccharides, leading to a less extensible cell wall.

59 BASIC BIOLOGICAL SCIENCES↗

Factors Affecting Fiber Design and Selection for Advanced Ceramic Composites

Structural Ceramic Matrix Composites (CMC) have the potential for application in the hot sections of a variety of advanced propulsion and power systems. It is therefore necessary to have a general understanding of the key properties of CMC and Reinforcing Fibers. This need is complicated by the wide variety of application conditions and structural requirements for which CMC's will be used, and the proprietary concerns of the design engineers. CMC's, to be successful, must display properties which are competitive with the currently used high temperature structural materials: (i.e., Iron and Nickel based superalloys, tough monolithic ceramics, and carbon/carbon composites.) Structural CMC offers several areas of competition: (1) performance, (i.e., strength and strength retention, creep resistance, and thermal conductivity), (2) reliability (i.e., environmental durability, and damage tolerance) and (3) processing (i.e., capability for varying sizes and shapes, and cost effective fabrication). The presentation further discusses, and illustrates with fiber and CMC data the key fiber properties and processes which strongly affect each CMC area of competition. The presentation further discusses the current knowledge of the important factors which control the key fiber properties. A design guidelines for the optimum fiber characteristics is developed, and the currently available fibers are compared against those guidelines.

DiCarlo, James A.↗

Experimental Study of Spontaneous Emission in the Bragg Multiple Quantum Wells Structure of InAs Monolayers Embedded in a GaAs Matrix

Time-resolved photoluminescence of a Bragg structure of InAs-monolayer quantum wells in GaAs matrix was experimentally studied with. Comparison of luminescence patterns from the side and from the surface of a sample showed that Bragg-type ordering of quantum wells leads to a substantial alteration of the photoluminescence spectra including appearance of additional radiative modes. The sample side spectrum contains a single line corresponding to a ground state of an exciton. The surface spectrum at high excitation levels a new radiation line appears whose frequency and propagation angle correspond to the Bragg condition for quantum wells. A numerical calculation of the modal Purcell factor explains why the radiative emission amplification occurs only at a set of specific angles and frequencies, as opposed to the whole range that satisfies the Bragg condition.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Structural characterization of HIV-1 matrix mutants implicated in envelope incorporation

During the late phase of HIV-1 infection, viral Gag polyproteins are targeted to the plasma membrane (PM) for assembly. Gag localization at the PM is a prerequisite for the incorporation of the envelope protein (Env) into budding particles. Gag assembly and Env incorporation are mediated by the N-terminal myristoylated matrix (MA) domain of Gag. Nonconservative mutations in the trimer interface of MA (A45E, T70R, and L75G) were found to impair Env incorporation and infectivity, leading to the hypothesis that MA trimerization is an obligatory step for Env incorporation. Conversely, Env incorporation can be rescued by a compensatory mutation in the MA trimer interface (Q63R). The impact of these MA mutations on the structure and trimerization properties of MA is not known. In this study, we employed NMR spectroscopy, X-ray crystallography, and sedimentation techniques to characterize the structure and trimerization properties of HIV-1 MA A45E, Q63R, T70R, and L75G mutant proteins. NMR data revealed that these point mutations did not alter the overall structure and folding of MA but caused minor structural perturbations in the trimer interface. Analytical ultracentrifugation data indicated that mutations had a minimal effect on the MA monomer–trimer equilibrium. The high-resolution X-ray structure of the unmyristoylated MA Q63R protein revealed hydrogen bonding between the side chains of adjacent Arg-63 and Ser-67 on neighboring MA molecules, providing the first structural evidence for an additional intermolecular interaction in the trimer interface. These findings advance our knowledge of the interplay of MA trimerization and Env incorporation into HIV-1 particles.

60 APPLIED LIFE SCIENCES↗

Characterization of silver/polystyrene nanocomposites prepared by in situ bulk radical polymerization

Graphical abstract: - Highlights: • Synthesis and characterization of polystyrene nanocomposites based on Ag nanoparticles. • The glass transition temperature decreased in nanocomposites with respect to the pure polymer. • Resistance of the polymer to thermal degradation enhanced with Ag nanoparticles content. - Abstract: Nanocomposites (NCs) with different content of silver nanoparticles (Ag NPs) embeded in polystyrene (PS) matrix were prepared by in situ bulk radical polymerization. The nearly monodisperse Ag NPs protected with oleylamine were synthesized via organic solvo-thermal method and further used as a filler. The as-prepared spherical Ag NPs with diameter of 7.0 ± 1.5 nm were well dispersed in the PS matrix. The structural properties of the resulting Ag/PS NCs were characterized by transmission electron microscope (TEM) and Fourier transform infrared (FTIR) spectroscopy, while optical properties were characterized using optical absorption measurements. The gel permeation chromatography (GPC) measurements showed that the presence of Ag NPs stabilized with oleylamine has no influence on the molecular weight and polydispersity of the PS matrix. The influence of silver content on the thermal properties of Ag/PS NCs was investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The results indicated that resistance of PS to thermal degradation was improved upon incorporation of Ag NPs. The Ag/PS NCs have lower glass transition temperatures than neat PS because loosely packed oleylamine molecules at the interface caused the increase of free volume and chain segments mobility near the surface of Ag NPs.

36 MATERIALS SCIENCE↗

Rapid adhesive bonding concepts

Adhesive bonding in the aerospace industry typically utilizes autoclaves or presses which have considerable thermal mass. As a consequence, the rates of heatup and cooldown of the bonded parts are limited and the total time and cost of the bonding process is often relatively high. Many of the adhesives themselves do not inherently require long processing times. Bonding could be performed rapidly if the heat was concentrated in the bond lines or at least in the adherends. Rapid adhesive bonding concepts were developed to utilize induction heating techniques to provide heat directly to the bond line and/or adherends without heating the entire structure, supports, and fixtures of a bonding assembly. Bonding times for specimens are cut by a factor of 10 to 100 compared to standard press bonding. The development of rapid adhesive bonding for lap shear specimens (per ASTM D1003 and D3163), for aerospace panel bonding, and for field repair needs of metallic and advanced fiber reinforced polymeric matrix composite structures are reviewed.

Stein, B. A.↗

Positive semidefinite tensor factorizations of the two-electron integral matrix for low-scaling ab initio electronic structure

Tensor factorization of the 2-electron integral matrix is a well-known technique for reducing the computational scaling of ab initio electronic structure methods toward that of Hartree-Fock and density functional theories. The simplest factorization that maintains the positive semidefinite character of the 2-electron integral matrix is the Cholesky factorization. In this paper, we introduce a family of positive semidefinite factorizations that generalize the Cholesky factorization. Using an implementation of the factorization within the parametric 2-RDM method [D. A. Mazziotti, Phys. Rev. Lett. 101, 253002 (2008)], we study several inorganic molecules, alkane chains, and potential energy curves and find that this generalized factorization retains the accuracy and size extensivity of the Cholesky factorization, even in the presence of multi-reference correlation. The generalized family of positive semidefinite factorizations has potential applications to low-scaling ab initio electronic structure methods that treat electron correlation with a computational cost approaching that of the Hartree-Fock method or density functional theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ordered mixed-layer structures in the Mighei carbonaceous chondrite matrix

High resolution transmission electron microscopy of the Mighei carbonaceous chondrite matrix has revealed the presence of a new mixed layer structure material. This mixed-layer material consists of an ordered arrangement of serpentine-type (S) and brucite-type (B) layers in the sequence SBBSBB. Electron diffraction and imaging techniques show that the basal periodicity is approximately 17 A. Discrete crystals of SBB-type material are typically curved, of small size (less than 1 micron) and show structural variations similar to the serpentine group minerals. Mixed-layer material also occurs in association with planar serpentine. Characteristics of SBB-type material are not consistent with known terrestrial mixed-layer clay minerals. Evidence for formation by a condensation event or by subsequent alteration of pre-existing material is not yet apparent.

Mackinnon, I. D. R.↗

Rapid adhesive bonding concepts for specimen and panel fabrication and field repair

The NASA Langley Research Center has developed bonding concepts for aerospace composite materials which employ induction heating to directly apply heat to the bond line and/or adherends without simultaneously heating the entire structure, supports, and fixtures of a bonding assembly. These methods have demonstrated bonding process time reductions of two to three orders of magnitude, by comparison with conventional press molding. Attention is presently given to rapid adhesive bonding for lap shear specimens for aerospace panel bonding or field repair, as well as for the field repair requirements of metallic and advanced polymeric matrix composite structures.

Stein, B. A.↗

Crazing of nanocomposites with polymer-tethered nanoparticles

The crazing behavior of polymer nanocomposites formed by blending polymer grafted nanoparticles with an entangled polymer melt is studied by molecular dynamics simulations. We focus on the three key differences in the crazing behavior of a composite relative to the pure homopolymer matrix, namely, a lower yield stress, a smaller extension ratio, and a grafted chain length dependent failure stress. The yield behavior is found to be mostly controlled by the local nanoparticle-grafted polymer interfacial energy, with the grafted polymer-polymer matrix interfacial structure being of little to no relevance. Increasing the attraction between nanoparticle core and the grafted polymer inhibits void nucleation and leads to a higher yield stress. In the craze growth regime, the presence of “grafted chain” sections of ≈100 monomers alters the mechanical response of composite samples, giving rise to smaller extension ratios and higher drawing stresses than for the homopolymer matrix. As a result, the dominant failure mechanism of composite samples depends strongly on the length of the grafted chains, with disentanglement being the dominant mechanism for short chains, while bond breaking is the failure mode for chain lengths >10N e , where N e is the entanglement length.

36 MATERIALS SCIENCE↗

Rapid adhesive bonding and field repair of aerospace materials

Adhesive bonding in the aerospace industry typically utilizes autoclaves or presses which have considerable thermal mass. As a consequence, the rates of heatup and cooldown of the bonded parts are limited and the total time and cost of the bonding process are often relatively high. Many of the adhesives themselves do not inherently require long processing times. Bonding could be performed rapidly if the heat was concentrated in the bond lines or at least in the adherends. Rapid Adhesive Bonding concepts are developed to utilize induction heating techniques to provide heat directly to the bond line and/or adherends without heating the entire structure, supports, and fixtures of a bonding assembly. Bonding times for specimens can be cut by a factor of 10 to 100 compared to standard press or autoclave bonding. The development of Rapid Adhesive Bonding for lap shear specimens (per ASTM D1002 and D3163), for aerospace panel or component bonding, and for field repair needs of metallic and advanced fiber reinforced polymeric-matrix composite structures is reviewed. Equipment and procedures are described for bonding and repairing thin sheets, simple geometries, and honeycomb core panels.

Stein, B. A.↗

Photoconductivity of Si/Ge multilayer structures with Ge quantum dots pseudomorphic to the Si matrix

Longitudinal photoconductivity spectra of Si/Ge multilayer structures with Ge quantum dots grown pseudomorphically to the Si matrix are studied. Lines of optical transitions between hole levels of quantum dots and Si electronic states are observed. This allowed us to construct a detailed energy-level diagram of electron-hole levels of the structure. It is shown that hole levels of pseudomorphic Ge quantum dots are well described by the simplest 'quantum box' model using actual sizes of Ge islands. The possibility of controlling the position of the long-wavelength photosensitivity edge by varying the growth parameters of Si/Ge structures with Ge quantum dots is determined.

36 MATERIALS SCIENCE↗

The Stomatopod Dactyl Club: A Formidable Damage-Tolerant Biological Hammer

Nature has evolved efficient strategies to synthesize complex mineralized structures that exhibit exceptional damage tolerance. One such example is found in the hypermineralized hammer-like dactyl clubs of the stomatopods, a group of highly aggressive marine crustaceans. The dactyl clubs from one species, Odontodactylus scyllarus, exhibit an impressive set of characteristics adapted for surviving high-velocity impacts on the heavily mineralized prey on which they feed. Consisting of a multiphase composite of oriented crystalline hydroxyapatite and amorphous calcium phosphate and carbonate, in conjunction with a highly expanded helicoidal organization of the fibrillar chitinous organic matrix, these structures display several effective lines of defense against catastrophic failure during repetitive high-energy loading events.

36 MATERIALS SCIENCE↗

Structural study of Ni- or Mg-based complexes incorporated within UiO-66-NH{sub 2} framework and their impact on hydrogen sorption properties

Nickel and magnesium acetylacetonate molecular complexes were post-synthetically incorporated into microporous zirconium-based MOF (UiO-66-NH{sub 2}) in order to introduce active open-metal sites for hydrogen sorption. Elemental analysis, nitrogen physisorption and DFT calculations revealed that 5 molecules of Ni(acac){sub 2} or 2 molecules of Mg(acac){sub 2} were incorporated into one unit cell of UiO-66-NH{sub 2}. {sup 1}H–{sup 13}C CPMAS and {sup 1}H MAS NMR spectroscopy showed that, although embedded within the pores, both Ni- and Mg-complexes interacted with the UiO-66-NH{sub 2} framework only through weak van der Waals bonds. Inclusion of metal complexes led to the decrease of hydrogen sorption capacities in Ni-modified as well as in Mg-modified samples in comparison with the parent UiO-66-NH{sub 2}. The isosteric hydrogen adsorption enthalpy slightly increased in the case of Ni-modified material, but not in the case of Mg-modified analogue. - Graphical abstract: A post-synthesis impregnation of Mg- and Ni-acetylacetonate complexes performed on zirconium-based MOF UiO-66-NH{sub 2} does influence the hydrogen sorption performance with respect to the parent matrix. The structural study revealed that Mg- and Ni-acetylacetonate molecules interact with zirconium-terephthalate framework only by weak interactions and they are not covalently bonded to aminoterephthalate ligand. Still, they remain confined into the pores even after hydrogen sorption experiments. - Highlights: • Mg- and Ni-acetylacetonate molecules embedded in the pores of UiO-66-NH{sub 2} by PSM. • Molecules of complexes interact with framework only by van der Waals interactions. • Type/structure of deposited metal-complex impact hydrogen enthalpy of adsorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The AGR-3/4 fission product transport irradiation experiment

AGR-3/4 was the combined third and fourth planned irradiations for the U.S. Department of Energy Advanced Gas Reactor (AGR) Fuel Development and Qualification Program. The primary purpose of the AGR program is to support the development and qualification of tristructural isotropic (TRISO) coated particle fuel for use in High Temperature Gas-cooled Reactors. AGR-3/4 was designed as a fission product transport irradiation experiment whose specific objectives were to: (1) irradiate fuel containing UCO (uranium oxycarbide) designed-to-fail (DTF) fuel particles that provide a fixed source of fission products for subsequent transport through compact matrix and structural graphite materials, (2) assess the effects of sweep gas impurities on fuel performance and fission product transport, (3) provide irradiated fuel and material samples for post-irradiation examination and post-irradiation heating, and (4) support the refinement of fuel performance and fission product transport models. The AGR-3/4 test train was irradiated in the northeast flux trap of the Advanced Test Reactor at Idaho National Laboratory for 369.1 effective full power days from December 2011 to April 2014. The experiment was successful in achieving its specification goals in terms of burnup and fast fluence levels reached at the end of irradiation and fuel temperature levels maintained throughout irradiation: peak compact burnup reached 15.27% fissions per initial heavy-metal atom and peak compact fast fluence reached 5.32 × 10 25 n/m 2 (E > 0.18 MeV), while the time-average volume-average temperatures of the compacts ranged from 854 to 1345°C. Fission product release to birth ratios reached values in the 10 -4 - 10 -3 range early during irradiation as the DTF particles started to fail. In conclusion, subsequent post-irradiation examination will provide information on fission product distributions in matrix and core graphite materials, enabling refinement of fission product transport models.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Microstructural and magnetic characterization of rapidly solidified and annealed Pt-Co-B alloys

Significant increases in intrinsic coercivity (Hic) of Pt-Co alloys have been obtained by the addition of boron and the application of rapid solidification processing. After rapid solidification by double anvil splat quenching with subsequent annealing at 650 C for 30 min, an alloy of Pt42Co45B13 exhibits an Hic as high as 14 kOe. Annealing of the Pt-Co-B influences the L1(0) superlattice structure and grain size of the matrix, the crystal structure and size of Co-boride precipitate, and the distribution of magnetic domain walls. A microstructural analysis shows that the maximum H(ic) occurs when Co borides, having the Co3B structure, are within the single magnetic domain size. The magnetic hardening mechanism in Pt-Co-B is believed to be a combination of inhibited magnetic domain nucleation and difficult reverse magnetic domain growth caused by the interaction of the magnetically anisotropic Co borides with the L1(0) Pt-Co matrix.

Qiu, N.↗