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At least 667 records · Page 37

Miniaturized Air-to-Refrigerant Heat Exchangers

Air-to-refrigerant Heat eXchangers (HX) are an essential component of Heating, Ventilation, Air-Conditioning, and Refrigeration (HVAC&R) systems, serving as the main heat transfer component. The major limiting factor to HX performance is the large airside thermal resistance. Recent literature aims at improving heat transfer performance by utilizing enhancement methods such as fins and small tube diameters; this has lead to almost exhaustive research on the microchannel HX (MCHX). The objective of this project is to develop a miniaturized air-to-refrigerant HX with at least 20% reduction in volume, material volume, and approach temperature compared to current state-of-the-art multiport flat tube designs and also be capable of production within five years. Moreover, the proposed HX’s are expected to have good water drainage and should succeed in both evaporator and condenser applications. The project leveraged Parallel-Parametrized Computational Fluid Dynamics (PPCFD) and Approximation-Assisted Optimization (AAO) techniques to perform multi-scale analysis and shape optimization with the intent of developing novel HX designs whose thermal-hydraulic performance exceeds that of state-of-the-art MCHX. Nine heat exchanger geometries were initially chosen for detailed analysis, selected from 35+ geometries which were identified in previous work at the University of Maryland, College Park. The newly developed optimization framework was exercised for three design optimization problems: (DP I) 1.0kW radiator, (DP II) 10kW radiator and (DP III) 10kW two-phase HX. DP I consisted of the design and optimization of 1.0kW air-to-water HX’s which exceeded the project requirements of 20% volume/material reduction and 20% better performance. Two prototypes for the 1.0kW HX were prototyped, tested and validated using newly-designed airside and refrigerant side test facilities. DP II, a scaled version DP I for 10kW air-to-water HX applications, also yielded optimized HX designs which met project requirements. Attempts to prototype a 10kW have presented unique manufacturing challenges, especially regarding tube blockages and structural stability. DP III comprised optimizing two-phase HX’s for a 3.0Ton capacity in a heat pump / air-conditioning unit for cooling mode application using R410A as the working fluid. The HX’s theoretically address the project requirements. System-level analysis showed the HX’s achieved up to 15% improvement in COP while also reducing overall unit charge by 30-40%. The project methodology was capable of developing HX’s which can outperform current state-of-the-art MCHX by at least 20% reduction in volume, material volume, and approach temperature. Additionally, the capability for optimization using refrigerant charge as an objective function was developed. The five-year manufacturing feasibility of the proposed HX’s was shown to have a good outlook. Successful prototyping through both conventional manufacturing methods and next generation methods such as additive manufacturing was achieved.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Co 11 Li[(OH) 5 O][(PO 3 OH)(PO 4 ) 5 ], a Lithium-Stabilized, Mixed-Valent Cobalt(II,III) Hydroxide Phosphate Framework

A new metastable phase, featuring a lithium-stabilized mixed-valence cobalt(II,III) hydroxide phosphate framework, Co 11.0(1) Li 1.0(2) [(OH) 5 O][(PO 3 OH)(PO 4 ) 5 ], corresponding to the simplified composition Co 1.84(2) Li 0.16(3) (OH)PO 4 , is prepared by hydrothermal synthesis. Because the pH-dependent formation of other phases such as Co 3 (OH) 2 (PO 3 OH) 2 and olivine-type LiCoPO 4 competes in the process, a pH value of 5.0 is crucial for obtaining a single-phase material. The crystals with dimensions of 15 μm × 30 μm exhibit a unique elongated triangular pyramid morphology with a lamellar fine structure. Powder X-ray diffraction experiments reveal that the phase is isostructural with the natural phosphate minerals holtedahlite and satterlyite, and crystallizes in the trigonal space group P31$m$ ($a$ = 11.2533(4) Å, c = 4.9940(2) Å, V = 547.70(3) Å 3 , Z = 1). The three-dimensional network structure is characterized by partially Li-substituted, octahedral [M 2 O 8 (OH)] (M = Co, Li) dimer units which form double chains that run along the [001] direction and are connected by [PO 4 ] and [PO 3 (OH)] tetrahedra. Because no Li-free P31$m$-type Co 2 (OH)PO 4 phase could be prepared, it can be assumed that the Li ions are crucial for the stabilization of the framework. Co L-edge X-ray absorption spectroscopy demonstrates that the cobalt ions adopt the oxidation states +2 and +3 and hence provides further evidence for the incorporation of Li in the charge-balanced framework. The presence of three independent hydroxyl groups is further confirmed by infrared spectroscopy. Magnetization measurements imply a paramagnetic to antiferromagnetic transition at around T = 25 K as well as a second transition at around 9–12 K with a ferromagnetic component below this temperature. The metastable character of the phase is demonstrated by thermogravimetric analysis and differential scanning calorimetry, which above 558 °C reveal a two-step decomposition to CoO, Co 3 (PO 4 ) 2 , and olivine-type LiCoPO 4 with release of water and oxygen.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Kinetics of α-MnOOH Nanoparticle Formation through Enzymatically Catalyzed Biomineralization inside Apoferritin

While biomineralization in apoferritin has effectively synthesized highly monodispersed nanoparticles of various metal oxides and hydroxides, the detailed kinetics and mechanisms of Mn(III) (hydr)oxide formation inside apoferritin cavities have not been reported. To address this knowledge gap, we first identified the phase of solid Mn(III) formed inside apoferritin cavities as α-MnOOH. To analyze the oxidation and nucleation mechanism of α-MnOOH inside apoferritin by quantifying oxidized Mn, we used a colorimetric method with leucoberbelin blue (LBB) solution. In this method, LBB disassembled apoferritin by inducing an acidic pH environment, and reduced α-MnOOH nanoparticles. The LBB-enabled kinetic analyses of α-MnOOH nanoparticle formation suggested that the orders of reaction with respect to Mn2+ and OH– are 2 and 4, respectively, and α-MnOOH formation follows two-step pathways: First, soluble Mn2+ undergoes apoferritin-catalyzed oxidation at the ferroxidase dinuclear center, forming a Mn(III)-protein complex, P-[Mn2O2(OH)2]. Second, the oxidized Mn(III) dissociates from the protein binding sites and is subsequently nucleated to form α-MnOOH nanoparticles in the apoferritin cavities. This study reveals key kinetics and mechanistic information on the Mn-apoferritin systems, and the results facilitate applications of apoferritin as a means of nanomaterial synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamic Hydride Vapor Phase Epitaxy (D-HVPE) as a Route to Inexpensive, High-Performance III-V Materials and Devices

This work describes the recent development of Dynamic Hydride Vapor Phase Epitaxy (D-HVPE), which extends the standard HVPE process to allow for the deposition of relatively complex heterostructures and devices at growth rates in excess of 300 um/h. This process uses low-cost elemental metal precursors, and uses all of the reactants efficiently to create high-performance devices. D-HVPE also lends itself to potential in-line growth, which when combined with the low-cost precursors and extremely fast growth rates for high-quality III-V materials, can lead to significantly lower epitaxial growth costs. Here, we focus on the growth of high-efficiency photovoltaics as an example device to show the capabilities of the D-HVPE growth process.

14 SOLAR ENERGY↗

Electrochemical (de)lithiation of silver ferrite and composites: mechanistic insights from ex situ, in situ, and operando X-ray techniques

Here, the structure of pristine AgFeO 2 and phase makeup of Ag 0.2 FeO1.6 (a one-pot composite comprised of nanocrystalline stoichiometric AgFeO 2 and amorphous γ-Fe 2 O 3 phases) was investigated using synchrotron x-ray diffraction. A new stacking-fault model was proposed for AgFeO2 powder synthesized using the co-precipitation method. The lithiation/de-lithiation mechanisms of silver ferrite, AgFeO 2 and Ag 0.2 FeO 1.6 were investigated using ex-situ, in-situ, and operando characterization techniques. An amorphous γ-Fe 2 O 3 component in the Ag 0.2 FeO 1.6 sample is quantified. Operando XRD of electrochemically reduced AgFeO 2 and Ag 0.2 FeO 1.6 composites demonstrated differences in the structural evolution of the nanocrystalline AgFeO 2 component. As complimentary techniques to XRD, ex-situ x-ray Absorption Spectroscopy (XAS) provided insight into the short-range structure of the (de)lithiated nanocrystalline electrodes, and a novel in-situ high energy x-ray fluorescence nanoprobe (HXN) mapping measurement was applied to spatially resolve the progression of discharge. Based on the results, a redox mechanism is proposed where the full reduction of Ag + to Ag0 and partial reduction of Fe 3+ to Fe 2+ occur on reduction to 1.0 V, resulting in a Li 1+y Fe III Fe II yO 2 phase. The Li 1+y Fe III Fe II yO 2 phase can then reversibly cycle between Fe 3+ and Fe 2+ oxidation states, permitting good capacity retention over 50 cycles. In the Ag 0.2 FeO 1.6 composite, a substantial amorphous γ-Fe 2 O 3 component is observed which discharges to rock salt LiFe 2 O 3 and Fe 0 metal phase in the 3.5 – 1.0 V voltage range (in parallel with the AgFeO 2 mechanism), and reversibly reoxidizes to a nanocrystalline iron oxide phase.

25 ENERGY STORAGE↗

Reactivity of Redox Cycled Fe-bearing Subsurface Sediments Towards Hexavalent Chromium Reduction

Structural Fe(II) in clay minerals and natural sediments is known to reduce Cr(VI) to Cr(III), but the effect of redox-cycled Febearing natural sediments on Cr(VI) reduction kinetics is poorly understood. The objective of this study was to understand the kinetics and mechanisms of Cr(VI) reduction by Fe(II) in redox cycled natural sediment. Fe-bearing sediment was collected from the Ringold formation in the 300 area of Hanford, Washington, United States. Fe redox cycling of the sediment was accomplished via four cycles of bioreduction of structural Fe(III) in Hanford sediment and air oxidation of the resulting Fe(II). Bio-produced Fe(II) in Hanford sediment from each redox cycle was utilized to reduce Cr(VI) at three temperatures (10, 20 and 30° C). The initial rate of Cr(VI) reduction generally increased with each redox cycle, which was more pronounced at high temperatures. The amount of Fe(II) oxidized to the amount of Cr(VI) reduced was close to the expected stoichiometric ratio of 3. Aqueous concentrations of Si, Al, and Fe revealed some dissolution of the sediment after reaction with Cr(VI). Xray diffraction (XRD) and scanning electron microscopy (SEM) detected secondary mineral formation. Mössbauer data showed that the oxidation of Fe(II) was coupled with the reduction of Cr(VI) but no Feoxides/ oxyhydroxides formed. Transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS), XANES, and EXAFS were performed for representative reduced Cr solids that formed from reduction of Cr(VI) by sediment-associated Fe(II) at 30oC. TEM revealed that the d-spacing of Cr-reacted montmorillonite at 30° C, a dominant Fe-bearing mineral in Hanford sediment, expanded from 10 Å to 13 Å. This layer expansion was likely due to intercalation of reduced Cr(III) into the interlayer space of the montmorillonite structure. EELS exhibited an L2 absorption peak at 586.0 eV and an L3 absorption peak at 577.0 eV, suggestive of Cr(III) in a hydroxide mineral phase. Similarly, XANES and EXAFS analyses confirmed Cr(VI) reduction to Cr(OH)3 at 30° C and indicated an edge-sharing coordination of the Cr(III) octahedra to 2-3 other Cr or metal ions. This study has important implications for understanding the reactivity of clay-rich sediment towards Cr(VI) reduction at contaminated sites and the stability of the reduced Cr(III).

Bishop, Michael E.↗

Theoretical study of optical properties of anti phase domains in GaP

III-V/Si heterostructures are currently investigated for silicon photonics and solar energy conversion. In particular, dilute nitride alloy GaAsPN grown on a GaP/Si platform exhibits lattice match with Si and an optimal band gap configuration for tandem solar cell devices. However, monolithic “coherent” growth of the GaP thin layer on Si suffers from the nucleation of extended structural defects, which can hamper device operation as well as the GaP/Si interface level and through their propagation inside the overall heterostructure. However, the effect of such structural defects on optical and transport properties is actually not well understood in details. In this letter, we investigate the anti phase domains defect (also called inversion domains) by means of ab initio calculations giving insights into the alteration of optical and transport properties of GaP due to the defective GaP/Si interface.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Morphology Control of Growth by Hydride Vapor Phase Epitaxy on Faceted GaAs Substrates Produced by Controlled Spalling for Low Cost III-V Devices

In this work, we apply the morphology control of hydride vapor phase epitaxial (HVPE) growth to planarize faceted, non-planar substrates. Controlled spalling is a promising high-throughput substrate reuse technology that could reduce substrate costs for III-V devices; however, the spalling fracture for (100)-oriented GaAs substrates produces a regularly corrugated surface of facets that are 5-20 um in height. We discuss how to planarize these surfaces using only a few minutes of HVPE growth and how to minimize the impact on throughput when integrating faceted wafers into a potential manufacturing process at scale.

epitaxy↗

DUST PRODUCTION FACTORIES IN THE EARLY UNIVERSE: FORMATION OF CARBON GRAINS IN RED-SUPERGIANT WINDS OF VERY MASSIVE POPULATION III STARS

We investigate the formation of dust in a stellar wind during the red-supergiant (RSG) phase of a very massive Population III star with a zero-age main sequence mass of 500 M {sub ☉}. We show that, in a carbon-rich wind with a constant velocity, carbon grains can form with a lognormal-like size distribution, and that all of the carbon available for dust formation finally condenses into dust for wide ranges of the mass-loss rate ((0.1-3) × 10{sup –3} M {sub ☉} yr{sup –1}) and wind velocity (1-100 km s{sup –1}). We also find that the acceleration of the wind, driven by newly formed dust, suppresses the grain growth but still allows more than half of the gas-phase carbon to finally be locked up in dust grains. These results indicate that, at most, 1.7 M {sub ☉} of carbon grains can form during the RSG phase of 500 M {sub ☉} Population III stars. Such a high dust yield could place very massive primordial stars as important sources of dust at the very early epoch of the universe if the initial mass function of Population III stars was top-heavy. We also briefly discuss a new formation scenario of carbon-rich ultra-metal-poor stars, considering feedback from very massive Population III stars.

79 ASTRONOMY AND ASTROPHYSICS↗

Disorder-Induced Quantum Spin Liquid in Spin Ice Pyrochlores

We propose that in a certain class of magnetic materials, known as non-Kramers “spin ice,” disorder induces quantum entanglement. Instead of driving glassy behavior, disorder provokes quantum superpositions of spins throughout the system and engenders an associated emergent gauge structure and set of fractional excitations. More precisely, disorder transforms a classical phase governed by a large entropy, classical spin ice, into a quantum spin liquid governed by entanglement. As the degree of disorder is increased, the system transitions between (i) a “regular” Coulombic spin liquid, (ii) a phase known as “Mott glass,” which contains rare gapless regions in real space, but whose behavior on long length scales is only modified quantitatively, and (iii) a true glassy phase for random distributions with large width or large mean amplitude.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Periphyton and abiotic factors influencing arsenic speciation in aquatic environments: Periphyton alters arsenic speciation

Benthic periphytic biofilms are important food sources at the base of aquatic ecosystems. These biofilms also sit at the interface of oxic waters and hypoxic sediments, and can be influenced by or influence trace element speciation. In the present study, we compared arsenic (As) enrichment in periphyton exposed to arsenate (As[V]) or arsenite (As[III]) (20 μg/L, static renewal, 7 d), and we found similar accumulation patterns of total As (101 ± 27 and 88 ± 22mgkg -1 dry wt, respectively). Periphyton As was 6281- and 6684-fold higher than their aqueous exposures and occurred primarily as As(V). When these biofilms were fed to larval mayflies, similar total As tissue concentrations (13.9 and 14.6mgkg -1 dry wt, respectively) were observed, revealing significant biodilution (~10% of their dietary concentrations). Finally, we investigated the influence of aeration and periphyton presence on As speciation in solutions and solid phases treated with As(III). Predominantly As(III) solutions were slowly oxidized over a 7-d time period, in the absence of periphyton, and aeration did not strongly affect oxidation rates. However, in the presence of periphyton, solution and solid-phase analyses (by microscale x-ray absorption spectroscopy) showed rapid As(III) oxidation to As(V) and an increasing proportion of organo-As forming over time. Thus periphyton plays several roles in As environmental behavior: 1) decreasing total dissolved As concentrations via abiotic and biotic accumulation, 2) rapidly oxidizing As(III) to As(V), 3) effluxing organo-As forms into solution, and 4) limiting trophic transfer to aquatic grazers.

59 BASIC BIOLOGICAL SCIENCES↗

Tunnel Junction Development Using Hydride Vapor Phase Epitaxy

We demonstrate for the first time III-V tunnel junctions grown using hydride vapor phase epitaxy (HVPE) with peak tunneling currents >8 A/cm 2 , sufficient for operation of a multijunction device to several hundred suns of concentration. Multijunction solar cells rely on tunneling interconnects between subcells to enable series connection with minimal voltage loss, but tunnel junctions have never been shown using the HVPE growth method. HVPE has recently reemerged as a low-cost growth method for high-quality III-V materials and devices, including the growth of high-efficiency III-V solar cells. We previously showed single-junction GaAs solar cells with conversion efficiencies of ~24% with a path forward to equal or exceed the practical efficiency limits of crystalline Si. Moving to a multijunction device structure will allow for even higher efficiencies with minimal impact on cost, necessitating the development of tunnel interconnects. Here in this paper, we demonstrate the performance of both isolated HVPE-grown tunnel junctions, as well as single-junction GaAs solar cell structures with a tunnel junction incorporated into the contact region. We observe no degradation in device performance compared to a structure without the added junction.

14 SOLAR ENERGY↗

Rise and fall of Mott insulating gaps in YNiO 3 paramagnets as a reflection of symmetry breaking and remaking

The YNiO 3 nickelate is a paradigm d-electron oxide that manifests the intriguing temperature-mediated sequence of three phases transitions from (i) magnetically ordered insulator to (ii) paramagnetic (PM) insulator and then to (iii) PM metal. Such phenomena raised the question of the nature of the association of magnetism and structural symmetry breaking with the appearance in (i) and (ii) and disappearance in (iii) of insulating band gaps. It is demonstrated here that first-principles mean-field–like density-functional theory (DFT), driven by molecular dynamics temperature evolution, can describe not only the origin of the magnetically long-range ordered insulating phase (i), but also the creation of an insulating paramagnet (ii) that lacks spin- long-range order, and of a metallic paramagnet (iii) as temperature rises. This approach provides the patterns of structural and magnetic symmetry breaking at different temperatures, in parallel with band gaps obtained when the evolving geometries are used as input to DFT electronic band-structure calculations. This disentangles the complex interplay among spin, charge, and orbital degrees of freedom. Analysis shows that the success in describing the rise and fall of the insulating band gaps along the phase transition sequence is enabled by allowing sufficient flexibility in describing diverse local structural and magnetic motifs as input to DFT. This entails the use of sufficiently large supercells that allow expressing structural disproportionation of octahedra, as well as a description of PM phases as a distribution of local magnetic moments (rather than using a single averaged moment). It appears that the historic dismissal of mean-field–like DFT as being unable to describe such Mott-like transitions was premature, as it was based on consideration of averaged crystallographic unit cells, a description that washes out local symmetry-breaking motifs. The magnetically ordered insulating YNiO 3 phase (i) and the PM insulating phase (ii) result in DFT from allowing symmetry breaking, evident already by considering the athermal internal energy. In contrast, the PM metallic phase (iii) is formed thermally by smearing out thus weakening symmetry breaking. Analysis of snapshots of the different forms of structural vs magnetic symmetry breaking shows that only the loss of the polymorphous distribution of magnetic moments existing in (ii) causes the fall of the band gap, resulting in the metallic state in (iii). Finally, the interesting conclusion is that such a description of the rise [in phases (i) and (ii)] and fall [in phase (iii)] of the insulating gap does not rely on the traditional Mott-like strong correlation understanding, but on breaking and remaking of magnetic and structural symmetries reflected in energy lowering.

36 MATERIALS SCIENCE↗

AlInP-passivated III–V solar cells grown by dynamic hydride vapor-phase epitaxy

We report the development of AlInP-passivated solar cells grown by dynamic hydride vapor-phase epitaxy (D-HVPE) with AM1.5G efficiencies of 26.0% for single-junction (1J) GaAs cells and 28.0% for GaInP/GaAs (2J) tandems. We compare the device performance of solar cells passivated with AlInP versus control cells passivated with GaInP, which has already enabled near-unity carrier collection in GaAs solar cells. 1J devices passivated with either AlInP or GaInP have an identical open-circuit voltage (V OC ) of 1.06 V and long-wavelength current collection near 95%, indicating that both window materials provide a similar degree of passivation. Adding AlInP passivation to each solar cell structure improves the current collection by 1.3 and 1 mA/cm 2 for the 1J and 2J, respectively. The AlInP also results in a top cell V OC boost of ~40 mV relative to a tandem device passivated only by a thin, highly doped GaInP emitter. Secondary-ion mass spectrometry measurements indicate that although O and Si both incorporate in the AlInP window, they do not appear in the subsequently grown absorber layers and do not impact its ability to passivate the front surface. We expect that these achievements, along with continued optimization, will enable parity of hydride vapor-phase epitaxy (HVPE)-grown device efficiencies with state-of-the-art devices grown by other epitaxial methods in the near future.

14 SOLAR ENERGY↗

Stellar yields of rotating first stars

First stars, also called population III stars, are born in the earliest universe without any heavy elements. These stars are the first nuclear reactor in the universe and affect their circumstances emitting synthesized materials. Not only the stellar evolution, but also their chemical yields have many distinctive characteristics. We have modeled evolution of population III stars including effect of stellar rotation. Internal mixing induced by rotation naturally results in primary nitrogen production. Evolution of rotating massive stars is followed until the core collapse phase. The new Pop III yield model will consistently explain the observed abundances of metal-poor systems.

79 ASTRONOMY AND ASTROPHYSICS↗

Efficient Conservative Reformulation Schemes for Lithium Intercalation

Porous electrode theory coupled with transport and reaction mechanisms is a widely used technique to model Li-ion batteries employing an appropriate discretization or approximation for solid phase diffusion with electrode particles. One of the major difficulties in simulating Li-ion battery models is the need to account for solid phase diffusion in a second radial dimension r, which increases the computation time/cost to a great extent. Various methods that reduce the computational cost have been introduced to treat this phenomenon, but most of them do not guarantee mass conservation. The aim of this paper is to introduce an inherently mass conserving yet computationally efficient method for solid phase diffusion based on Lobatto III A quadrature. This paper also presents coupling of the new solid phase reformulation scheme with a macro-homogeneous porous electrode theory based pseudo 20 model for Li-ion battery. (C) The Author(s) 2015. Published by ECS. All rights reserved.

Urisanga, PC↗

Calcium looping process for high purity hydrogen production integrated with capture of carbon dioxide, sulfur and halides

A process for producing hydrogen comprising the steps of: (i) gasifying a fuel into a raw synthesis gas comprising CO, hydrogen, steam, sulfur and halide contaminants in the form of H.sub.2S, COS, and HX, wherein X is a halide; (ii) passing the raw synthesis gas through a water gas shift reactor (WGSR) into which CaO and steam are injected, the CaO reacting with the shifted gas to remove CO.sub.2, sulfur and halides in a solid-phase calcium-containing product comprising CaCO.sub.3, CaS and CaX.sub.2; (iii) separating the solid-phase calcium-containing product from an enriched gaseous hydrogen product; and (iv) regenerating the CaO by calcining the solid-phase calcium-containing product at a condition selected from the group consisting of: in the presence of steam, in the presence of CO.sub.2, in the presence of synthesis gas, in the presence of H.sub.2 and O.sub.2, under partial vacuum, and combinations thereof.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗