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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Magnetism and structure of Fe- and Co-substituted Mn 2 NiSn

Mn-containing Heuslers are important magnetic shape-memory alloys for fast and precise actuators in manufacturing, robotics, surgery, and other applications. Among the key requirements are a high magnetization and favorable thermal properties, especially a high Curie temperature. In this work, the effect of Fe and Co substitution on the structure and magnetism of Mn 2 NiSn alloys is investigated. The Heusler alloys have been produced by melt spinning and characterized by X-ray diffraction, magnetometry, and electron-transport measurements. It was found that Co substitution for Mn enhances the Curie temperature of Mn 2 NiSn and both Co and Fe substitution improve its magnetization. Further, these improvements are accompanied by reduced thermal and magnetic hysteresis losses and by interesting structural changes, namely improved chemical order and site occupancies characteristic of quaternary (Y-ordered) Heuslers.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Defect evolution in Ni and NiCoCr by in situ 2.8 MeV Au irradiation

The evolution of radiation-induced defects in Ni and the single-phase concentrated solid solution alloy, NiCoCr, were investigated during in situ 2.8 MeV Au ion irradiation and post-irradiation analysis using transmission electron microscopy. Compared to Ni, both the size and area density of defect clusters decreased in NiCoCr under the same irradiation conditions, suggesting that the chemical complexity, i.e., randomness of lattice site occupations, of NiCoCr suppressed radiation-induced damage. One-dimensional glide of defect clusters was observed in Ni but not in the NiCoCr alloy. The structural nature of small defect clusters in NiCoCr were further investigated using high-angle annular dark field scanning transmission electron microscopy.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Density functional theory calculations of the mixing enthalpy of ternary uranium carbide compounds

The high melting point of uranium-zirconium carbides (U,Zr)C makes them an ideal fuel for nuclear thermal propulsion (NTP) reactors. Gaps remain in the current understanding of the U-Zr-C system due to the difficulty of conducting thermodynamic experiments at NTP operation conditions. Density functional theory calculations using the Hubbard U model (DFT+U) were performed using orbital matrix occupation (OMC) to obtain the mixing enthalpy for UC and ZrC for (U,Zr)C ternary compounds. Similarly, DFT+U calculations were also carried out for the (U,Nb)C and (U,Ta)C systems. In conclusion, the DFT results are envisioned to be used in thermodynamic assessments of the uranium carbide systems based on the CALPHAD approach to supplement the lack of experimental data for the mixing thermodynamics.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Model predictive control of heating, ventilation, and air conditioning (HVAC) systems: A state-of-the-art review

Due to the fast advancement of communication and information technology, intelligent buildings have garnered great interest. These buildings can forecast weather, ambient temperature, and sun irradiation and can modify heating, ventilation, and air conditioning (HVAC) operations appropriately, based on current and previous data. This change is intended to reduce HVAC system energy usage while maintaining an appropriate degree of thermal comfort and indoor air quality. Since its inception, model predictive control (MPC) has been one of the prospective solutions for HVAC management systems to reduce both costs and energy usage. Additionally, MPC is becoming increasingly practical as the processing capacity of building automation systems increases and a large quantity of monitored building data becomes available. MPC also provides the potential to improve the energy efficiency of HVAC systems via its capacity to consider limitations, to predict disruptions, and to factor in multiple competing goals such as interior thermal comfort and building energy consumption. Although substantial research has been conducted on MPC in building HVAC systems, there is a shortage of critical reviews and a lack of a comprehensive framework that formulates and defines the applications. Here, this article provides a comprehensive state-of-the-art overview of MPC in HVAC systems. Detailed discussions of modeling approaches and optimization algorithms are included. Numerous design aspects such as prediction horizon, occupancy behavior, building type, and cost function, that impact MPC performance are discussed in detail. The technical characteristics, advantages, and disadvantages of various types of modeling software are discussed. The primary objective of this work is to highlight critical design characteristics for the MPC control scheme and to give improved suggestions for future research. Moreover, numerous prospective scenarios have been suggested that might provide future research direction.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2023

JUST-R metrics for considering energy justice in early-stage energy research

We report achieving sustainable decarbonization of the energy sector requires implementing and improving energy technologies while simultaneously managing sources of social inequity in the energy system. Centering energy justice, which has "the goal of achieving equity in both the social and economic participation in the energy system, while also remediating social, economic, and health burdens on those historically harmed by the energy system," in the transition to clean energy has become an increasingly urgent priority for social scientists, policymakers, and community activists alike. However, late-stage consideration of social impacts of energy technologies may result in identifying inequities only after substantial time, money, and effort have been expended on research and development (R&D). This issue is exemplified by concerns over environmental and human health impacts related to cobalt in lithium-ion batteries, which has spurred research into alternatives only after decades of R&D and the establishment of supply chains, infrastructure, and markets for cobalt-containing chemistries. Other examples include issues with land use and resource consumption related to first-generation biofuel feedstocks as well as occupational hazards and pollution associated with photovoltaics manufacturing. In all these cases, subsequent R&D to improve technologies or processes cannot undo the effects already experienced. Incorporating energy justice from the earliest stage of R&D will enable more just technology implementation, but integrating justice considerations into early-stage research is a challenge due to a lack of tools to assess and manage them. To fill this gap, we center early-stage research to develop the Justice Underpinning Science and Technology Research (JUST-R) metrics framework - energy justice metrics specifically targeted at early-stage researchers to assess their work on an immediate timescale. By applying these metrics to a case study focused on materials for next-generation photovoltaics, we highlight potential benefits and barriers to implementing this framework in early-stage research and discuss necessary institutional and individual actions needed for researchers to effectively leverage the tool to incorporate justice-focused criteria into R&D decision making.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2014

Pulsed sonication for alumina coatings on high-capacity oxides: Performance in lithium-ion cells

High-capacity xLi2MnO3•(1-x)LiMO2 (M=Ni, Mn, Co) oxides show relatively rapid performance degradation when cycled at voltages >4.5V vs. Li/Li+. Previous research has indicated that modifying the oxide surfaces with coatings, such as alumina, reduces cell impedance rise and improves capacity retention. In this article, we demonstrate pulsed-sonication as a rapid and effective approach for coating alumina on Li1.2Ni0.175Mn0.525Co0.1O2 (0.5Li2MnO3•0.5LiNi0.44Mn0.31Co0.25O2) particles. Oxide integrity and morphology is maintained after the sonochemical process and subsequent heat-treatment. Energy dispersive spectroscopy (EDS) X-ray elemental maps show uniform coating of all secondary particles. 27Al Magic Angle Spinning (MAS) NMR data confirm the presence of alumina and mainly indicate octahedral aluminum occupancy in a six-coordinate environment with oxygen. Full cells containing electrodes with the alumina-coated particles demonstrate lower initial impedance rise and better capacity retention during extended cycling to high voltages. However, the coating has a negligible effect on the voltage hysteresis and voltage fade behavior displayed by these oxides. The various data indicate that the pulsed sonochemical technique is a viable approach for coating oxide particles. The methodology described herein can easily be extended beyond alumina to include coatings such as AlF3, MgO, and MgF2.

1H NMR↗
DOE OSTI2020

Cloud-based implementation of white-box model predictive control for a GEOTABS office building: A field test demonstration

Model predictive control (MPC) has been proven in simulations and pilot case studies to be a superior control strategy for large buildings. MPC can utilize the weather and occupancy schedule forecasts, together with the system model, to predict the future thermal behavior of the building and minimize the overall energy use and maximize thermal comfort. However, these advantages come with the cost of increased modeling effort, computational demands, communication infrastructure, and commissioning efforts. Thus a typical approach is to, often rapidly, simplify the building modeling and MPC optimization problem while paying a price of not reaching the full performance potential. It has been shown that by employing accurate physics-based models, MPC performance can be notably increased closer to its theoretical performance bound. However, implementation of such high-fidelity MPC in real buildings remains a challenge, resulting in a lack of successful field test studies. This work presents the methodology and field test demonstration of a computationally efficient implementation of the white-box MPC in an office building in Belgium. The detailed model of the building is based on first-principle physical equations. The deployment and supervision of MPC operation in a practical setting are supported by an automated cloud-based communication infrastructure. The motivating factor behind the cloud-based architecture is its compatibility with a commercially appealing control as a service concept. The building is equipped with a ground source heat pump (GSHP) and thermally activated building structures (TABS), where the combination of both is also known as GEOTABS. From a control perspective, GEOTABS buildings are particularly challenging systems due to large scale, complex heating, ventilation and air conditioning (HVAC) system, and slow dynamics with time delays. On the other hand, there is an increased potential for energy savings due to the high thermal mass, which acts as thermal storage. The MPC operation is demonstrated during the challenging transient seasons (switching between heating and cooling), and its performance is compared to a traditional rule-based controller (RBC). We provide a proof of concept of real MPC operation for the most difficult seasons with notable GSHP energy use savings equal to 53.5% and thermal comfort improvement by 36.9%. Other MPC applications found in the literature describe tests for only cooling or only heating, and up to now only for a black-box or a grey-box approach.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2017

Crystal structures reveal a new and novel FoxO1 binding site within the human glucose-6-phosphatase catalytic subunit 1 gene promoter

Human glucose-6-phosphatase plays a vital role in blood glucose homeostasis and holds promise as a therapeutic target for diabetes. Expression of its catalytic subunit gene 1 (G6PC1) is tightly regulated by metabolic-response transcription factors such as FoxO1 and CREB. Although at least three potential FoxO1 binding sites (insulin response elements, IREs) and one CREB binding site (cAMP response element, CRE) within the proximal region of the G6PC1 promoter have been identified, the interplay between FoxO1 and CREB and between FoxO1 bound at multiple IREs has not been well characterized. Here we present the crystal structures of the FoxO1 DNA binding domain in complex with the G6PC1 promoter. Here, these complexes reveal the presence of a new non-consensus FoxO1 binding site that overlaps the CRE, suggesting a mutual exclusion mechanism for FoxO1 and CREB binding at the G6PC1 promoter. Additional findings include (i) non-canonical FoxO1 recognition sites, (ii) incomplete FoxO1 occupancies at the available IRE sites, and (iii) FoxO1 dimeric interactions that may play a role in stabilizing DNA looping. These findings provide insight into the regulation of G6PC1 gene transcription by FoxO1, and demonstrate a high versatility of target gene recognition by FoxO1 that correlates with its diverse roles in biology.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2012

The T2 phase in the Nb-Si-B system studied by ab initio calculations and synchrotron X-ray diffraction

The solid solution based on Nb{sub 5}Si{sub 3} (Cr{sub 5}B{sub 3} structure type, D8{sub l}, tI32, I4/mcm, No140, a=6.5767 A, c=11.8967 A) in the Nb-Si-B system was studied from the structural and thermodynamic point of view both experimentally and by ab initio calculations. Rietveld refinement of powder X-ray synchrotron data allowed to determine the boron to silicon substitution mechanism and the structural parameters. Ab initio calculations of different ordered compounds and selected disordered alloys allowed to obtain in addition to the enthalpy of formation of the solution, substitution mechanism and structural parameters which are in excellent agreement with the experimental data. The stability of the phase is discussed. - Graphial abstract: Valence-charge electron localization function in the z=0 plane of the D8{sub l} structure for the ordered compound Nb{sub 5}SiB{sub 2}. Highlights: Black-Right-Pointing-Pointer Coupling between ab initio data and experimental results from synchrotron powder diffraction. Black-Right-Pointing-Pointer Excellent agreement between the two techniques for the site occupancies and internal coordinates. Black-Right-Pointing-Pointer Explanation of the phase stability up to Nb{sub 5}SiB{sub 2}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

NaCu(Ta{sub 1-y}Nb{sub y}){sub 4}O{sub 11} solid solution: A tunable band gap spanning the visible-light wavelengths

The new solid-solution NaCu(Ta{sub 1-y}Nb{sub y}){sub 4}O{sub 11} (0{<=}y{<=}0.7) was synthesized by solid-state methods in the form of bulk powders that ranged from light-yellow to brown colored and were characterized by powder X-ray diffraction techniques (Space group R-3c (no. 167); Z=6; a=6.214(1)-6.218(1) Angstrom-Sign and c=36.86(1)-36.94(1) Angstrom-Sign ). Full-profile Rietveld refinements confirmed a site-differentiated ordering of the Cu(I) and Na cations, i.e., occupying the 12c (linear environment) and 18d (seven-coordinate environment) crystallographic sites respectively. Conversely, a statistical mixture of Ta(V) and Nb(V) cations occurred over the 6b (octahedral environment) or the 18e (pentagonal-bipyramidal environment) crystallographic sites, without any preferential segregation. The UV-Vis diffuse reflectance spectra showed a significant red-shift of the optical bandgap size (indirect) from {approx}2.70 eV to {approx}1.80 eV across the solid solution with increasing Nb(V) content. Electronic-structure calculations using the tight-binding linear-muffin-tin-orbital approach showed that the reduction in bandgap size arises from the introduction of the lower-energy Nb 4d{sup 0} orbitals into the conduction band and consequently a lower energy of the conduction band edge. The lowest-energy bandgap transitions were found to be derived from electronic transitions between the filled Cu(I) and the empty Nb(V) d-orbitals, with a small amount of mixing with the O 2p orbitals. The resulting conduction and valence band energies are found to approximately bracket the redox potentials for water reduction and oxidation, and meeting the thermodynamic requirements for photocatalytic water-splitting reactions. - Graphical Abstract: The NaCu(Ta{sub 1-y}Nb{sub y}){sub 4}O{sub 11} (0{<=}y{<=}0.7) solid solution shows a statistical occupancy of the Ta(V) and Nb(V) cations in both octahedral and pentagonal bipyramidal environments. An increasing Nb(V) content also causes a significant red-shift of the bandgap size from {approx}2.70 eV to {approx}1.80 eV. Highlights: Black-Right-Pointing-Pointer Double solid-solution of M(I) (=Cu, Na) and M(V) (=Nb, Ta) crystallographic sites. Black-Right-Pointing-Pointer Increasing Nb content leads to tunable bandgap size from {approx}2.70 eV to {approx}1.80 eV across the solid solution. Black-Right-Pointing-Pointer Layers of MO{sub 7} (M=Ta, Nb) pentagonal bipyramids and isolated MO{sub 6} octahedra.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

The effect of doping on global lattice properties of magnetite Fe{sub 3-x}Me{sub x}O{sub 4} (Me=Zn, Ti and Al)

X-ray powder diffraction was measured in Fe{sub 3-x}Me{sub x}O{sub 4} (Me=Zn, Ti, Al; x<0.065), in T range 70-300 K to see the effect of different doping on global lattice properties. The experimental results have shown that some lattice properties (e.g., the cell volume) are dopand specific. This can be attributed to the difference in preferential sites occupation by dopants. As confirmed by EXAFS, Zn enters tetrahedral, while Ti octahedral lattice sites, differently affecting crucial octahedral iron positions in the spinel lattice. However, despite this fact, it was found that T dependence of both monoclinic angle and lattice parameters is universal for studied samples above and below the Verwey transition temperature T{sub V}. So, not the iron atoms in octahedral positions individually, but interactions between them are responsible for the Verwey transition character change with doping. - Graphical abstract: A low temperature magnetite cell volume vs. dopants content. Apparently, Zn, Ti and Al atoms have different effect on the global lattice properties at individual temperatures. However, the Verwey transition reacts to dopants in a similar manner, despite the different way the octahedral iron positions are affected. Highlights: Black-Right-Pointing-Pointer We measure powder diffraction and EXAFS on Fe{sub 3-x}Me{sub x}O{sub 4}, Me=Zn, Ti, Al (x<0.065), in T range 70-300 K. Black-Right-Pointing-Pointer XRD: atom-type independent changes of lattice parameters with T. Black-Right-Pointing-Pointer EXAFS: Zn replaces Fe on tetrahedral positions, Ti on octahedral positions. Black-Right-Pointing-Pointer Thus, some secondary interactions between ordering orbitals, not the primary one driving the Verwey transition, control the transition order.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

The crystal structure of aluminum doped {beta}-rhombohedral boron

A crystal structure of aluminum doped {beta}-rhombohedral boron was studied by single-crystal X-ray diffraction at 80 K. The crystals were synthesized using high-pressure high temperature technique at 3 GPa and 2100 K. The structure is based on three-dimensional framework made of B{sub 12} icosahedra with voids occupied by the B{sub 28}-B-B{sub 28} units, it has the R-3m space group with a=10.9014(3), c=23.7225(7) A lattice dimensions in hexagonal setting. Aluminum atoms are located in A1 and D special positions of the {beta}-B structure with occupancies of 82.7(6)% and 11.3(4)%, respectively. Additional boron atoms are located near the D-site. Their possible distribution is discussed. Finally we have found two appropriate structural models whose refinement suggests two possible chemical compositions, AlB{sub 44.8(5)} and AlB{sub 37.8(5)}, which are in a good agreement with the chemical analysis data obtained from EDX. The crystal structure of AlB{sub 44.8(5)} is described in detail. - Graphical abstract: The atomic distribution near the B(15) atom (non-labeled atom in the center of the picture) shown along the c axis. Anisotropic displacement ellipses for Al(2) (D-site) and B(15) are shown with 50 % probability level. The mirror plane with Miller indices (1 1 0) and related to it (-1 2 0) and (-2 1 0) generated by the 3-fold rotation-inversion axis parallel to the c axis splits the position of B(16) over two sites. Highlights: Black-Right-Pointing-Pointer The crystal structure of the AlB{sub 44.8(5)} has been refined. Black-Right-Pointing-Pointer Aluminum atoms partially fill certain types of voids (the A1- and D-sites). Black-Right-Pointing-Pointer We have got two possible models of atomic distribution near the D-site.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Phase relations and crystal structures in the system Ce-Ni-Zn at 800 Degree-Sign C

Phase relations have been established for the system Ce-Ni-Zn in the isothermal section at 800 Degree-Sign C using electron microprobe analysis and X-ray powder diffraction. Phase equilibria at 800 Degree-Sign C are characterized by a large region for the liquid phase covering most of the Ce-rich part of the diagram, whereas a Zn-rich liquid is confined to a small region near the Zn-corner of the Gibbs triangle. Whereas solubility of Ce in the binary Ni-Zn phases is negligible, mutual solubilities of Ni and Zn at a constant Ce content are large at 800 Degree-Sign C for most Ce-Zn and Ce-Ni compounds. The solid solution Ce(Ni{sub 1-x}Zn{sub x}){sub 5} with the CaCu{sub 5}-type is continuous throughout the entire section and for the full temperature region from 400 to 800 Degree-Sign C. Substitution of Zn by Ni is found to stabilize the structure of CeZn{sub 11} to higher temperatures. At 800 Degree-Sign C Ce(Ni{sub x}Zn{sub 1-x}){sub 11} (0.03{<=}x{<=}0.22) appears as a ternary solution phase. Similarly, a rather extended solution forms for Ce{sub 2}(Ni{sub x}Zn{sub 1-x}){sub 17} (0{<=}x{<=}0.53). Detailed data on atom site occupation and atom parameters were derived from X-ray structure analyses for single crystals of Ce{sub 2+y}(Ni{sub x}Zn{sub 1-x}){sub 17}, y=0.02, x=0.49 (a=0.87541(3), c=1.25410(4) nm; Th{sub 2}Zn{sub 17} type with space group R3{sup Macron }m,R{sub F{sup 2}}=0.018) and Ce(Ni{sub 0.18}Zn{sub 0.82}){sub 11} (a=1.04302(2), c=0.67624(3)nm, BaCd{sub 11} type with space group I4{sub 1}/amd, R{sub F{sup 2}}=0.049). - Graphical abstract: Ce-Ni-Zn isothermal section at 800 Degree-Sign C. Highlights: Black-Right-Pointing-Pointer Phase relations were determined for the system Ce-Ni-Zn in the section at 800 Degree-Sign C. Black-Right-Pointing-Pointer A continuous solid solution Ce(Ni{sub 1-x}Zn{sub x}){sub 5}, 0{<=}x{<=}1, forms between 400 and 800 Degree-Sign C. Black-Right-Pointing-Pointer Zn/Ni substitution stabilizes the ternary phase Ce(Zn{sub 1-x}Ni{sub x}){sub 11}, 0.03{<=}x{<=}0.22, 800 Degree-Sign C. Black-Right-Pointing-Pointer An extended solution forms for Ce{sub 2}(Ni{sub x}Zn{sub 1-x}){sub 17} (0{<=}x{<=}0.53). Black-Right-Pointing-Pointer Crystal data are given: Ce{sub 2+y}(Ni{sub x}Zn{sub 1-x}){sub 17} (Th{sub 2}Zn{sub 17}), Ce(Ni{sub 0.18}Zn{sub 0.82}){sub 11} (BaCd{sub 11}).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Manganese valence and coordination structure in Mn,Mg-codoped {gamma}-AlON green phosphor

The valence and coordination structure of manganese in a Mn,Mg-codoped {gamma}-AlON spinel-type oxynitride green phosphor were studied by synchrotron X-ray diffraction and absorption fine structure measurements. The absorption edge position of the XANES revealed the bivalency of Mn. Two cation sites are available in the spinel structure for cation doping: a tetrahedral site and an octahedral site. The pre-edge of the XANES and the distance to the nearest neighbor atoms obtained from the EXAFS measurement showed that Mn was situated at the tetrahedral site. Rietveld analysis showed that the vacancy occupied the octahedral site. The preferential occupation of the tetrahedral site by Mn and the roles of N and Mg are discussed in relation to the spinel crystal structure. - Graphical Abstract: Fourier transform of EXAFS of Mn K-edge for Mn,Mg-codoped green phosphor and Mn coordination structure. Highlights: Black-Right-Pointing-Pointer Mn, Mg-codoped {gamma}-AlON green phosphor for white LED. Black-Right-Pointing-Pointer The valence of Mn is divalent. Black-Right-Pointing-Pointer Mn occupies the tetrahedral site in the spinel structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Synthesis and crystal structure of Mg{sub 0.5}NbO{sub 2}: An ion-exchange reaction with Mg{sup 2+} between trigonal [NbO{sub 2}]{sup -} layers

A new layered niobate, Mg{sub 0.5}NbO{sub 2}, was synthesized from LiNbO{sub 2} through a cation-exchange reaction with Mg{sup 2+} at 450-550 Degree-Sign C. This is the first example of a topotactic reaction with an aliovalent cation between trigonal [NbO{sub 2}]{sup -} layers. It is proposed to be isostructural with LiNbO{sub 2} (space group; P6{sub 3}/mmc) with lattice parameters of a=2.9052(6) A, c=10.625(15) A. The lattice parameters and formation energy of Mg{sub 0.5}NbO{sub 2} crystallized in LiNbO{sub 2} form and other layered CaNb{sub 2}O{sub 4} one were calculated by density functional theory. - Graphical abstract: A new layered niobate, Mg{sub 0.5}NbO{sub 2}, was synthesized from LiNbO{sub 2} through a cation-exchange reaction with Mg{sup 2+} at 450-550 Degree-Sign C. It is isostructural with LiNbO{sub 2} with lattice parameters of a=2.9052(6) A, c=10.625(15) A. Mg{sup 2+} are described in spheres located between [NbO{sub 2}]{sup -} trigonal layers and its occupancy is 0.5. Highlights: Black-Right-Pointing-Pointer A new layered niobate, Mg{sub 0.5}NbO{sub 2}, was synthesized from LiNbO{sub 2}. Black-Right-Pointing-Pointer Cation-exchange reaction converted two monovalent Li{sup +} into one divalent Mg{sup 2+} at 450-550 Degree-Sign C. Black-Right-Pointing-Pointer Mg{sub 0.5}NbO{sub 2} was isostructural with LiNbO{sub 2} (space group; P6{sub 3}/mmc). Black-Right-Pointing-Pointer Its lattice parameters were a=2.9052(6) A and c=10.625(15) A. Black-Right-Pointing-Pointer Synthesized Mg{sub 0.5}NbO{sub 2} was calculated to be thermodynamically more favorable.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Structure refinements of members in the brownmillerite solid solution series Ca{sub 2}Al{sub x}(Fe{sub 0.5}Mn{sub 0.5}){sub 2-x}O{sub 5+{delta}} with 1/2{<=}x{<=}4/3

Four different brownmillerite solid solutions Ca{sub 2}Al{sub x}(Fe{sub 0.5}Mn{sub 0.5}){sub 2-x}O{sub 5+{delta}} with 1/2{<=}x{<=}4/3 were synthesized by a solid oxide ceramic method. The phases crystallize either in a primitive centered orthorhombic cell with space group Pnma or in a body centered cell with space group I2mb dependent on the aluminum concentration present in the solid solution. Mn{sup 3+} ions occupy exclusively site 4a coordinated by six oxygen anions. Increasing Mn{sup 3+} concentrations cause a remarkable distortion of the octahedron and indirectly of the tetrahedron, resulting in twisted and tilted octahedral layers as well as buckled tetrahedral chains. The influences are discussed on the site 4a of trivalent manganese due to its Jahn-Teller activity, with regard to the occupation of octahedron and tetrahedron with different sized iron and aluminum ions. - Graphical Abstract: The coupled substitution Fe{sup 3+}>Mn{sup 3+}+Fe{sup 3+} <=>2 Al{sup 3+} in brownmillerite phases (Ca{sub 2}(Fe{sub 0.5}Mn{sub 0.5}){sub 2-x}Al{sub x}O{sub 5+{delta}}) changes predominantly their structural properties, which is essential for the hydration performance of the calcium aluminate cement, where brownmillerites occur as clinker phases. Highlights: Black-Right-Pointing-Pointer We present structural data of four Ca-Al-Fe-Mn-brownmillerites. Black-Right-Pointing-Pointer Mn{sup 3+}-ions occupy exclusively the octahedrally coordinated site 0,0,0. Black-Right-Pointing-Pointer Bonds and angles of the octahedrally coordinated site are distorted strongly. Black-Right-Pointing-Pointer Mn{sup 3+}-ions influence indirectly the shape of the tetrahedron. Black-Right-Pointing-Pointer Mn{sup 3+}-ions stabilize Pnma instead of I2mb in Ca-Al-Fe-Mn-brownmillerites.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Crystal structure, morphotropic phase transition and luminescence in the new cyclosilicates Sr{sub 3}R{sub 2}(Si{sub 3}O{sub 9}){sub 2}, R=Y, Eu-Lu

A new series of promising luminescent materials, cyclosilicates Sr{sub 3}R{sub 2}(Si{sub 3}O{sub 9}){sub 2}, R=Y, Eu-Lu, has been synthesized via a solid-state reaction. X-ray and neutron powder diffraction studies show that these oxides crystallize in the monoclinic crystal system (S.G. C2/c, Z=4) and have a morphotropic phase transition between Er and Tm compounds followed by a step-like change of the unit cell constants. Isolated [Si{sub 3}O{sub 9}] rings located in layers are basic building units and stack with Sr/R layers along the [1 0 1{sup Macron }] direction. The rare earth atoms are distributed among three independent Sr/R sites coordinated by 8, 7 and 6 oxygen atoms, and the Sr-R populations change from mixed to 0.5/0.5 over site (1) and full occupation of sites (2) and (3) by Sr and R, respectively, at the transition. Changes of the conformation and mutual arrangement of [Si{sub 3}O{sub 9}] rings, as well as exchange of oxygen atoms from the first and the second coordination sphere of two Sr/R sites also feature the phase transition. Luminescence in Sr{sub 3}Y{sub 2}(Si{sub 3}O{sub 9}){sub 2}:Eu{sup 3+} under ultraviolet (UV) excitation has been discussed. - Graphical abstract: The change of the [Si{sub 3}O{sub 9}] ring conformation in Sr{sub 3}R{sub 2}(Si{sub 3}O{sub 9}){sub 2}, R=Eu, Er, Tm and Lu. Highlights: Black-Right-Pointing-Pointer A new group of cyclosilicates Sr{sub 3}R{sub 2}(Si{sub 3}O{sub 9}){sub 2}, R=Y, Eu-Lu, was first synthesized. Black-Right-Pointing-Pointer Isolated [Si{sub 3}O{sub 9}] rings located in layers are basic building units and stack with Sr/R layers along the [1 0 1{sup Macron }] direction. Black-Right-Pointing-Pointer The rare earth atoms are distributed among three independent Sr/R sites coordinated by 6, 7 and 8 oxygen ligands. Black-Right-Pointing-Pointer A step-like change of the unit cell parameters is observed in the Sr{sub 3}R{sub 2}(Si{sub 3}O{sub 9}){sub 2} structure for R=Er{yields}Tm. Black-Right-Pointing-Pointer Sr{sub 3}Y{sub 2}(Si{sub 3}O{sub 9}){sub 2}:Eu{sup 3+} demonstrates intense multiband orange-red photoluminescence.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Controlling structure distortions in 3-layer ferroelectric Aurivillius oxides

Combined Rietveld refinements of x-ray and neutron powder diffraction data were used to understand the subtle structure distortions in 3-layer Aurivillius oxides that yield off-centering displacements in ferroelectric and multiferroic compositions. Ferroelectric phases including Bi{sub 2}A{sub 2}Ti{sub 3}O{sub 12} (A=La, Pr, Nd, La/Pr, La/Nd, Pr/Nd), Bi{sub 2}A{sub 2}TiNb{sub 2}O{sub 12} (A=Ca/Sr, Sr, and Sr/Ba) and Bi{sub 2}A{sub 2}TiTa{sub 2}O{sub 12} (A=Ca/Sr, and Sr/Ba) were studied to separate the effects of cation size and charge on the structure distortions and properties. A new approach to describing the local coordination around the Ti, Nb, and/or Ta ions is presented, where the oxygen octahedra are characterized as containing kinks in three dimensions. The kink angles follow trends with the A-site ionic radius and the ferroelectric polarization. The driving force for extensive cation site mixing between the Bi and A-site cations has been clearly established, with site mixing required to maintain interlayer bonding. - Graphical abstract: Distortion of the oxygen octahedra from planar geometries can be controlled via choice of the perovskite A-site cation, and the kink angle correlates with cation off-centering and ferroelectric polarization. Highlights: Black-Right-Pointing-Pointer A-site cations define the tilt and distortion of the octahedral. Black-Right-Pointing-Pointer Distortions of oxygen octahedra, ignoring the central cation, link to ferroelectric polarization. Black-Right-Pointing-Pointer Bi ion occupancy in the perovskite causes distortion of the oxygen sublattice. Black-Right-Pointing-Pointer We predict multiferroic behavior from off-centering caused by the Bi ion lone pair.

36 MATERIALS SCIENCE↗