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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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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Electronic Structure, Lattice Dynamics, and Superconducting Properties of Mercury-Alkaline Earth Metal Compounds: a First-Principles Study

The electronic structure, lattice dynamics, and superconducting properties of SrHg and BaHg intermetallic compounds are investigated using plane wave pseudo-potential and linear response methods based on density functional theory. The ground state properties such as lattice parameters are in good agreement with previously reported results. The positive phonon frequencies reveal the stability of both compounds in B{sub 2} (CsCl-type) structure. The metallic nature of SrHg and BaHg is confirmed by the electronic band structure as well as phonon dispersion curves. The superconducting behavior described in terms of Eliashberg spectral function (α{sup 2}F(ω)) and electron-phonon coupling constant (λ). The calculated values of superconducting transition temperatures (T{sub c}) show good agreement with available experimental data.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Structures and Heats of Formation of Simple Alkaline Earth Metal Compounds II: Fluorides, Chlorides, Oxides, and Hydroxides for Ba, Sr, and Ra

Here, geometry parameters, vibrational frequencies, heats of formation, bond dissociation energies, cohesive energies, and selected fluoride affinities (difluorides) are predicted for the late alkaline earth (Sr, Ba and Ra) oxides, fluorides, chlorides, and hydroxides at the coupled cluster theory [CCSD(T)] level. Additional corrections (scalar relativistic and pseudopotential corrections, vibrational zero-point energies, and atomic spin-orbit effects) were included to accurately calculate the total atomization energies and heats of formation following the Feller-Peterson-Dixon methodology. The calculated values are compared to the experimental data where available. In some cases, especially for Ra compounds, there are no experimental results or the experimental energetics and geometries are not reliable or have very large error bars. All of the Sr, Ba and Ra difluorides, dichlorides and dihydroxides are bent structures with the OMO bond angles decreasing going down the group. The cohesive energy of bulk Be dihalides are predicted to be quite low while those of Ra are relatively large. The fluoride affinities show that the difluorides are moderately strong Lewis acids and that such trifluorides may form under the appropriate experimental conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Ultrasound nondestructive characterization of transparent spinel

Ceramic materials have attractive attributes for applications that experience high stresses or strain rates. Compared to metal-based systems, ceramics offer a lower areal density which reduces weight, but do not depreciate the integrity of other properties. The ability to tailor the microstructure of ceramics used in armor systems is a common way to increase specific mechanical properties or obtain certain material characteristics. Properties such as elastic modulus, hardness, and density are those that are typically desired to be enhanced. By modifying the microstructure one can obtain a ceramic with these enhanced properties as well as high optical transmission across a wide range of the electromagnetic spectrum. The testing of these properties and ballistic performance is usually destructive, expensive, and time consuming. Common assessments using ultrasonic NDE usually include spatially locating large flaws, sonic velocity measurements, and elastic property measurements. The use of acoustic spectroscopy to go beyond typical ultrasonic NDE in structural ceramics and allow for the use of a microstructural characterization tool is investigated in this paper. Ultrasound absorption by lithium fluoride precipitates in aluminate spinel (MgAl{sub 2}O{sub 4}) present as defined spectral peaks. Average heterogeneity size determination in magnesium aluminate spinel MgAl{sub 2}O{sub 4} by method of acoustic spectroscopy is shown.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Comparison of different procedures to stabilize biogas formation after process failure in a thermophilic waste digestion system: Influence of aggregate formation on process stability

Highlights: Black-Right-Pointing-Pointer Mechanism of process recovery with calcium oxide. Black-Right-Pointing-Pointer Formation of insoluble calcium salts with long chain fatty acids and phosphate. Black-Right-Pointing-Pointer Adsorption of VFAs by the precipitates resulting in the formation of aggregates. Black-Right-Pointing-Pointer Acid uptake and phosphate release by the phosphate-accumulating organisms. Black-Right-Pointing-Pointer Microbial degradation of volatile fatty acids in the aggregates. - Abstract: Following a process failure in a full-scale biogas reactor, different counter measures were undertaken to stabilize the process of biogas formation, including the reduction of the organic loading rate, the addition of sodium hydroxide (NaOH), and the introduction of calcium oxide (CaO). Corresponding to the results of the process recovery in the full-scale digester, laboratory experiments showed that CaO was more capable of stabilizing the process than NaOH. While both additives were able to raise the pH to a neutral milieu (pH > 7.0), the formation of aggregates was observed particularly when CaO was used as the additive. Scanning electron microscopy investigations revealed calcium phosphate compounds in the core of the aggregates. Phosphate seemed to be released by phosphorus-accumulating organisms, when volatile fatty acids accumulated. The calcium, which was charged by the CaO addition, formed insoluble salts with long chain fatty acids, and caused the precipitation of calcium phosphate compounds. These aggregates were surrounded by a white layer of carbon rich organic matter, probably consisting of volatile fatty acids. Thus, during the process recovery with CaO, the decrease in the amount of accumulated acids in the liquid phase was likely enabled by (1) the formation of insoluble calcium salts with long chain fatty acids, (2) the adsorption of volatile fatty acids by the precipitates, (3) the acid uptake by phosphorus-accumulating organisms and (4) the degradation of volatile fatty acids in the aggregates. Furthermore, this mechanism enabled a stable process performance after re-activation of biogas production. In contrast, during the counter measure with NaOH aggregate formation was only minor resulting in a rapid process failure subsequent the increase of the organic loading rate.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2011

Sintering Effects on Morphology, Thermal Stability and Surface Area of Sol-Gel Derived Nano-Hydroxyapatite Powder

Hydroxyapatite (HAP) ceramics have been recognized as substitute materials for bone and teeth in orthopedic and dentistry field due to their chemical and biological similarity to human hard tissue. The nanosized and nanocrystalline forms of HAP have great potential to revolutionize the hard tissue-engineering field, starting from bone repair and augmentation to controlled drug delivery systems. This paper reports the synthesis of biomimetic nano-hydroxyapatite (HAP) by sol-gel method using calcium nitrate tetrahydrate (CNT) and potassium dihydrogen phosphate (KDP) as calcium and phosphorus precursors, respectively to obtain a desired Ca/P ratio of 1.67. Deionized water was used as a diluting media for HAP sol preparation and ammonia was used to adjust the pH to 11. After aging, the HAP gel was dried at 55 deg. C and sintered to different temperatures (200 deg. C, 400 deg. C, 600 deg. C, 800 deg. C, 1000 deg. C and 1200 deg. C). The dried and sintered powders were characterized for phase composition using Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD). The particle size and morphology was studied using transmission electron microscopy (TEM). The thermal behavior of the dried HAP nanopowder was studied in the temperature range of 55 deg. C to 1000 deg. C using thermal gravimetric analyser (TGA). The BET surface area of absorbance was determined by Nitrogen adsorption using Brunauer-Emmett-Teller (BET) method. The presence of characteristic peaks of the phosphate and OH groups in FTIR spectrums confirmed the formation of pure HAP in dried as well as sintered powders. XRD results also confirmed the formation of stoichiometric nano-HAP. Sintering revealed that with increase in temperature, both the crystallinity and crystallite size of nano-HAP particles increased. The synthesized nano-HAP powder was found to be stable upto 1000 deg. C without any additional phase other than HAP, whereas peak of {beta}-TCP (tricalcium phosphate) was observed at 1200 deg. C. Photomicrograph of TEM showed that the nanopowder sintered at 600 deg. C is composed of hydroxyapatite nanoparticles (26.0-45.6 nm), which is well in agreement with the crystallite size calculated using XRD data. TGA study showed the thermal stability of the synthesized nano-HAP powder. The BET surface area decreased with increase in sintering temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2010

Solvothermal synthesis of designed nonstoichiometric strontium titanate for efficient visible-light photocatalysis

SrTiO{sub 3} powders with various Sr/Ti atomic ratios were synthesized by microwave-assisted solvothermal reactions of SrCl{sub 2} and Ti(OC{sub 3}H{sub 7}){sub 4} in KOH aqueous solutions. The nanoparticles of perovskite type SrTiO{sub 3} structure with the particle size of 30-40 nm were synthesized. The photocatalytic activity was determined by deNO{sub x} ability using light emitting diode lamps of various wavelengths such as 627 nm (red), 530 nm (green), 445 nm (blue), and 390 nm (UV). The photocatalytic activity significantly changed depending on the Sr/Ti atomic ratio, i.e., the strontium rich sample (Sr/Ti atomic ratio>1) showed excellent visible light responsive photocatalytic activity for the oxidative destruction of NO.

36 MATERIALS SCIENCE↗
DOE OSTI2010

Chemical model for cement-based materials: Thermodynamic data assessment for phases other than C-S-H

In the context of waste confinement, concrete may be used both as a confinement and as a building material. Concerning radwaste, the heat released during radioactive decay will modify the equilibrium constants of the minerals forming the concrete. The present work aims to elucidate the temperature dependency of the thermodynamic functions related to minerals from the concrete or associated with some of its degradation products. A large set of experimental data has been collected, for the chemical systems SO{sub 3}-Al{sub 2}O{sub 3}-CaO-CO{sub 2}-Cl-H{sub 2}O and SiO{sub 2}-Al{sub 2}O{sub 3}-CaO-H{sub 2}O, including iron and magnesium bearing phases. Most of the data collected concern experiments in aqueous media but results from calorimetric studies were also included, when available. Based on selected thermodynamic properties for each phase, predominance diagrams were drawn for the chemical elements listed above. Phase relations reported into predominance diagram appear rather consistent with most of the literature results. The case of katoite has been especially discussed, because it shows inconsistencies with respect to a hydrogarnet-grossular solid solution and with respect to phase relations reported into already published works. Finally, we underline the chemical compatibility of Portland cement pastes with carbonate aggregates, compared to silicates, for long-term storage applications.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Density and water content of nanoscale solid C-S-H formed in alkali-activated slag (AAS) paste and implications for chemical shrinkage

Alkali-activated slag (AAS) paste was analyzed using small-angle neutron scattering (SANS). The scattering response indicates that the microstructure consists of a uniform matrix of hydration product with a high surface area studded with unhydrated cores of slag particles. In contrast with portland cement paste, no surface fractal scattering regime was detected, and elevated temperature curing (at 60 Degree-Sign C) had no detectable effect on the microstructure at any length scale studied. The specific surface area of the AAS pastes is about 25% higher than that of a portland cement paste cured under the same conditions. The composition and mass density of the nanoscale solid C-S-H phase formed in the AAS paste was determined using a previously developed neutron scattering method, in conjunction with a hydration model. The result ((CaO){sub 0.99}-SiO{sub 2}-(Al{sub 2}O{sub 3}){sub 0.06}-(H{sub 2}O){sub 0.97}, d = (2.73 {+-} 0.02) g/cm{sup 3}) is significantly lower in calcium and in water as compared to portland cement or pure tricalcium silicate paste. These values were used to calculate the chemical shrinkage that would result from complete hydration of the AAS paste. The result, (12.2 {+-} 1.5) cm{sup 3} of volumetric shrinkage per 100 g of unhydrated cement, is about twice the amount of chemical shrinkage exhibited by normal cement pastes.

36 MATERIALS SCIENCE↗
DOE OSTI2011

X-ray photoelectron (XPS) and Diffuse Reflectance Infra Fourier Transformation (DRIFT) study of Ba{sub 0.5}Sr{sub 0.5}Co{sub x}Fe{sub 1-x}O{sub 3-{delta}} (BSCF: x=0-0.8) ceramics

The X-ray photoelectron spectra (XPS) of sintered BSCF ceramics (Ba{sub 0.5}Sr{sub 0.5}Co{sub x}Fe{sub 1-x}O{sub 3-{delta}},0{<=}x{<=}0.8) were measured at room temperature (RT). Peak areas of Fe{sub 2p1}, Fe{sub 2p3}, Fe{sub 3p} and Co{sub 3p} increased systematically with increasing cobalt concentration, while their binding energies (BEs) remained the same (723.3, 710.0, 55.0 and 60.9 eV, respectively). However, the BEs of lattice oxygen in O{sub 1s} (528.1 eV) and Ba{sub 4d} for the BaO bond (87.9V and 90.2 eV) increased with increasing cobalt concentration. The shoulder peak of Ba{sub 3d}/Co{sub 2p} increased from 778.0 to 778.7 eV, which implies that this peak can be attributed to another Ba XPS peak (described as Ba{sub 2nd} in this study) due to the overlapping area between barium cations and oxygen anions. The overall peak areas of Ba{sub 4d} increased up to x=0.4, and then decreased, which coincides with the behavior of the Diffuse Reflectance Infrared Fourier Transform (DRIFT) bands representing adsorbed CO{sub 3}{sup 2-} ({nu}CO{sub 3}{sup 2-}) and structurally bonded CO{sub 3}{sup 2-} ({nu}{sub 2}, {nu}{sub 3}) (800-1200 and 862/1433 cm{sup -1}, respectively). - Graphical abstract: The bonding of CO{sub 3}{sup 2-} to the surface of BSCF perovskite and the bonding state between cations vs. oxygen have been suggested. Highlights: > XPS and DRIFT were measured on BSCF (BSCF: x=0-0.8) samples. > The identity of Ba{sub 3d}/Co{sub 2p} XPS shoulder peak at {approx}778.0 was suggested. > The bonding behavior of CO{sub 3}{sup 2-} to the BSCF prevoskite structure was studied substantially.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Heavy doping of H{sup -} ion in 12CaO.7Al{sub 2}O{sub 3}

12CaO.7Al{sub 2}O{sub 3} (C12A7, mayenite), which has a nanoscale porous structure that can accommodate extraframework species such as hydride (H{sup -}), oxide (O{sup 2-}), hydroxide (OH{sup -}) ions, and electrons, has been doped with H{sup -} ions to investigate its effects as dominant extraframework species. Chemical doping with CaH{sub 2} enables the concentration of H{sup -} ions to reach almost the theoretical maximum. The concentration of H{sup -} ions is characterized by optical absorption intensity ascribed to photoionization of H{sup -} ions, and {sup 1}H magic angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopy. Persistent electron generation, which is accompanied by the formation of an F{sup +} absorption band and electrical conductivity, by irradiation with ultraviolet light at room temperature increases as the H{sup -} ion doping increases until it reaches half the theoretical maximum and then decreases as the H{sup -} ion concentration increases further. This dependence indicates that both H{sup -} and O{sup 2-} ions are necessary for the generation of persistent electrons. - Graphical abstract: CaH{sub 2} reduction markedly enhances H{sup -} ion doping in 12CaO.7Al{sub 2}O{sub 3}. The H{sup -} ion incorporation is evaluated using optical absorption and {sup 1}H-MAS-NMR spectra. Both H{sup -} and O{sup 2-} ions are responsible for photogeneration of electrons. Highlights: > CaH{sub 2} reduction markedly enhances H{sup -} ion doping in 12CaO.7Al{sub 2}O{sub 3}. {yields}The H{sup -} ion incorporation is evaluated using optical absorption and {sup 1}H-MAS-NMR spectra. > Both H{sup -} and O{sup 2-} ions are responsible for photogeneration of electrons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Phase relations in a barium-rich high-temperature region (25-45 mol% CuO, 900-1100 deg. C) of the BaO-CuO{sub x} system

The phase relations have been studied in the BaO-CuO{sub x} system in the range of 25.0-45.0 mol% CuO at 900-1100 deg. C at P(O{sub 2})=21 kPa (air) by visual polythermal analysis (VPA), powder X-ray diffraction (XRD), electron diffraction (ED) with simultaneous energy-dispersive X-ray (EDX) elemental analysis in a transmission electron microscope (TEM), and iodometric chemical analysis. The discrete deviations 2.02 (101:50), 2.04 (102:50), 2.10 (105:50) of Ba/Cu (Ba:Cu) composition from the stoichiometric ratio 2:1 have been found for the known Ba{sub 2}CuO{sub 3+{delta}} oxides in the subsolidus region 900-970 deg. C. Unit cell parameters of the 101:50 orthorhombic oxide, 102:50 tetragonal one, 105:50 orthorhombic one are, respectively, a=4.049, b=3.899, c=13.034 A; a=3.985, c=12.968 A; a=4.087, b=3.897 and c=12.950 A. ED patterns of the 101:50, 102:50, 105:50 oxides show characteristic supercell reflections with the respective vector 1/60[5 4 0], {approx}2/11<1 1 0> and 1/6[2 0 0]. Oxides of the 2:1, 7:4, 5:3 and 23:20 compositions have been found in the crystallization region 970-1050 deg. C. Unit cell parameters of the 2:1 orthorhombic oxide are a=4.095, b=3.795, c=13.165 A. Interplanar spacings and X-ray characteristic peak intensities of the 7:4, 5:3 and 23:20 oxides are given. Oxides 2:1 and 7:4 melt pseudocongruently at 1020 and 1005 deg. C, oxides 5:3 and 23:20 melt incongruently at 995 and 980 deg. C, respectively. A diagram of the phase relations in the studied region of the BaO-CuO{sub x} system has been constructed, whose structure is considered as the total projection of phase states of the system existing for different x. - Graphical Abstract: A diagram of phase relations in the BaO-CuO{sub x} system in the range of 30.0-45.0 mol% CuO at 900-1050 deg. C at P(O{sub 2})=21 kPa (air) constructed on the data obtained by visual polythermal analysis (the liquidus line), XRD and ED with elemental analysis. Highlights: > A combination of physical-chemical and structural methods was used. > New discrete oxides have been found. > The diagram reflects the total projection of phase states at different x.

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

Thermodynamic restrictions on mechanosynthesis of strontium titanate

Chemical potential phase stability diagrams were calculated from relevant thermodynamic properties and used to predict the thermodynamic driving force under prospective conditions of room temperature mechanosynthesis. One analysed the dependence of chemical potential diagrams on temperature and partial pressure of evolving gases such as oxygen or carbon dioxide, as expected on using strontium peroxide or strontium carbonate as precursor reactants for the alkali earth component. Thermodynamic calculations were also obtained for changes in titania precursor reactants, including thermodynamic predictions for reactivity of strontium carbonate with amorphous titania. Experimental evidence showed that strontium titanate can be obtained by mechanosynthesis of strontium carbonate+anatase mixtures, due to previous amorphization under high energy milling. Ability to perform mechanosynthesis with less energetic milling depends on the suitable choice of alternative precursor reactants, which meet the thermodynamic requirements without previous amorphization; this was demonstrated by mechanosynthesis from anatase+strontium peroxide mixtures. - Graphical abstract: X-Ray diffractograms of the starting TiO{sub 2} (anatase)+SrCO{sub 3} mixture and after mechanical activation at 650 rpm, for 1, 2, and 7 h. Different symbols are used to identify reflections ascribed to anatase (diamonds), SrCO{sub 3} (squares) and SrTiO{sub 3} (triangles). Highlights: Black-Right-Pointing-Pointer Prediction of thermodynamic driving force for room temperature mechanosynthesis. Black-Right-Pointing-Pointer Dependence of chemical potential diagrams on temperature and partial pressure. Black-Right-Pointing-Pointer Thermodynamic calculations for changes in titania precursor. Black-Right-Pointing-Pointer Experimental support for thermodynamic predictions.

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

Cr{sup 6+}-containing phases in the system CaO-Al{sub 2}O{sub 3}-CrO{sub 4}{sup 2-}-H{sub 2}O at 23 Degree-Sign C

Synthesis and investigation of lamellar calcium aluminium hydroxy salts was performed to study the incorporation of chromate ions in the interlayer of lamellar calcium aluminium hydroxy salts. Different AFm-phases (calcium aluminate hydrate with alumina, ferric oxide, mono-anion phase) containing chromate were synthesized. These AFm-phases belong to the group of layered double hydroxides (LDHs). 3CaO{center_dot}Al{sub 2}O{sub 3}{center_dot}CaCrO{sub 4}{center_dot}nH{sub 2}O and C{sub 3}A{center_dot}1/2Ca(OH){sub 2}{center_dot}1/2CaCrO{sub 4}{center_dot}12H{sub 2}O were obtained as pure phases and their different distinct interlayer water contents and properties determined. Solid solution of chromate-containing phases and tetracalcium-aluminate-hydrate (TCAH) were studied. The uptake of chromate into TCAH from solutions was proven. Chromate contents in solution decrease to <0.2 mg/l. - Graphical abstract: Chromate can be incorporated in LDH-phases with compositions like: 3CaO{center_dot}Al{sub 2}O{sub 3}{center_dot}1/2CaCrO{sub 4}{center_dot}1/2Ca(OH){sub 2}{center_dot}nH{sub 2}O, 3CaO{center_dot}Al{sub 2}O{sub 3}{center_dot}CaCrO{sub 4}{center_dot}nH{sub 2}O, 3CaO{center_dot}Al{sub 2}O{sub 3}{center_dot}1/6CaCrO{sub 4}.{center_dot}5/6Ca(OH){sub 2}{center_dot}nH{sub 2}O, 3CaO{center_dot}Al{sub 2}O{sub 3}(0-x)CaCrO{sub 4}(1-x) Ca(OH){sub 2}{center_dot}12H{sub 2}O, (0<x<0.17). Highlights: Black-Right-Pointing-Pointer Solid solutions and properties of 3CaO{center_dot}Al{sub 2}O{sub 3}{center_dot}CaCrO{sub 4}{center_dot}nH{sub 2}O and C{sub 3}A{center_dot}1/2 Ca(OH){sub 2}{center_dot}1/2 CaCrO{sub 4}{center_dot}12 H{sub 2}O are given. Black-Right-Pointing-Pointer Different hydrates of Ca-Al-hydroxysalts (LDH) with chromate-anions synthesized and characterized. Black-Right-Pointing-Pointer Interlayer exchange reaction of 2OH{sup -} and CrO{sub 4}{sup 2-} investigated. Black-Right-Pointing-Pointer Thermal dehydration and change of lattice parameters are given

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Evolution of the surface structures on SrTiO{sub 3}(110) tuned by Ti or Sr concentration

The surface structure of the SrTiO{sub 3}(110) polar surface is studied by scanning tunneling microscopy and x-ray photoelectron spectroscopy. Monophased reconstructions in (5 x 1), (4 x 1), (2 x 8), and (6 x 8) are obtained, respectively, and the evolution between these phases can be tuned reversibly by adjusting the Ar{sup +} sputtering dose or the amount of Sr/Ti evaporation. Upon annealing, the surface reaches the thermodynamic equilibrium that is determined by the metal concentration. The different electronic structures and absorption behaviors of the surface with different reconstructions are investigated.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Ca-intercalated graphite as a hydrogen storage material: Stability against decomposition into CaH{sub 2} and graphite

We have used calculations based on density functional theory to investigate the energetics of hydrogen absorption in calcium-intercalated graphites. We focus particularly on the absorption energy and the stability of the hydrogenated material with respect to decomposition into graphite and calcium hydride, which is essential if this material is to be used for practical H{sub 2} storage. The calculations are performed with two commonly used approximations for the exchange-correlation energies. Our calculations confirm earlier predictions that the absorption energy is approximately -0.2 to -0.4 eV, which is favourable for practical use of Ca-intercalated graphite as a hydrogen storage medium. However, we find that the hydrogenated material is strongly unstable against decomposition. Our results therefore explain recent experiments which show that H{sub 2} does not remain stable in CaC{sub 6} but instead forms a hydride plus graphite. - Graphical abstract: The hydrogenation of Ca-graphite (left) results in its decomposition into pure graphite (middle) and CaH{sub 2} (right). Highlights: > We investigate the stability of hydrogenated Ca-intercalated graphite with DFT. > Dissociated H absorption in CaC{sub 6} is most favourable, with reasonable binding energies. > Molecular H{sub 2} absorption is most favourable in CaC{sub 8} and CaC{sub 14}. > We find all scenarios are unstable against decomposition into CaH{sub 2} and graphite. > The decomposition will be strongly exothermic in agreement with experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

3D Chemical and Elemental Imaging by STXM Spectrotomography

Spectrotomography based on the scanning transmission x-ray microscope (STXM) at the 10ID-1 spectromicroscopy beamline of the Canadian Light Source was used to study two selected unicellular microorganisms. Spatial distributions of sulphur globules, calcium, protein, and polysaccharide in sulphur-metabolizing bacteria (Allochromatium vinosum) were determined at the S 2p, C 1s, and Ca 2p edges. 3D chemical mapping showed that the sulphur globules are located inside the bacteria with a strong spatial correlation with calcium ions (it is most probably calcium carbonate from the medium; however, with STXM the distribution and localization in the cell can be made visible, which is very interesting for a biologist) and polysaccharide-rich polymers, suggesting an influence of the organic components on the formation of the sulphur and calcium deposits. A second study investigated copper accumulating in yeast cells (Saccharomyces cerevisiae) treated with copper sulphate. 3D elemental imaging at the Cu 2p edge showed that Cu(II) is reduced to Cu(I) on the yeast cell wall. A novel needle-like wet cell sample holder for STXM spectrotomography studies of fully hydrated samples is discussed.

43 PARTICLE ACCELERATORS↗
DOE OSTI2011

Preparation and formation mechanism of three-dimensionally ordered macroporous (3DOM) MgO, MgSO{sub 4}, CaCO{sub 3}, and SrCO{sub 3}, and photonic stop band properties of 3DOM CaCO{sub 3}

Three-dimensionally ordered macroporous (3DOM) magnesium (Mg) oxide (MgO), MgSO{sub 4}, calcium (Ca) carbonate (CaCO{sub 3}), and strontium (Sr) carbonate (SrCO{sub 3}) were prepared using a colloidal crystal of polymer spheres as a template. Ethanol or ethanol-water solution of metal salts (acetate or nitrate) and citric acid was infiltrated into the void of the colloidal crystal template of a monodispersed poly(methyl methacrylate) (PMMA) sphere. Heating of this PMMA-metal salt-citric acid composite produced the desired well-ordered 3DOM materials with a high pore fraction, which was confirmed by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and ultraviolet-visible (UV-vis) diffuse reflectance spectra. The presence of citric acid is crucial for production of the 3DOM structures. Reaction of citric acid with metal salt produces metal citrate solid in the void of PMMA spheres, which is necessary to maintain the 3DOM structure during the calcination process. 3DOM CaCO{sub 3} shows opalescent colors because of it's photonic stop band properties. - Graphical abstract: Well-ordered 3-dimensionally ordered macroporous MgO, MgSO{sub 4}, CaCO{sub 3}, and SrCO{sub 3} materials were obtained in a high pore fraction. Highlights: > An easy preparation method of 3D ordered macroporous (3DOM) MgO, MgSO{sub 4}, CaCO{sub 3}, and SrCO{sub 3} materials. > Their structural characterization. > Their formation mechanism. > Photonic properties of 3DOM CaCO{sub 3}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Chemical pathways in ultracold reactions of SrF molecules

We present a theoretical investigation of the chemical reaction SrF + SrF {yields} products, focusing on reactions at ultralow temperatures. We find that bond swapping SrF + SrF {yields} Sr{sub 2} + F{sub 2} is energetically forbidden at these temperatures. Rather, the only energetically allowed reaction is SrF + SrF {yields} SrF{sub 2} + Sr, and even then only singlet states of the SrF{sub 2} trimer can form. A calculation along a reduced reaction path demonstrates that this abstraction reaction is barrierless and proceeds by one SrF molecule ''handing off'' a fluorine atom to the other molecule.

74 ATOMIC AND MOLECULAR PHYSICS↗