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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 667 records · Page 37
All sourcesNASA NTRSDOE OSTI
DOE OSTI2011

Role of oxygen on the optical properties of borate glass doped with ZnO

Lithium tungsten borate glass (0.56-x)B{sub 2}O{sub 3}-0.4Li{sub 2}O-xZnO-0.04WO{sub 3} (0{<=}x{<=}0.1 mol%) is prepared by the melt quenching technique for photonic applications. Small relative values of ZnO are used to improve the glass optical dispersion and to probe as well the role of oxygen electronic polarizability on its optical characteristics. The spectroscopic properties of the glass are determined in a wide spectrum range (200-2500 nm) using a Fresnel-based spectrophotometric technique. Based on the Lorentz-Lorenz theory, as ZnO content increases on the expense of B{sub 2}O{sub 3} the glass molar polarizability increased due to an enhanced unshared oxide ion 2p electron density, which increases ionicity of the chemical bonds of glass. The role of oxide ion polarizability is explained in accordance with advanced measures and theories such as optical basicity, O 1s binding energy, the outer most cation binding energy in Yamashita-Kurosawa's interionic interaction parameter and Sun's average single bond strength. FT-IR measurements confirm an increase in bridging oxygen bonds, as a result of replacement of ZnO by B{sub 2}O{sub 3}, which increase the UV glass transmission window and transmittance. - Graphical abstract: O1s, Yamashita-Kurosawa's parameter and average single bond strength of charge overlapping between electronic shells are used to explain enhanced oxide ion 2p electron density, which increases refractive index of glasses. Highlights: > New borate glass for photonic application is prepared. > The dispersion property of the glass is effectively controlled using small amounts of ZnO. > ZnO is used to probe the glass structure and investigate the role of oxygen on the obtained optical properties of the glasses. > Modern theories are used to explain enhanced unshared oxide ion 2p electron density, which increases ionicity of chemical bonds of the glass.

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

Alpha self-irradiation effect on the local structure of the U{sub 0.85}Am{sub 0.15}O{sub 2{+-}x} solid solution

Uranium-americium mixed oxides are promising fuels for achieving an efficient Am recycling. Previous studies on U{sub 0.85}Am{sub 0.15}O{sub 2{+-}x} materials showed that the high {alpha} activity of {sup 241}Am induces pellet swelling which is a major issue for cladding materials design. In this context, X-ray Diffraction and X-ray Absorption Spectroscopy measurements were used to study self-irradiation effects on U{sub 0.85}Am{sub 0.15}O{sub 2{+-}x} local structure and to correlate these results with those obtained at the macroscopic scale. For a cumulative {alpha} decay dose equal to 0.28 dpa, it was shown that non-defective fluorite solid solutions were achieved and therefore, that the fluorite structure is stable for the studied doses. In addition, both interatomic distance and lattice parameter expansions were observed, which only partially explains the macroscopic swelling. As expected, an increase of the structural disorder with self-irradiation was also observed. - Graphical abstract: X-ray Diffraction and X-ray Absorption Spectroscopy measurements were performed on U{sub 0.85}Am{sub 0.15}O{sub 2{+-}x}, exhibiting various cumulative {alpha} decay doses, in order to study self-irradiation effects on local structure and to correlate these results with those obtained at the macroscopic scale. Thus, it was shown that the fluorite structure is stable for the studied doses. In addition, both interatomic distance and lattice parameter expansions were observed, explaining partially the macroscopic swelling. Highlights: Black-Right-Pointing-Pointer Non-defective fluorite U{sub 0.85}Am{sub 0.15}O{sub 2{+-}x} solid solutions were achieved. Black-Right-Pointing-Pointer The fluorite structure is stable for the studied doses. Black-Right-Pointing-Pointer A lattice parameter increase was observed, which partially explains the macroscopic swelling. Black-Right-Pointing-Pointer The increase of the structural disorder can be understood from the ballistic effect associated to the Am high alpha activity.

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

Multiple nonlinear dielectric resonance of ultra-long silver trimolybdate nanowires

The silver molybdate nanowires (NWs) have been synthesized and characterized. The multiple dielectric resonant peaks of the nanocomposites filled with silver molybdate nanowires have been studied from 2 to 18 GHz. The as-established equivalent circuit model of the silver molybdate nanowires were employed to explain the nonlinear dielectric resonant behavior. - Graphical abstract: The ultra-long silver trimolybdate nanowires were synthesized and the dielectric peoperties of the products were studied from 2 to 18 GHz. The as-established equivalent circuit model of the silver molybdate nanowires were employed to explain the nonlinear dielectric resonant behavior. Highlights: • The silver molybdate nanowires have been synthesized and characterized. • The dielectric properties of the silver molybdate/ paraffin nanocomposites have been studied. • Higher concentration of silver trimolybdate enhances the dielectric properties of composite. • The dielectric behaviors were explained based on the as-established equivalent circuit mode.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Synthesis and characterization of hollow mesoporous BaFe{sub 12}O{sub 19} spheres

A facile method is reported to synthesize hollow mesoporous BaFe{sub 12}O{sub 19} spheres using a template-free chemical etching process. Hollow BaFe{sub 12}O{sub 19} spheres were synthesized by conventional spray pyrolysis. The mesoporous structure is achieved by alkaline ethylene glycol etching at 185 °C, with the porosity controlled by the heating time. The hollow porous structure is confirmed by SEM, TEM, and FIB-FESEM characterization. The crystal structure and magnetic properties are not significantly affected after the chemical etching process. The formation mechanism of the porous structure is explained by grain boundary etching. - Graphical abstract: Hollow spherical BaFe{sub 12}O{sub 19} particles are polycrystalline with both grains and grain boundaries. Grain boundaries have less ordered structure and lower stability. When the particles are exposed to high temperature alkaline ethylene glycol, the grain boundaries are etched, leaving small grooves between grains. These grooves allow ethylene glycol to diffuse inside to further etch the grains. As the grain size decreases, gaps appear on the particle surfaces, and a porous structure is finally formed. - Highlights: • Two-step synthesis method for hollow mesoporous BaFe{sub 12}O{sub 19} spheres is proposed. • Porosity of the product can be regulated by controlling the second step of chemical etching. • The crystal structure and magnetic properties are examined to be little affected during the chemical etching. • The mesoporous structure formation mechanism is explained by grain boundary etching.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Inorganic anion-dependent assembly of zero-, one-, two- and three-dimensional Cu(II)/Ag(I) complexes under the guidance of the HSAB theory: Synthesis, structure, and magnetic property

To systematically explore the influence of inorganic anions on building coordination complexes, five novel complexes based on 1-(benzotriazole-1-methyl)−2-propylimidazole (bpmi), [Cu(bpmi){sub 2}(Ac){sub 2}]·H{sub 2}O (1), [Cu(bpmi){sub 2}(H{sub 2}O){sub 2}]·2NO{sub 3}·2H{sub 2}O (2), [Cu(bpmi)(N{sub 3}){sub 2}] (3), [Ag(bpmi)(NO{sub 3})] (4) and [Cu{sub 3}(bpmi){sub 2}(SCN){sub 4}(DMF)] (5) (Ac{sup −}=CH{sub 3}COO{sup −}, DMF=N,N-Dimethylformamide) are synthesized through rationally introducing Cu(II) salts and Ag(I) salt with different inorganic anions. X-ray single-crystal analyses reveal that these complexes show interesting structural features from mononuclear (1), one-dimensional (2 and 3), two-dimensional (4) to three-dimensional (5) under the influence of inorganic anions with different basicities. The structural variation can be explained by the hard-soft-acid-base (HSAB) theory. Magnetic susceptibility measurement indicates that complex 3 exhibits an antiferromagnetic coupling between adjacent Cu(II) ions. - Graphical abstract: Five new Cu(II)/Ag(I) complexes show interesting structural features from mononuclear, one-dimension, two-dimension to three-dimension under the influence of inorganic anions. The structural variation can be explained by the HSAB theory. - Highlights: • Five inorganic anion-dependent complexes are synthesized. • Structural variation can be explained by the hard-soft-acid-base (HSAB) theory. • The magnetic property of complex has been studied.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2010

Effects of strain amplitude and temperature on the damping capacity of an Fe-19Mn alloy with different microstructures

The influences of strain amplitude (10{sup -5}-10{sup -4}) and temperature (25 deg. C-500 deg. C) on the internal friction of a cold-drawn and solution treated Fe-19Mn alloy were investigated. The internal friction was measured using reversal torsion pendulum and multifunction internal friction equipment. The microstructure was observed using scanning electron microscopy. The phase transformation temperatures were determined using differential scanning calorimetry. The results indicated that the internal friction of the solution treated alloy was related to strain amplitude, which could be explained using the movement of Shockley partial dislocations (bowing out and breaking away). But the internal friction of the cold-drawn alloy was independent of strain amplitude because of high density dislocations formed by cold forming. Moreover, when the temperature was changed between 25 deg. C and 500 deg. C, the internal friction of the cold-drawn alloy increased slowly from 25 deg. C to 375 deg. C, and then increased quickly from 375 deg. C to 500 deg. C. However, for the solution treated alloy, there was an internal friction peak at about 210 deg. C in the heating process (from 25 deg. C to 500 deg. C), and there was another internal friction peak at about 150 deg. C in the cooling process. These peaks could be explained using the heat-assisted movement of dislocations. - Research Highlights: {yields}Internal friction of solution treated Fe-19Mn alloy is related to strain amplitude. {yields}Internal friction of cold-drawn Fe-19Mn alloy is independent of strain amplitude. {yields}IF of cold-drawn alloy increases from RT to 500 deg. C. {yields}There is an IF peak of solution treated alloy in heating and cooling process separately. {yields}The results can be explained using the movement of dislocations.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Microstructure of selective laser melted nickel–titanium

In selective laser melting, the layer-wise local melting of metallic powder by means of a scanning focused laser beam leads to anisotropic microstructures, which reflect the pathway of the laser beam. We studied the impact of laser power, scanning speed, and laser path onto the microstructure of NiTi cylinders. Here, we varied the laser power from 56 to 100 W and the scanning speed from about 100 to 300 mm/s. In increasing the laser power, the grain width and length increased from (33 ± 7) to (90 ± 15) μm and from (60 ± 20) to (600 ± 200) μm, respectively. Also, the grain size distribution changed from uni- to bimodal. Ostwald-ripening of the crystallites explains the distinct bimodal size distributions. Decreasing the scanning speed did not alter the microstructure but led to increased phase transformation temperatures of up to 40 K. This was experimentally determined using differential scanning calorimetry and explained as a result of preferential nickel evaporation during the fabrication process. During selective laser melting of the NiTi shape memory alloy, the control of scanning speed allows restricted changes of the transformation temperatures, whereas controlling the laser power and scanning path enables us to tailor the microstructure, i.e. the crystallite shapes and arrangement, the extent of the preferred crystallographic orientation and the grain size distribution. - Highlights: • Higher laser powers during selective laser melting of NiTi lead to larger grains. • Selective laser melting of NiTi gives rise to preferred <111> orientation. • The observed Ni/Ti ratio depends on the exposure time. • Ostwald ripening explains the bimodal grain size distribution.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Large-scale and shape-controlled synthesis and characterization of nanorod-like nickel powders under microwave radiation

Graphical abstract: The nanorod-like pure nickel were fabricated via hydrothermal liquid phase reduction route under microwave irradiation with hydrazine hydrate as a reducing agent as well as polyvinyl alcohol as a dispersant and/or structure directing agent. The materials were characterized by XRD, SEM, EDS, HRTEM, and selected-area electron diffraction, etc. The lattice expansion for Ni powders was explained in detail. As-prepared Ni sample was of obvious shape anisotropy with length diameter ratio of 5. Magnetic measurements shown that the magnetic properties of Ni nanorod-like (fcc) were quite different from those of hexagonal closed-packed (hcp) Ni nanoparticles. Highlights: Black-Right-Pointing-Pointer The synthesis of nanorod-like nickel under microwave irradiation. Black-Right-Pointing-Pointer Nitrogen generated in reaction as a shielding gas. Black-Right-Pointing-Pointer The lattice expansion for Ni powders was explained in detail. Black-Right-Pointing-Pointer Magnetic properties of Ni were quite different from those of Ni nanoparticles. -- Abstract: The nanorod-like nickel powders were fabricated via hydrothermal liquid phase reduction route under microwave irradiation with hydrazine hydrate as a reducing agent as well as polyvinyl alcohol as a dispersant and/or structure directing agent. The morphology and structure of as-prepared products could be easily tuned by adjusting process parameters such as pH value and microwave irradiation time. The resulting materials were characterized by X-ray diffraction (XRD), scanning electron microscope, transmission electron microscopy and selected-area electron diffraction (SAED). The results demonstrated that pure nickel powders with face-centered cubic (fcc) structure were prepared at relatively mild condition and no characteristic peaks of nickel oxide in the XRD pattern were found. The phenomenon of lattice expansion for Ni powders was explained in details according to the XRD theory. As-prepared Ni sample was of obvious shape anisotropy with length diameter ratio of 5. Magnetic measurements shown that the magnetic properties of nanorod-like (fcc) Ni powders were quite different from those of hexagonal closed-packed (hcp) Ni nanoparticles. Furthermore, it had more strong ferromagnetic properties than that of Ni powders both bulk and nanoparticles.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Magnetic properties of nanocrystalline ε-Fe{sub 3}N and Co{sub 4}N phases synthesized by newer precursor route

Graphical abstract: Nanocrystalline ε-Fe{sub 3}N and Co{sub 4}N nitride phases are synthesized first time by newer chemical routes. The ε-Fe{sub 3}N phase crystallizes in hexagonal structure with unit cell parameters, a = 4.76 Å and c = 4.41 Å. The Co{sub 4}N phase crystallizes in face centred cubic (fcc) structure with unit cell parameters, a = 3.55 Å. The estimated crystallite size for ε-Fe{sub 3}N and Co{sub 4}N phases are 29 nm and 22 nm, respectively. The values of saturation magnetization for ε-Fe{sub 3}N and Co{sub 4}N phases are found to be 28.1 emu/g and 123.6 emu/g respectively. The reduction of magnetic moments in ultrafine materials compared to bulk materials has been explained by fine particle size and surface effects. We have synthesized the high moment ε-Fe{sub 3}N and Co{sub 4}N nitride with reduced coercivity which may find applications as soft magnetic materials. - Highlights: • Nanocrystalline ε-Fe{sub 3}N and Co{sub 4}N nitride phases are synthesized. • The ε-Fe{sub 3}N and Co{sub 4}N crystallizes in hexagonal and fcc structure respectively. • The observed magnetic parameters indicate soft magnetic properties. • The magnetic properties have been explained on the basis of fine particle magnetism. - Abstract: Nanocrystalline ε-Fe{sub 3}N and Co{sub 4}N nitride phases are synthesized first time by using tris(1,2-diaminoethane)iron(II) chloride and tris(1,2-diaminoethane)cobalt(III) chloride precursors, respectively. To prepare ε-Fe{sub 3}N and Co{sub 4}N nitride phases, the synthesized precursors were mixed with urea in 1:12 ratio and heat treated at various temperatures in the range of 450–900 °C under the ultrapure nitrogen gas atmosphere. The precursors are confirmed by FT-IR study. The ε-Fe{sub 3}N phase crystallizes in hexagonal structure with unit cell parameters, a = 4.76 Å and c = 4.41 Å. The Co{sub 4}N phase crystallizes in face centred cubic (fcc) structure with unit cell parameters, a = 3.55 Å. The estimated crystallite size for ε-Fe{sub 3}N and Co{sub 4}N phases are 29 nm and 22 nm, respectively. The scanning electron microscopy (SEM) studies confirm the nanocrystalline nature of the materials. The values of saturation magnetization for ε-Fe{sub 3}N and Co{sub 4}N phases are found to be 28.1 emu/g and 123.6 emu/g, respectively. The reduction of magnetic moments in ultrafine materials compared to bulk materials have been explained by spin pairing effect, lattice expansion, superparamagnetic behaviour and canted spin structures at the surface of the particles.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Effect of sintering temperature on structural, magnetic and electrical transport properties of La0.67Ca0.33MnO3 ceramics prepared by Plasma Activated Sintering

Highlights: • La{sub 0.67}Ca{sub 0.33}MnO{sub 3} were prepared by using Plasma Activated Sintering technology. • Detailed studies of sintering temperature effect on structural, magnetic and electrical transport behaviors were investigated. • The observed behaviors have been explained by oxygen vacancy effect in combination with grain size effect. - Abstract: La{sub 0.67}Ca{sub 0.33}MnO{sub 3} (LCMO) ceramics were prepared by Plasma Activated Sintering (PAS). The effect of sintering temperature on structural, magnetic and electrical transport properties of the LCMO ceramics were investigated. XRD and SEM characterizations of the LCMO ceramics indicated that all samples exhibited single orthorhombic phase. Also, through PAS dense LCMO ceramics were obtained. Certain interesting phenomena were observed from the PAS sintering temperature effect on the magnetic and transport behaviors of LCMO ceramics, which were significantly different from traditional sintering methods The magnetization decreased and the resistivity increased as the sintering temperature increased, whereas the T{sub C} and T{sub IM} shifted towards the lower temperature side. The conduction mechanism of all samples was electron-magnon scattering process in the ferromagnetic low-temperature region, while the paramagnetic high-temperature region mechanism was explained with the variable range hopping (VRH) model. All these behaviors were explained through the oxygen vacancy effect in combination with the grain size effect.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Synthesis and effect of Ba2+ ions on the dielectric properties of the layered-perovskite KSr2NaNb4O13 ceramics

Highlights: • 25 mol% excess K{sub 2}O was added to densify the pure K(Sr{sub 2}Na)Nb{sub 4}O{sub 13} ceramic at 1275 °C. • K(Sr{sub 2}Na)Nb{sub 4}O{sub 13} ceramic has an increased ε{sub r} compared with that of KSr{sub 2}Nb{sub 3}O{sub 10} ceramic. • K(Sr{sub 0.8}Ba{sub 0.2}){sub 2}NaNb{sub 4}O{sub 13} ceramic has a highest ε{sub r} of 67.4 with a small tan δ of 0.14. • Large ε{sub r} is explained by the increased dipole moment and NbO{sub 6} octahedron distortion. - Abstract: The 25 mol% K{sub 2}O-added K(Sr{sub 2}Na)Nb{sub 4}O{sub 13} ceramic sintered at 1275 °C exhibited a pure and dense K(Sr{sub 2}Na)Nb{sub 4}O{sub 13} phase, which had four octahedral layers. Synthesis of a pure K(Sr{sub 2}Na)Nb{sub 4}O{sub 13} ceramic was not possible without excess K{sub 2}O, due to the formation of a Na-deficient K(Sr{sub 2}Na{sub 2})Nb{sub 5}O{sub 16} secondary phase, because of K{sub 2}O evaporation during sintering. The dielectric constant (ε{sub r}) of the K(Sr{sub 2}Na)Nb{sub 4}O{sub 13} ceramic was 43.8 at 100 kHz, two times higher compared to the KSr{sub 2}Nb{sub 3}O{sub 10} ceramic, which has three octahedral layers. The increased ε{sub r} can be explained by the increased number of octahedral layers. Some of the Sr{sup 2+} ions in K(Sr{sub 2}Na)Nb{sub 4}O{sub 13} ceramic were replaced by Ba{sup 2+} ions, which have high ionic polarizability, to further increase ε{sub r}. The 25 mol% K{sub 2}O-excess K(Sr{sub 0.8}Ba{sub 0.2}){sub 2}NaNb{sub 4}O{sub 13} ceramic sintered at 1250 °C showed a high ε{sub r} of 67.4 at 100 kHz, which can be explained by the increased dipole moments and distortion of the NbO{sub 6} octahedra.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Structural, magnetic and impedance spectroscopy analysis of (0.7)CoFe2O4+(0.3)BaTiO3 magnetoelectric composite

Highlights: • Successfully synthesized (0.7)CoFe{sub 2}O{sub 4}+(0.3)BaTiO{sub 3} composite by ball-milling method. • Structural properties confirmed the presence of both constituent phases. • Dielectric properties showed high value of permittivity and diminished dielectric loss at higher frequency. • Electric response of the constituent phases explained the observed relaxation processes. • Small polaron hopping mechanism governed the conduction mechanism. - Abstract: Magnetoelectric composite of particular composition (0.7)CoFe{sub 2}O{sub 4}+(0.3)BaTiO{sub 3} was synthesized by ball-milling method. X-ray diffraction pattern confirmed the presence of cubic spinel phase for CoFe{sub 2}O{sub 4} and the coexistence of tetragonal phase along with a small fraction of hexagonal phase for BaTiO{sub 3} in the prepared composite. The dielectric permittivity increased with increasing temperature (298–373 K); however, it showed relatively high magnitude of permittivity (∼1100) and diminished dielectric loss (∼0.045) at higher frequency. Complex impedance and modulus plots exhibited responses of different electro-active regions which are explained on the basis of coexistence of resistive and comparatively conductive phases in the prepared composite. Small polaronic hopping model was employed to explain the n-type carrier’s mobility as a possible conduction mechanism; whereas the activation energies calculated from the conduction and relaxation processes were found to be comparable. These results indicate that electric/dielectric properties and relaxation phenomenon are associated to the same origin.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Anisotropy in the deep Earth

Not provided.Seismic anisotropy has been found in many regions of the Earth's interior. Its presence in the Earth's crust has been known since the 19th century, and is due in part to the alignment of anisotropic crystals in rocks, and in part to patterns in the distribution of fractures and pores. In the upper mantle, seismic anisotropy was discovered 50 years ago, and can be attributed for the most part, to the alignment of intrinsically anisotropic olivine crystals during large scale deformation associated with convection. There is some indication for anisotropy in the transition zone, particularly in the vicinity of subducted slabs. Here we focus on the deep Earth – the lower mantle and core, where anisotropy is not yet mapped in detail, nor is there consensus on its origin. Most of the lower mantle appears largely isotropic, except in the last 200–300 km, in the D" region, where evidence for seismic anisotropy has been accumulating since the late 1980s, mostly from shear wave splitting measurements. Recently, a picture has been emerging, where strong anisotropy is associated with high shear velocities at the edges of the large low shear velocity provinces (LLSVPs) in the central Pacific and under Africa. These observations are consistent with being due to the presence of highly anisotropic MgSiO3 post-perovskite crystals, aligned during the deformation of slabs impinging on the core-mantle boundary, and upwelling flow within the LLSVPs. In this report we also discuss mineral physics aspects such as ultrahigh pressure deformation experiments, first principles calculations to obtain information about elastic properties, and derivation of dislocation activity based on bonding characteristics. Polycrystal plasticity simulations can predict anisotropy but models are still highly idealized and neglect the complex microstructure of polyphase aggregates with strong and weak components. A promising direction for future progress in understanding the origin of seismic anisotropy in the deep mantle and its relation to global mantle circulation, is to link macroscopic information from seismology and microscopic information mineral physics through geodynamics modeling. Anisotropy in the inner core was proposed 30 years ago to explain faster P wave propagation along the direction of the Earth's axis of rotation as well as anomalous splitting of core sensitive free oscillations. There is still uncertainty about the origin of this anisotropy. In particular, it is difficult to explain its strength, based on known elastic properties of iron, as it would require almost perfect alignment of iron crystals. Indeed, the strongly anomalous P travel times observed on paths from the South Sandwich Islands to Alaska may or may not be due to inner core anisotropy, and will need to be explained before consensus can be reached on the strength of anisotropy in the inner core and its origin.

58 GEOSCIENCES↗
DOE OSTI2023

Revising the dynamic energy budget theory with a new reserve mobilization rule and three example applications to bacterial growth

Dynamic energy budget (DEB) theory has been applied to model a wide range of organisms, including microbes. In the standard DEB model, biomass is partitioned into reserve and structural compartments, where reserve biomass is mobilized in a pseudolinear manner (while the reserve biomass density, defined as the ratio between reserve and structural biomass, decays linearly) to drive maintenance and the growth of structural biomass (and extracellular enzyme production if it is considered). However, the linear dynamics of the reserve biomass density makes the standard DEB model incapable of explaining the slowdown of microbial growth at high reserve density that is caused by macromolecular crowding effect which reduces biochemical reaction rates (a typical situation occurs when microbes are experiencing severe moisture stress) and is inconsistent with the observation that intracellular enzymatic reactions generally follow non-linear kinetics. By partitioning biomass into reserve, kinetic, and structural compartments, we show here that the Equilibrium Chemistry Approximation (ECA) kinetics can be used to represent enzymatically catalyzed reserve biomass mobilization that can then drive the kinetic and structural biomass synthesis. This revised DEB model better represents the tradeoff in ribosome allocation for structural growth and internal enzyme production, is structurally compatible with metabolic models of cell individuals, and includes the standard DEB model and the popular compromise model as special cases for representing population growth. We then applied the revised DEB model to interpret components of bacterial respiration, their dependence on substrate availability, and emergent microbial carbon use efficiency dynamics for an exponentially growing population. We found that the revised DEB model enables a better understanding of bacterial substrates use (carbon in our examples) than that can be derived from a few other models in the literature. In particular, the revised DEB model explains why carbon use efficiency may first increase, then plateau, and finally decrease with growth rate (and substrate uptake rate), as a function of proteomics. Additionally, the revised DEB model explains why the kinetic biomass compartment needs to be divided to reasonably incorporate proteomic control of microbial growth.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2011

Metal Speciation in Landfill Leachates with a Focus on the Influence of Organic Matter

This study characterizes the heavy-metal content in leachates collected from eight landfills in France. In order to identify heavy metal occurrence in the different size fractions of leachates, a cascade filtration protocol was applied directly in the field, under a nitrogen gas atmosphere to avoid metal oxidation. The results of analyses performed on the leachates suggest that most of the metals are concentrated in the <30 kDa fraction, while lead, copper and cadmium show an association with larger particles. Initial speciation calculations, without considering metal association with organic matter, suggest that leachate concentrations in lead, copper, nickel and zinc are super-saturated with respect to sulphur phases. Speciation calculations that account for metal complexation with organic matter, considered as fulvic acids based on C1(s) NEXAFS spectroscopy, show that this mechanism is not sufficient to explain such deviation from equilibrium conditions. It is therefore hypothesized that the deviation results also from the influence of biological activity on the kinetics of mineral phase precipitation and dissolution, thus providing a dynamic system. The results of chemical analyses of sampled fluids are compared with speciation calculations and some implications for the assessment of metal mobility and natural attenuation in a context of landfill risk assessment are discussed.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Identify the Removable Substructure in Carbon Activation

Activated carbon plays a pivotal role in achieving critical functions, such as separation, catalysis, and energy storage. A remaining question of carbon activation is which substructures in amorphous carbon are preferentially removed during activation. Herein, we report the first structure–activation correlation elucidated on the basis of unprecedented comprehensive characterization on carbon activation. We discover that activation under CO2 preferentially removes graphenic layers that are more defective. Therefore, the resulting activated carbon contains thinned turbostratic nanodomains that are of a higher local graphenic order. The mechanistic insights explain why more defective soft carbon is “burned” under CO2 at a much faster rate than hard carbon. The mechanism leads to an activation-based design principle of mesoporous carbon. Guided by this principle, a bimodal micromesoporous carbon is prepared simply by CO2 activation. Our findings may cause a paradigm shift for the rational design of nanoporous carbon.

Xing, Zhenyu↗
DOE OSTI2016

Thermodynamic and mass transfer modeling of carbon dioxide absorption into aqueous 2-amino-2-methyl-1-propanol

Explanations for the mass transfer behavior of 2-amino-2-methyl-1-propanol (AMP) are conflicting, despite extensive study of the amine for CO 2 capture. At equilibrium, aqueous AMP reacts with CO 2 to give bicarbonate in a 1:1 ratio. While this is the same stoichiometry as a tertiary amine, the reaction rate of AMP is 100 times faster. This work aims to explain the mass transfer behavior of AMP, specifically the stoichiometry and kinetics. An eNRTL thermodynamic model was used to regress wetted-wall column mass transfer data with two activity-based reactions: formation of carbamate and formation of bicarbonate. Data spanned 40–100 C and 0.15–0.60 mol CO 2 /mol alk). The fitted carbamate rate constant is three orders of magnitude greater than the bicarbonate rate constant. Rapid carbamate formation explains the kinetics, while the stoichiometry is explained by the carbamate reverting in the bulk liquid to allow CO 2 to form bicarbonate. Understanding the role of carbamate formation and diffusion in hindered amines enables optimizing solvent amine concentration by balancing viscosity and free amine concentration. Furthermore, this improves absorber design for CO 2 capture.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2020

Atomistic Insight into Cation Effects on Binding Energies in Cu-Catalyzed Carbon Dioxide Reduction

Electrolyte properties in general and electrolyte ions in particular have been shown to have significant effects on the kinetics of electrochemical CO 2 and CO reduction at metal electrodes, but these effects have not yet been fully understood. Here, we investigate the effects of cations at the aqueous electrolyte–Cu(211) interface on adsorbate binding energies and the electrolyte structure using density functional theory (DFT). Charging the interface via explicit Na + has systematic effects on adsorbate–electrolyte interactions and conformations. We describe specific local adsorbate–ion interactions, including direct alkali ion–adsorbate coordination and hydrogen bonding via ion-coordinated water molecules. The relative importance of these specific interactions and purely electrostatic field–adsorbate interactions is investigated by comparing the DFT-calculated ion effects to those predicted by purely electrostatic models of the interface and the adsorbates. We find that the trend in ion effects among different adsorbates at constant surface charge density is well explained by a purely electrostatic interaction model. The binding energy of OCCHO is found to depend strongly on the surface charge density as well as the spatial distribution of ions at constant surface charge density. These effects are also explained by a purely electrostatic local electrostatic field–adsorbate model. This indicates that alkali ion effects can be mainly attributed to purely electrostatic field interactions and that the local field at ion-stabilized active sites can depend significantly on both the overall charge density and on the spatial distribution of ions at constant charge density. This work provides new insight on alkali ion effects on a variety of adsorbates relevant to the CO 2 and CO reduction reactions by describing specific local ion–adsorbate interactions, systematic changes in adsorbate–electrolyte interactions induced by explicit surface charge, and comparisons of the calculated effects on binding energies to simple electrostatic field–adsorbate models to explain trends among various adsorbates and at varying surface charge densities and supercell configurations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗