SEARCH · Engineering Papers
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.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
The spontaneous alpha promoted PuO 2 -H 2 O reaction proceeds with establishment of a steady state that is unattainable via an equilibrium-controlled reaction or a sequence of equilibrium reactions.
A combination of kinetic, thermodynamic, and spectroscopic techniques demonstrates that increasing the water fraction within organic solvents accelerates alkene epoxidations while suppressing the undesired H 2 O 2 decomposition pathway.
Here, the vibrational properties of CO 2 –H 2 O-bearing and dry synthetic K-rich basaltic glasses were investigated at room temperature and pressures between 0.0001–5.5 GPa using the diamond anvil cell combined with in situ reflectance and transmittance Fourier Transform infrared micro-spectroscopy. The absorption coefficient a(v) calculated from the Kramers-Kronig relation shows that glasses are dominated by the Q 2 aluminosilicate unit followed by Q 1 , Q 3 . The variation in Q n concentration upon compression suggests that glasses undergo polymerization from ambient pressure to 2 GPa followed by less marked structural changes up to 4 GPa, above which the structure is further polymerized. Once decompressed, glasses retained a polymerized structure. Our results show that 1.03 wt% CO 2 -1.42 wt% H 2 O in a glass with 3.10 wt% K 2 O and 46.77 wt% SiO 2 prevent the formation of fully polymerized connections when cold-compressed. Our results can be used to explain the effect of volatiles and alkali on the rheology of natural basaltic magmas.
This report provides an overview of engineering and experimental efforts to establish a new capability for measuring H2 uptake rates for Tritium Producing Abosrber Rod (TPBAR) getter materials. This new system was used to gain a better understanding of the impact of contaminant species (CO 2 , CO, CH 4 , and H 2 O) on getter performance under relevant hydrogen uptake conditions (350 °C, 20 torr). Herein, we successfully established a high-resolution gravimetric sorption (HRGS) system in a flow through configuration that can measure sample mass changes with high resolution (1 µg or 10 µg) over long experiment times (days), high temperature, and varying pressures. We coupled this capability with an in-line universal gas analyzer (UGA) system to characterize potential surface chemistry side reactions occurring after contaminant gas exposure. The major findings of this study suggest that methane and CO have the most detrimental effects on getter H 2 uptake performance showing large changes in rate after exposure compared to CO 2 and water. The effect of these contaminant species did not influence getter sample capacity (~ 1.8 wt% H 2 ). After CO and methane exposure, changes in getter rate were accompanied by observable Ni-surface defects and pinholes via SEM imaging suggesting possible Ni- layer corrosion. Additionally, the increase in C and O signal in the zircaloy layer, observed via EDX, point to C and O species transport through the getter sample resulting in the formation of carbides and oxide species. Thus, co-exposure studies where mixed gases or water vapor are introduced together will be important to further understand what mechanisms are contributing to Ni-layer corrosion and changes in getter performance.
We combined synchrotron-based infrared absorbance and Raman scattering spectroscopies with diamond anvil cell techniques and a symmetry analysis to explore the properties of multiferroic (NH 4 ) 2 FeCl 5 ·H 2 O under extreme pressure–temperature conditions. Compression-induced splitting of the Fe–Cl stretching, Cl–Fe–Cl and Cl–Fe–O bending, and NH 4 + librational modes defines two structural phase transitions, and a group–subgroup analysis reveals space group sequences that vary depending upon proximity to the unexpectedly wide order–disorder transition. Here, we bring these findings together with prior high-field work to develop the pressure–temperature–magnetic field phase diagram uncovering competing polar, chiral, and magnetic phases in this system.
A systematic investigation of uranyl borates under different synthetic conditions resulted in five new 2D compounds, namely, (H 3 O)[(UO 2 )(BO 3 )], Li[(UO 2 )(BO 3 )] · (H 2 O), α-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ], β-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ] and K 2.5 [(UO 2 ) 5 (BO 3 ) 2 O 2.5 (OH) 1.5 ] · (H 2 O) 2.5 . (H 3 O)[(UO 2 )(BO 3 )] and Li[(UO 2 )(BO 3 )] · (H 2 O) were obtained from hydrothermal reactions at 220 °C using the same mineralizer. Both materials possess the uranophane sheet topology with different symmetry of the unit cells. In the structure of (H 3 O)[(UO 2 )(BO 3 )] and Li[(UO 2 )(BO 3 )] · (H 2 O), UO 7 pentagonal bipyramids share edges and vertexes with four BO 3 planar triangles. α-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ] and β-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ] are polytypes. α-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ] was synthesized from a high-temperature solid-state reaction under ambient pressure; whereas β-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ] was obtained from a high-temperature/high-pressure (HT/HP) reaction. Both structures have an identical anion topology, but β-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ] crystallizes in space group with higher symmetry. In K 2.5 [(UO 2 ) 5 (BO 3 ) 2 O 2.5 (OH) 1.5 ] · (H 2 O) 2.5 , which was obtained from a hydrothermal reaction, UO 7 polyhedra share vertexes and edges with two independent BO 3 triangles, forming the most complex uranyl borate layers among all five compounds. The different synthetic routes, novel topologies, thermal behavior and Raman spectra are discussed.
Here, we measured the elastic velocities of a synthetic polycrystalline β-Mg 2 SiO 4 containing 0.73 wt.% H 2 O to 10 GPa and 600 K using ultrasonic interferometry combined with synchrotron X-radiation. Third-order Eulerian finite strain analysis of the high P and T data set yielded K so = 161.5(2) GPa, G o = 101.6(1) GPa, and (∂K s /∂P) T = 4.84(4), (∂G/∂P) T = 1.68(2) indistinguishable from K so = 161.1(3) GPa, G o = 101.4(1) GPa, and (∂K s /∂P) T = 4.93(4), (∂G/∂P) T = 1.73(2) from the linear fit. The hydration of the wadsleyite by 0.73 wt.% decreases K s and G moduli by 5.3% and 8.6%, respectively, but no measurable effect was noted for (∂K s /∂P) T and (∂G/∂P) T . The temperature derivatives of the K s and G moduli from the finite strain analysis (∂K S /∂T) P = –0.013(2) GPaK –1 , (∂G/∂T) P = –0.015(0.4) GPaK –1 , and the linear fit (∂K S /∂T) P = –0.015(1) GPaK –1 , (∂G/∂T) P = –0.016(1) GPaK –1 are in agreement, and both data sets indicating the |(∂G/∂T) P | to be greater than |(∂K S /∂T) P |. Calculations yield ΔV p(α-β) = 9.88% and ΔV S(α-β) = 8.70% for the hydrous β-Mg 2 SiO 4 and hydrous α-Mg 2 SiO 4 , implying 46–52% olivine volume content in the Earth’s mantle to satisfy the seismic velocity contrast ΔV s = ΔV P = 4.6% at the 410 km depth.
In this work we report the first full-dimensional quantum mechanical calculations of the ro-vibrational inelastic scattering dynamics between water molecules and argon atoms on an accurate potential energy surface, using a recently developed time-independent quantum method based on the close-coupling approach. The state-to-state integral cross-sections and rate coefficients show strong observance of gap laws. The calculated thermal rate coefficients for the relaxation of the stretching fundamental states of H 2 O are in good agreement with experimental values, while those for the bending overtone state are approximately five times smaller than the values extracted through a previous kinetic modeling of fluorescence decay data. Our state-specific quantum scattering results suggest the need to reassess the kinetic modeling of the experimental data. This work advanced our understanding of the quantum dynamics of vibrationally inelastic energy transfer processes involving polyatomic molecules.
The formation of isomers when trapping floppy cluster ions in a temperature-controlled ion trap is a generally observed phenomenon. This involves collisional quenching of the ions initially formed at high temperature by buffer gas cooling until their internal energies fall below the barriers in the potential energy surface that separate them. Here we explore the kinetics at play in the case of the two isomers adopted by the H + (H 2 O) 6 cluster ion that differ in the proton accommodation motif. One of these is most like the Eigen cation with a tricoordinated hydronium motif (denoted E), and the other is most like the Zundel ion with the proton equally shared between two water molecules (denoted Z). After initial cooling to about 20 K in the radiofrequency (Paul) trap, the relative populations of these two spectroscopically distinct isomers are abruptly changed through isomer-selective photoexcitation of bands in the OH stretching region with a pulsed (~6 ns) infrared laser while the ions are in the trap. We then monitor the relaxation of the vibrationally excited clusters and reformation of the two cold isomers by recording infrared photodissociation spectra with a second IR laser as a function of delay time from the initial excitation. The latter spectra are obtained after ejecting the trapped ions into a time-of-flight photofragmentation mass spectrometer, thus enabling long (~0.1 s) delay times. Excitation of the Z isomer is observed to display long-lived vibrationally excited states that are collisionally cooled on a ms time scale, some of which quench into the E isomer. These excited E species then display spontaneous interconversion to the Z form on a ~10 ms time scale. Furthermore, these qualitative observations set the stage for a series of experimental measurements that can provide quantitative benchmarks for theoretical simulations of cluster dynamics and the potential energy surfaces that underlie them.
Here, empirical, highly accurate non-relativistic electronic total atomization energies (eTAEs) are established by combining experimental or computationally converged treatments of the nuclear motion and relativistic contributions with the total atomization energies of HF, CO, N 2 , and H 2 O obtained from the Active Thermochemical Tables. These eTAEs, which have estimated (2σ) uncertainties of less than 10 cm -1 (0.12 kJ mol -1 ), form the basis for an analysis of high-level ab initio quantum chemical calculations that aim at reproducing these eTAEs for the title molecules. The results are then employed to analyze the performance of the high-accuracy extrapolated ab initio thermochemistry, or High-Accuracy Extrapolated Ab Initio Thermochemistry (HEAT), family of theoretical methods. The method known as HEAT-345(Q), in particular, is found to benefit from fortuitous error cancellation between its treatment of the zero-point energy, extrapolation errors in the Hartree-Fock and coupled cluster contributions, neglect of post-(T) core-correlation, and the basis-set error involved in higher-level correlation corrections. In addition to shedding light on a longstanding curiosity of the HEAT protocol—where the cheapest HEAT-345(Q) performs comparably to the theoretically more complete HEAT-456QP procedure—this study lays the foundation for extended HEAT variants that offer substantial improvements in accuracy relative to the established approaches.
The emergence of novel magnetic states becomes more likely when the inversion symmetry of the crystal field, relative to the center between two spins, is broken. We propose that placing magnetic spins in inequivalent sites in a polar lattice can promote a realization of nontrivial magnetic states and associated magnetic properties. To test our hypothesis, we study Fe 2 (SeO 3 )(H 2 O) 3 as a model system that displays two distinct Fe(1) and Fe(2) magnetic sites in a polar structure (R3c space group). At low fields μ 0 H≤ 0.06 T, the material undergoes an antiferromagnetic ordering with T N1 = 77 K and a second transition at T N2 ≈ 4 K. At μ 0 H≥ 0.06 T and 74 K ≤T≤ 76 K, a positive entropy change of ∼0.12 mJ mol −1 K −1 can be associated with a metamagnetic transition to possibly nontrivial spin states. At zero field, Fe(1) is nearly fully ordered at T≈ 25 K, while Fe(2) features magnetic frustration down to T = 4 K. The magnetic ground state, a result corroborated by single-crystal neutron diffraction and 57 Fe Mössbauer spectroscopy, is a noncollinear antiparallel arrangement of ferrimagnetic Fe(1)–Fe(2) dimers along the c-axis. The results demonstrate that placing distinct magnetic sites in a polar crystal lattice can enable a new pathway to modifying spin, orbital, and lattice degrees of freedom for unconventional magnetism.
We report a simple route based upon seed-mediated growth to the synthesis of Pd@Au x Pd 1-x (0.8≤x≤1) core–shell nanocubes. Benefiting from the well-defined {100} facets and an optimal Au/Pd ratio for the surface, the nanocubes bearing a shell made of Au 0.95 Pd 0.05 work as an efficient electrocatalyst toward H 2 O 2 production, with high selectivity of 93–100 % in the low-overpotential region of 0.4–0.7 V. When the Au 0.95 Pd 0.05 alloy is confined to a shell of only three atomic layers in thickness, the electrocatalyst is able to maintain its surface structure and elemental composition, endowing continuous and stable production of H2O2 during oxygen reduction at a high rate of 1.62 mol g( Pd+Au ) -1 h -1 . This work demonstrates a versatile route to the rational development of active and durable electrocatalysts based upon alloy nanocrystals.
This paper introduces inverse backscatter absorption gas imaging (iBAGI), a transparent gas imaging technique based on absorption spectroscopy of gases naturally present in ambient air being displaced by transparent gases. We demonstrate reconstruction of a 2-D image of a dry gas plume by measuring light of a raster-scanned diode laser tuned to an absorption line of atmospheric H 2 O. We quantify the performance depending on the distance to the backdrop and show that the key transmission metric is independent of absorption path length. We conclude with an outlook toward calibration-free, single-ended iBAGI using scattering from low-reflectivity backdrops.
The crystal structure of indacaterol hydrogen maleate has been solved and refined using synchrotron X-ray powder diffraction data, and optimized using density functional techniques. Indacaterol hydrogen maleate crystallizes in space groupP-1 (#24) witha= 8.86616(9),b= 9.75866(21),c= 16.67848(36) Å,α= 102.6301(10), β = 94.1736(6),γ= 113.2644(2)°,V= 1273.095(7) Å 3 , andZ= 2 at 295 K. The crystal structure consists of layers of cations and anions parallel to theab-plane. Traditional N–H⋯O and O–H⋯O hydrogen bonds link the cations and anions into chains along thea-axis. There is a strong intramolecular charge-assisted O–H⋯O hydrogen bond in the non-planar hydrogen maleate anion. There are also two C–H⋯O hydrogen bonds between the anion and cation. The cation makes a strong N–H⋯O hydrogen bond to the anion, but also acts as a hydrogen bond donor to an aromatic C in another cation. The amino group makes bifurcated N–H⋯O hydrogen bonds, one intramolecular and the other intermolecular. The hydroxyl group acts as a donor to another cation. The powder pattern has been submitted to ICDD for inclusion in the Powder Diffraction File™ (PDF®).
A metal–organic framework, MIL-47(V) containing coordinatively saturated V +IV sites linked together by terephthalic linkers, was prepared by a solvothermal method and evaluated as a catalyst in the epoxidation of cyclohexene. We have compared the catalytic activity in the condensed and gas phase oxidation of cyclohexene to discuss the effect of temperature and reaction phase in cyclohexene epoxidation over MIL-47(V). The catalysts were examined for the epoxidation of cyclohexene with H 2 O 2 at 50, 65, 120, and 150 °C. Finally, we observed significant differences in product selectivity between liquid-phase and gas-phase operations and confirmed that the active sites are tightly incorporated into the MOF as node channels and thus resistant to leaching.
A reaction usually involves a few active modes while the other modes are largely preserved throughout the reaction as spectators. Excitation of an active mode is expected to promote the reaction, but depositing energy in a spectator mode typically has no effect, because of the differing ability for energy flow to the reaction coordinate. Here, we report a surprising case of mode specificity in a key radical–radical reaction OH + HO 2 → H 2 O + O 2 , where such canonical expectations fail to hold. Despite its spectator nature, the vibrational excitation of the OH reactant is shown at low collision energies to enhance the reactivity significantly. This unique effect can be attributed to the increased attraction with HO 2 due to the larger dipole of the stretched OH. At low collision energies, the stronger attraction increases the chance of capturing the reactants to form a hydrogen-bonded complex, thus of passing through the submerged barrier. The novel mechanism differs from the conventional vibrational enhancement via coupling to the reaction coordinate at the transition state, enriching our understanding of mode specificity in chemistry.
Formation of vitreous ice during rapid compression of water at room temperature is important for biology and the study of biological systems. Here, we show that Raman spectra of rapidly compressed water at greater than 1 GPa at room temperature exhibits the signature of high-density amorphous ice, whereas the X-ray diffraction (XRD) pattern is dominated by crystalline ice VI. To resolve this apparent contradiction, we used molecular dynamics simulations to calculate full vibrational spectra and diffraction patterns of mixtures of vitreous ice and ice VI, including embedded interfaces between the two phases. We show quantitatively that Raman spectra, which probe the local polarizability with respect to atomic displacements, are dominated by the vitreous phase, whereas a small amount of the crystalline component is readily apparent by XRD. The results of our combined experimental and theoretical studies have implications for detecting vitreous phases of water, survival of biological systems under extreme conditions, and biological imaging. The results provide additional insight into the stable and metastable phases of H 2 O as a function of pressure and temperature, as well as of other materials undergoing pressure-induced amorphization and other metastable transitions.
Negative linear compressibility (NLC) is a rare high-pressure observation that lattice contraction is accompanied by the structural expansion along a specific direction. Generally, this counterintuitive phenomenon only derives from the intrinsic structural characteristics of materials and cannot be tuned by external perturbations. Searching for an effective method to control NLC effect is still a challenge in both chemical and material science. In this work, we successfully discover and select the NLC behaviors in the metal-organic framework (MOF) of [Cu(4,4'-bpy) 2 (H 2 O) 2 ]·SiF 6 (Cu(bpy)·SiF) through controlling the pressure conditions therein. The NLC effect of Cu(bpy)·SiF originates from the wine-rack mechanism that quasi-square grids transfer to rhombic ones with the structural expansion along the diagonal direction at high pressure. Meanwhile, both of the pressure range and magnitude of the NLC responses are enlarged with optimized pressure conditions. This study not only presents the intriguing selected NLC behaviors of a MOF but also proves the effects of pressure conditions on NLC, which offers promising strategies for further design and applications of NLC materials.