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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 1,099 records · Page 61
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

The many phases of CaC{sub 2}

Polymorphic CaC{sub 2} was prepared by reacting mixtures of CaH{sub 2} and graphite with molar ratios between 1:1.8 and 1:2.2 at temperatures between 700 and 1400 °C under dynamic vacuum. These conditions provided a well controlled, homogeneous, chemical environment and afforded products with high purity. The products, which were characterized by powder X-ray diffraction, solid state NMR and Raman spectroscopy, represented mixtures of the three known polymorphs, tetragonal CaC{sub 2}-I and monoclinic CaC{sub 2}-II and -III. Their proportion is dependent on the nominal C/CaH{sub 2} ratio of the reaction mixture and temperature. Reactions with excess carbon produced a mixture virtually free from CaC{sub 2}-I, whereas high temperatures (above 1100 °C) and C-deficiency favored the formation of CaC{sub 2}-I. From first principles calculations it is shown that CaC{sub 2}-I is dynamically unstable within the harmonic approximation. This indicates that existing CaC{sub 2}-I is structurally/dynamically disordered and may possibly even occur as slightly carbon-deficient phase CaC{sub 2-δ}. It is proposed that monoclinic II is the ground state of CaC{sub 2} and polymorph III is stable at temperatures above 200 °C. Tetragonal I represents a metastable, heterogeneous, phase of CaC{sub 2}. It is argued that a complete understanding of the occurrence of three room temperature modifications of CaC{sub 2} will require a detailed characterization of compositional and structural heterogeneities within the high temperature form CaC{sub 2}-IV, which is stable above 450 °C. The effect of high pressure on the stability of the monoclinic forms of CaC{sub 2} was studied in a diamond anvil cell using Raman spectroscopy. CaC{sub 2}-II and -III transform into tetragonal CaC{sub 2}-I at about 4 and 1GPa, respectively. - Graphical abstract: The famous tetragonal form of CaC{sub 2}, CaC{sub 2}-I, is dynamically unstable. Why does it exist? Display Omitted - Highlights: • Critical review of complex polymorphism of the commodity chemical CaC{sub 2}. • Tetragonal CaC{sub 2}-I is identified as dynamical instable and its existence attributed to disorder. • With pressure monoclinic CaC{sub 2}-II and –III transform into tetragonal CaC{sub 2}-I. • The high temperature form CaC{sub 2}-IV is assigned a key role for understanding the polymorphism of CaC{sub 2}.

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

Lattice parameters and Raman-active phonon modes of β-(Al{sub x}Ga{sub 1−x}){sub 2}O{sub 3}

We present X-ray diffraction and Raman spectroscopy investigations of a (100)-oriented (Al{sub x}Ga{sub 1–x}){sub 2}O{sub 3} thin film on MgO (100) and bulk-like ceramics in dependence on their composition. The thin film grown by pulsed laser deposition has a continuous lateral composition spread allowing to determine precisely the dependence of the phonon mode properties and lattice parameters on the chemical composition. For x < 0.4, we observe the single-phase β-modification. Its lattice parameters and phonon energies depend linearly on the composition. We determined the slopes of these dependencies for the individual lattice parameters and for nine Raman lines, respectively. While the lattice parameters of the ceramics follow Vegard's rule, deviations are observed for the thin film. This deviation has only a small effect on the phonon energies, which show a reasonably good agreement between thin film and ceramics.

36 MATERIALS SCIENCE↗
DOE OSTI2014

High-quality InN films on MgO (100) substrates: The key role of 30° in-plane rotation

High crystalline layers of InN were grown on MgO(100) substrates by gas source molecular beam epitaxy. Good quality films were obtained by means of an in-plane rotation process induced by the annealing of an InN buffer layer to minimize the misfit between InN and MgO. In situ reflection high-energy electron diffraction showed linear streaky patterns along the [011{sup ¯}0] azimuth and a superimposed diffraction along the [112{sup ¯}0] azimuth, which correspond to a 30° α-InN film rotation. This rotation reduces the mismatch at the MgO/InN interface from 19.5% to less than 3.5%, increasing the structural quality, which was analyzed by high-resolution X-ray diffraction and Raman spectroscopy. Only the (0002) c plane diffraction of α-InN was observed and was centered at 2θ = 31.4°. Raman spectroscopy showed two modes corresponding to the hexagonal phase: E1(LO) at 591 cm{sup −1} and E2(high) at 488 cm{sup −1}. Hall effect measurements showed a carrier density of 9 × 10{sup 18} cm{sup −3} and an electron Hall mobility of 340 cm{sup 2}/(V s) for a film thickness of 140 nm.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Vibrational spectroscopy of shock compressed condensed phase nitrous oxide: Frequency shifts in the ν 1 mode

Over many years, we have published vibrational spectra of molecular materials at extreme pressure and temperature obtained using shock compression and coherent Raman spectroscopy methods. For diatomic molecules, we were able to extract vibrational temperatures from the intensities of spectrally resolved vibrational hot bands. Larger molecules in the condensed phase suffer band broadening effects that obscure the vibrational hot bands as the anharmonicities are typically smaller than the widths of the bands. This inability to resolve the hot bands inhibits the extraction of vibrational temperature and the measurement of the vibrational frequency of the fundamental. Here, we use a hot band model based on gas-phase anharmonic coupling coefficients to fit coherent anti-Stokes Raman spectra of the ν 1 vibrational mode of shock compressed condensed phase N 2 O with shock pressures and temperatures estimated from literature equations of state and compare to fits from a model using a single Gaussian peak. We report the resulting vibrational frequency shifts with shock pressure.

36 MATERIALS SCIENCE↗
DOE OSTI2023

In Situ Raman Mapping of Si Island Electrodes and Stress Modeling as a Function of Lithiation and Size

Si is known for cracking and delamination during electrochemical cycling of a battery due to the large volume change associated with Li insertion and extraction. However, it has been found experimentally that patterned Si island electrodes that are 200 nm thick and less than 7 μm wide can deform in a purely elastic manner. Inspired by this, we performed in situ Raman stress characterization of model poly-crystalline Si island electrodes using an electrochemical cell coupled with an immersion objective lens and designed for a short working distance. A 5 μm wide Si island electrode showed a parabolic stress profile during lithiation, while for a 15 μm Si island electrode, a stress plateau in the center of the electrode was observed. A continuum model with coupled electro-chemo-mechanical (ECM) physics was established to understand the stress measurement. A qualitative agreement was reached between modeling and experimental data, and the critical size effect could be explained by the Li diffusive flux as governed by competition between the Li concentration and hydrostatic stress gradients. Below the critical size, the stress gradient drives Li toward the edges, where the electrode volume is free to expand, while above the critical size, the stress plateau inhibits Li diffusion to the edge and forces destructive stress relief by cracking. Furthermore, this work represents a promising methodology for in situ characterization of ECM coupling in battery electrodes, with suggestions provided for further improvement.

25 ENERGY STORAGE↗
DOE OSTI2021

Electrocatalytic Isoxazoline–Nanocarbon Metal Complexes

In this work, we report the synthesis of new carbon-nanomaterial-based metal chelates that enable effective electronic coupling to electrocatalytic transition metals. In particular, multiwalled carbon nanotubes (MWCNTs) and few-layered graphene (FLG) were covalently functionalized by a microwave-assisted cyclo-addition with nitrile oxides to form metal-binding isoxazoline functional groups with high densities. The covalent attachment was evidenced by Raman spectroscopy, and the chemical identity of the surface functional groups was confirmed by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The functional carbon nanomaterials effectively chelate precious metals Ir(III), Pt(II), and Ru(III), as well as earth-abundant metals such as Ni(II), to afford materials with metal contents as high as 3.0 atom %. The molecularly dispersed nature of the catalysts was confirmed by X-ray absorption spectroscopy (XAS) and energy-dispersive X-ray spectroscopy (STEM-EDS) elemental mapping. The interplay between the chelate structure on the graphene surface and its metal binding ability has also been investigated by a combination of experimental and computational studies. The defined ligands on the graphene surfaces enable the formation of structurally precise heterogeneous molecular catalysts. The direct attachment of the isoxazoline functional group on the graphene surfaces provides strong electronic coupling between the chelated metal species and the conductive carbon nanomaterial support. We demonstrate that the metal-chelated carbon nanomaterials are effective heterogeneous catalysts in the oxygen evolution reaction with low overpotentials and tunable catalytic activity.

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

Quantum Dynamics and Spectroscopy of Ab Initio Liquid Water: The Interplay of Nuclear and Electronic Quantum Effects

Understanding the reactivity and spectroscopy of aqueous solutions at the atomistic level is crucial for the elucidation and design of chemical processes. However, the simulation of these systems requires addressing the formidable challenges of treating the quantum nature of both the electrons and nuclei. Exploiting our recently developed methods that provide acceleration by up to 2 orders of magnitude, we combine path integral simulations with on-the-fly evaluation of the electronic structure at the hybrid density functional theory level to capture the interplay between nuclear quantum effects and the electronic surface. Here we show that this combination provides accurate structure and dynamics, including the full infrared and Raman spectra of liquid water. This allows us to demonstrate and explain the failings of lower-level density functionals for dynamics and vibrational spectroscopy when the nuclei are treated quantum mechanically. Finally, these insights thus provide a foundation for the reliable investigation of spectroscopy and reactivity in aqueous environments.

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

Spectroscopic ellipsometry on Si/SiO{sub 2}/graphene tri-layer system exposed to downstream hydrogen plasma: Effects of hydrogenation and chemical sputtering

In this work, the optical response of graphene to hydrogen plasma treatment is investigated with spectroscopic ellipsometry measurements. Although the electronic transport properties and Raman spectrum of graphene change after plasma hydrogenation, ellipsometric parameters of the Si/SiO2/graphene tri-layer system do not change. This is attributed to plasma hydrogenated graphene still being electrically conductive, since the light absorption of conducting 2D materials does not depend on the electronic band structure. A change in the light transmission can only be observed when higher energy hydrogen ions (30 eV) are employed, which chemically sputter the graphene layer. An optical contrast is still apparent after sputtering due to the remaining traces of graphene and hydrocarbons on the surface. In brief, plasma treatment does not change the light transmission of graphene; and when it does, this is actually due to plasma damage rather than plasma hydrogenation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Structural and optical properties of cobalt slanted nanopillars conformally coated with few-layer graphene

Optical characterization of anisotropic multicomponent nanostructures is generally not a trivial task, since the relation between a material's structural properties and its permittivity tensor is nonlinear. In this regard, an array of slanted cobalt nanopillars that are conformally coated with few-layer graphene is a particularly challenging object for optical characterization, as it has a complex anisotropic geometry and comprises several materials with different topologies and filling fractions. Normally, a detailed characterization of such complex nanostructures would require a combination of several microscopic and spectroscopic techniques. In this letter, we demonstrate that the important structural parameters of these graphene-coated sculptured thin films can be determined using a fast and simple generalized spectroscopic ellipsometry test combined with an anisotropic Bruggeman effective medium approximation. The graphene coverage as well as structural parameters of nanostructured thin films agree excellently with electron microscopy and Raman spectroscopy observations. The demonstrated optical approach may also be applied to the characterization of other nanostructured materials.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Electric field-induced tuning of magnetism in PbFe{sub 0.5}Nb{sub 0.5}O{sub 3} at room temperature

We study the influence of electrical poling, carried out at room temperature, on the structure and magnetism of Pb(Fe{sub 0.5}Nb{sub 0.5})O{sub 3} by analyzing the differences observed in structural and magnetic properties before and after the electrical poling. The changes observed in magnetization of Pb(Fe{sub 0.5}Nb{sub 0.5})O{sub 3} before and after electrical poling exhibit considerably strong converse magnetoelectric effect at room temperature. In addition, the strengthening of Fe/Nb-O bond due to electrical poling is discussed on the basis of Raman spectral studies and analysis of neutron diffraction patterns. The potential tunability of magnetization with electrical poling can be an ideal tool for realization of application potential of this multiferroic material.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2019

The Effect of Fuel Stratification on the Detonation Wave Structure

Rotating detonation engines are a promising technology for stationary and mobile power generation applications. A form of pressure gain combustion, detonation engines allow for the recovery of the gas pressure lost in traditional constant pressure combustion and the fuel and oxidizer injection schemes. The rotating detonation engine annulus features a complex distribution of fuel-oxidizer due to the turbulent mixing of the fuel and oxidizer streams, with regions of varying equivalence ratio arranged in irregular patches within the domain. The primary objective of this work is to gain an understanding of the interaction between the detonation wave and the fuel-oxidizer mixture inhomogeneity. Past studies have found that inhomogeneities result in irregular detonation cell structures and affect wave propagation. To this end, the influence of a stratified fuel-oxidizer mixture on the behavior and structure of the detonation wave is simulated through a direct numerical simulation approach. Three different fuel-oxidizer stratification length scales are evaluated, and their effects on the properties of the detonation wave are discussed.

Prakash, Supraj↗
DOE OSTI2024

Low-Temperature Annealing of Nanoscale Defects in Polycrystalline Graphite

Polycrystalline graphite contains multi-scale defects, which are difficult to anneal thermally because of the extremely high temperatures involved in the manufacturing process. In this study, we demonstrate annealing of nuclear graphite NBG-18 at temperatures below 28 °C, exploiting the electron wind force, a non-thermal stimulus. High current density pulses were passed through the specimens with a very low-duty cycle so that the electron momentum could mobilize the defects without heating the specimen. The effectiveness of this technique is presented with a significant decrease in electrical resistivity, defect counts from X-ray computed tomography, Raman spectroscopy, and nanoindentation-based mechanical characterization. Such multi-modal evidence highlights the feasibility of nanoscale defect control at temperatures about two orders of magnitude below the graphitization temperature.

Liu, Gongyuan↗
NASA NTRS2012

Correction Technique for Raman Water Vapor Lidar Signal-Dependent Bias and Suitability for Water Wapor Trend Monitoring in the Upper Troposphere

The MOHAVE-2009 campaign brought together diverse instrumentation for measuring atmospheric water vapor. We report on the participation of the ALVICE (Atmospheric Laboratory for Validation, Interagency Collaboration and Education) mobile laboratory in the MOHAVE-2009 campaign. In appendices we also report on the performance of the corrected Vaisala RS92 radiosonde measurements during the campaign, on a new radiosonde based calibration algorithm that reduces the influence of atmospheric variability on the derived calibration constant, and on other results of the ALVICE deployment. The MOHAVE-2009 campaign permitted the Raman lidar systems participating to discover and address measurement biases in the upper troposphere and lower stratosphere. The ALVICE lidar system was found to possess a wet bias which was attributed to fluorescence of insect material that was deposited on the telescope early in the mission. Other sources of wet biases are discussed and data from other Raman lidar systems are investigated, revealing that wet biases in upper tropospheric (UT) and lower stratospheric (LS) water vapor measurements appear to be quite common in Raman lidar systems. Lower stratospheric climatology of water vapor is investigated both as a means to check for the existence of these wet biases in Raman lidar data and as a source of correction for the bias. A correction technique is derived and applied to the ALVICE lidar water vapor profiles. Good agreement is found between corrected ALVICE lidar measurments and those of RS92, frost point hygrometer and total column water. The correction is offered as a general method to both quality control Raman water vapor lidar data and to correct those data that have signal-dependent bias. The influence of the correction is shown to be small at regions in the upper troposphere where recent work indicates detection of trends in atmospheric water vapor may be most robust. The correction shown here holds promise for permitting useful upper tropospheric water vapor profiles to be consistently measured by Raman lidar within NDACC (Network for the Detection of Atmospheric Composition Change) and elsewhere, despite the prevalence of instrumental and atmospheric effects that can contaminate the very low signal to noise measurements in the UT.

MOHAVE-2009↗
DOE OSTI2017

Quantum interference effects on the intensity of the G modes in double-walled carbon nanotubes

The effects of quantum interferences on the excitation dependence of the intensity of G modes have been investigated on single-walled carbon nanotubes [Duque et al., Phys. Rev. Lett.108, 117404 (2012)]. In this work, by combining optical absorption spectroscopy and Raman scattering on individual index identified double-walled carbon nanotubes, we examine the experimental excitation dependence of the intensity of longitudinal optical and transverse optical G modes of the constituent inner and outer single-walled carbon nanotubes. The observed striking dependencies are understood in terms of quantum interference effects. Considering such effects, the excitation dependence of the different components of the G modes permit to unambiguously assign each of them as originating from the longitudinal or transverse G modes of inner and outer tubes.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Size-Dependent Optical Properties of Colloidal CdS Quantum Dots Passivated by Thioglycolic Acid

The results of studies of the optical properties of ensembles of colloidal CdS quantum dots passivated by thioglycolic acid are reported. The average dimensions of the quantum dots lie in the range from 1.7 to 5.8 nm. By X-ray diffraction studies and Raman spectroscopy, it is established that quantum dots crystallize with the formation of a cubic crystal lattice. The systematic features of the quantum-confinement effect in the optical absorption and luminescence spectra, as well as in the luminescence excitation spectra, are established. The features manifest themselves as a blue shift of the corresponding bands with decreasing quantum-dot dimensions. From analysis of the nanosecond luminescence kinetics, it is concluded that experimentally observed radiative recombination proceeds by the donor–acceptor mechanism.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Online Monitoring of Catalytic Processes by Fiber-Enhanced Raman Spectroscopy

An innovative solution for real-time monitoring of reactions within confined spaces, optimized for Raman spectroscopy applications, is presented. This approach involves the utilization of a hollow-core waveguide configured as a compact flow cell, serving both as a conduit for Raman excitation and scattering and seamlessly integrating into the effluent stream of a cracking catalytic reactor. The analytical technique, encompassing device and optical design, ensures robustness, compactness, and cost-effectiveness for implementation into process facilities. Notably, the modularity of the approach empowers customization for diverse gas monitoring needs, as it readily adapts to the specific requirements of various sensing scenarios. As a proof of concept, the efficacy of a spectroscopic approach is shown by monitoring two catalytic processes: CO 2 methanation (CO 2 + 4H 2 → CH 4 + 2H 2 O) and ammonia cracking (2NH 3 → N 2 + 3H 2 ). Leveraging chemometric data processing techniques, spectral signatures of the individual components involved in these reactions are effectively disentangled and the results are compared to mass spectrometry data. This robust methodology underscores the versatility and reliability of this monitoring system in complex chemical environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Effect of cleaning procedures on the electrical properties of carbon nanotube transistors—A statistical study

The interface between a carbon nanotube (CNT) and its environment can dramatically affect the electrical properties of CNT-based field-effect transistors (FETs). For such devices, the channel environment plays a significant role inducing doping or charge traps giving rise to hysteresis in the transistor characteristics. Thereby the fabrication process strongly determines the extent of those effects and the final device performance. In CNT-based devices obtained from dispersions, a proper individualization of the nanotubes is mandatory. This is generally realized by an ultrasonic treatment combined with surfactant molecules, which enwrap nanotubes forming micelle aggregates. To minimize impact on device performance, it is of vital importance to consider post-deposition treatments for removal of surfactant molecules and other impurities. In this context, we investigated the effect of several wet chemical cleaning and thermal post treatments on the electrical characteristics as well as physical properties of more than 600 devices fabricated only by wafer-level compatible technologies. We observed that nitric acid and water treatments improved the maximum-current of devices. Additionally, we found that the ethanol treatment successfully lowered hysteresis in the transfer characteristics. The effect of the chemical cleaning procedures was found to be more significant on CNT-metal contacts than for the FET channels. Moreover, we investigated the effect of an additional thermal cleaning step under vacuum after the chemical cleaning, which had an exceptional impact on the hysteresis behavior including hysteresis reversal. The presence of surfactant molecules on CNT was evidenced by X-ray photoelectron and Raman spectroscopies. By identifying the role of surfactant molecules and assessing the enhancement of device performance as a direct consequence of several cleaning procedures, these results are important for the development of CNT-based electronics at the wafer-level.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗