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At least 649 records · Page 36

SPADE: A Rock Crushing and Sample Handling System Developed for Mars Missions

Access to the interior of rocks on Mars is an important goal for understanding Mars petrology and geologic history. The spectral signature of the potentially diverse mineralogy of rocks on Mars is veiled by the ubiquitous dust and may be further hidden by weathered rind. We have developed a rock crusher and sample distribution system under the auspices of NASA s PIDDP program. We call it the SPADE : the Sample Processing and Distribution Experiment. Its purpose is to access the interiors of rocks on Mars and prepare samples for analysis by a suite of in situ instruments.

Hansen, Candice J.↗

Dielectric and electrical studies of Pr{sup 3+} doped nano CaSiO{sub 3} perovskite ceramics

Highlights: • CaSiO{sub 3}:Pr{sup 3+} was prepared by facile low temperature solution combustion method. • The crystalline phase of the product is obtained by adopting sintering method. • Samples prepared at 500 °C and calcined at 900 °C for 3 h showed β-phase. • The Pr{sup 3+} doped CaSiO{sub 3} shows “unusual results”. • The electrical microstructure has been accepted to be of internal barrier layer capacitor. - Abstract: CaSiO{sub 3} nano-ceramic powder doped with Pr{sup 3+} has been prepared by solution combustion method. The powder Ca{sub 0.95}Pr{sub 0.05}SiO{sub 3} is investigated for its dielectric and electrical properties at room temperature to study the effect of doping. The sample is characterized by X-ray diffraction and infrared spectroscopy. The size of either of volume elements of CaSiO{sub 3}:Pr{sup 3+} estimated from transmission electron microscopy is about 180–200 nm. The sample shows colossal dielectric response at room temperature. This colossal dielectric behaviour follows Debye-type relaxation and can be explained by Maxwell–Wagner (MW) polarization. However, analysis of impedance and electric modulus data using Cole–Cole plot shows that it deviates from ideal Debye behaviour resulting from the distribution of relaxation times. The distribution in the relaxation times may be attributed to existence of electrically heterogeneous grains, insulating grain boundary, and electrode contact regions. Doping, thus, results in substantial modifications in the dielectric and electrical properties of the nano-ceramic CaSiO{sub 3}.

36 MATERIALS SCIENCE↗

Magnetocaloric Effect and Critical Behavior Investigations in La{sub 0.45}Pr{sub 0.2}Sr{sub 0.35}MnO{sub 3} Manganite Oxide

Structural, magnetic, and magnetocaloric effect (MCE) properties and the critical behavior of the La{sub 0.45}Pr{sub 0.2}Sr{sub 0.35}MnO{sub 3} sample prepared by the sol–gel method have been investigated. The X-ray diffraction characterization reveals that our sample crystallizes in the orthorhombic structure with Pnma space group. Magnetization versus temperature measurement shows that our compound exhibits a ferromagnetic–paramagnetic transition. The Curie temperature is found to be 348 K. Close to this temperature, the maximum values of the magnetic entropy change (ΔS{sub M}) and the relative cooling power (RCP) are found to be 2.84 J/kg/K and 230 J/K under µ{sub 0}H = 5 T, respectively. The Arrott plots revealed that this compound exhibits a second-order magnetic phase transition at T{sub C}. The critical behavior has been investigated by several techniques which are the modified Arrott plot method, the Kouvel–Fisher method, and the critical isotherm analysis. The obtained critical exponents β, γ, and δ are consistent with those predictions of the mean-field model. Their reliability was confirmed by Widom’s scaling relation, as well as the universal scaling hypothesis.

36 MATERIALS SCIENCE↗

Sol–gel synthesis and enhanced photocatalytic activity of doped bismuth tungsten oxide composite

Highlights: • Co dopant results in the phase change from Bi{sub 2}WO{sub 6} to Bi{sub 2}WO{sub 6}/Bi{sub 14}W{sub 2}O{sub 27} heterostructure. • Enhanced photocatalytic activity of Bi{sub 2}WO{sub 6}/Bi{sub 14}W{sub 2}O{sub 27} heterostructure. • Synergistic effects coming from the interactions between Bi{sub 14}W{sub 2}O{sub 27} and Bi{sub 2}WO{sub 6} - Abstract: Pristine Bi{sub 2}WO{sub 6} and Bi{sub 2}WO{sub 6}/Bi{sub 14}W{sub 2}O{sub 27} photocatalysts were synthesized by sol–gel method using Co(II) cation as dopant. The influence of Co dopant to the formation of Bi{sub 2}WO{sub 6}/Bi{sub 14}W{sub 2}O{sub 27} heterostructure composite was discussed. The photocatalytic activities of as-prepared samples were evaluated sufficiently by using rhodamine B as target organic pollutants under visible light. The as-prepared Bi{sub 2}WO{sub 6}/Bi{sub 14}W{sub 2}O{sub 27} heterostructure achieved enhanced optical absorption in the visible-light region, and exhibited much higher photocatalytic activities than that of pristine Bi{sub 2}WO{sub 6}. The optimum Bi/Co molar ratio and calcining temperature were also explored. The enhanced activities were attributed to the formation of heterostructure in suppressing the recombination of photo-generated carriers. The Co dopant species would participate to reduce the charge carrier recombination by acting as trapping sites for photogenerated charges. A possible photocatalytic mechanism over Bi{sub 2}WO{sub 6}/Bi{sub 14}W{sub 2}O{sub 27} heterostructure was proposed.

36 MATERIALS SCIENCE↗

Diffusion phenomenon at the interface of Cu-brass under a strong gravitational field

To investigate diffusion phenomenon at the interface between Cu and brass under a strong gravitational field generated by ultracentrifuge apparatus, we performed gravity experiments on samples prepared by electroplating with interfaces normal and parallel to the direction of gravity. For the parallel-mode sample, for which sedimentation cannot occur thorough the interface, the concentration change was significant within the lower gravity region; many pores were observed in this region. Many vacancies arising from crystal strain due to the strong gravitational field moved into the lower gravity region, and enhanced the atoms mobilities. For the two normal-mode samples, which have interface normal to the direction of gravity, the composition gradient of the brass-on-Cu sample was steeper than that for Cu-on-brass. This showed that the atoms of denser Cu diffuse in the direction of gravity, whereas Zn atoms diffuse in the opposite direction by sedimentation. The interdiffusion coefficients became higher in the Cu-on-brass sample, and became lower in the brass-on-Cu sample. This rise may be related to the behavior of the vacancies.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Anisotropic Thermal Transport in Quasi-2D Ruddlesden-Popper Hybrid Perovskite Superlattices

Two-dimensional hybrid metal-halide perovskites (2D-MHPs) have emerged as important solution-processed semiconductors with favorable optical and electronic properties for diverse applications in photovoltaics, optoelectronics, and spintronics. The quasi-2D layered structures, featuring large acoustic impedance mismatches between the organic and inorganic sublattices, are expected to result in distinct and anisotropic thermal transport properties along the cross-plane and in-plane directions. Here, we introduce transducer-free vibrational-pump-visible-probe (VPVP) approaches that enable accurate quantification of anisotropic thermal transport properties in various archetypical single-crystalline 2D-MHPs. Specifically, using VPVP spectroscopy and VPVP microscopy, we measure the anisotropic thermal diffusivities of 2D-MHPs with systematically varied Pb-I octahedral layer thicknesses, as well as organic spacer types and lengths, revealing how these structural parameters alter the cross-plane and in-plane thermal transport properties in distinct ways. While diffuse interface scattering plays an important role in dictating cross-plane thermal transport, in-plane thermal transport is primarily determined by phonon transport within interconnected inorganic layers. Density functional theory incorporating four-phonon scatterings provides further insight into the low thermal conductivity and modest thermal conduction anisotropy in 2D-MHPs. Our work demonstrates a new all-optical and noncontact method, which requires minimal sample preparation and allows direct visualization of cross-plane and in-plane thermal transport, potentially compatible with sample environments. The demonstrated VPVP approaches can advance understanding of thermal transport in 2D-MHPs as well as wide-ranging hybrid and polymeric semiconductors beyond 2D-MHPs.

36 MATERIALS SCIENCE↗

Mars ultraviolet simulation facility

A facility was established for long-duration ultraviolet (UV) radiation exposure of natural and synthetic materials in order to test hypotheses concerning Martian soil chemistry observed by the Viking Mars landers. The system utilized a 2500 watt xenon lamp as the radiation source, with the beam passing through a heat-dissipating water filter before impinging upon an exposure chamber containing the samples to be irradiated. The chamber was designed to allow for continuous tumbling of the samples, maintenance of temperatures below 0 C during exposure, and monitoring of beam intensity. The facility also provided for sample preparation under a variety of atmospheric conditions, in addition to the Mars nominal. As many as 33 sealed sample ampules have been irradiated in a single exposure. Over 100 samples have been irradiated for approximately 100 to 700 h. The facility has performed well in providing continuous UV irradiation of multiple samples for long periods of time under simulated Mars atmospheric and thermal conditions.

Zill, L. P.↗

Comet composition and density analyzer

Distinctions between cometary material and other extraterrestrial materials (meteorite suites and stratospherically-captured cosmic dust) are addressed. The technique of X-ray fluorescence (XRF) for analysis of elemental composition is involved. Concomitant with these investigations, the problem of collecting representative samples of comet dust (for rendezvous missions) was solved, and several related techniques such as mineralogic analysis (X-ray diffraction), direct analysis of the nucleus without docking (electron macroprobe), dust flux rate measurement, and test sample preparation were evaluated. An explicit experiment concept based upon X-ray fluorescence analysis of biased and unbiased sample collections was scoped and proposed for a future rendezvous mission with a short-period comet.

Clark, B. C.↗

Improved measurement of thermal effects on microstructure

The objectives were to introduce a simple methodology which could be used to replace the time-consuming and expensive conventional methods of metallographic and quantitative analysis of thermal treatment effect on microstructure. Metallurgical analysis continually calls for the evaluation of thermal treatment effects on microstructure. This commonly demands metallographic sample preparation and microscopic examination, which are time absorbing and costly. These drawbacks are burdensome when large numbers of samples must be levied fast. Mechanical testing can sometimes be substituted, but sample size and shape frequently make these methods impractical. The experiment described here is ideal for the microstructural evaluation of lamp filaments and other wire samples such as copper wire which can be conveniently coiled.

Rastani, Mansur↗

Highlights from the Postirradiation Examination of AFC-3A and AFC-3B

Highlights from the postirradiation examination of the AFC-3A and AFC-3B irradiation test are presented. Baseline non-destructive and destructive examinations of these tests have been completed at this time. Results from visual examination, neutron radiography, gamma spectrometry, dimensional inspection, fission gas release, chemical burnup analysis, and optical microscopy have been collected. All the rodlets from these irradiations appear to have performed well during irradiation. Baseline PIE has been completed on rodlets from AFC- 3A, and AFC-3B. This includes visual exams, neutron radiography, gamma spectrometry. dimensional inspection, fission gas release evaluation, optical microscopy. microhardness evaluation. and chemical analysis. The results compiled here are a sampling of the full results. Baseline PIE provides an engineering or macroscopic scale evaluation of fuel performance and prepares samples for a more detailed phenomenological study of observed performance. Advanced PIE techniques are desired to obtain microscopic elemental and structural information both in the fuel, in the cladding, and in the interface where the composition of the FCCI layer is of great interest. The AFC-3 tests do appear to have performed roughly as designed during the irradiation. The FCCI behavior of Mo alloy metallic fuel versus Zr alloy metallic fuel has been confirmed. Results from this irradiation such as the FCCI observed in AFC-3A R1 and AFC-3A R2 can be used to eliminate Mo alloys as a choice in future irradiations where ultra-high burnup is a stated goal. Annular fuels are a preferred method for many high burnup core designs. The redistribution behavior of the annular U-Zr alloys should be studied further to better understand how this might impact high burnup annular fuel performance. The thermal bonding between annular fuel and cladding should also be studied further as there appear to be localized areas of FCCI forming in both AFC-3A R4 and AFC-3B R2, while no FCCI was observed in the Zr-based Na-bonded or Mo-based low smear density Na-bonded fuel. The performance of the low smear density. solid fuels is less clear. The neutron radiography and optical microscopy cross sections suggest the fuel is not forming a radially symmetric structure which may be causing undesirable localized temperature variations. Further study both by electron microscopy and by simulation to evaluate the implications of the non-symmetric fuel form are needed to better understand whether this fuel form merits further study under irradiation. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Spontaneous formation of circular and vortex ferroelectric domain structure in hexagonal YMnO{sub 3} and YMn{sub 0.9}Fe{sub 0.1}O{sub 3} prepared by low temperature solution synthesis

We report an experimental study of the domain structure of ferroelectric YMnO{sub 3} and YMn{sub 0.9}Fe{sub 0.1}O{sub 3} using polycrystalline samples prepared by direct hydrothermal crystallisation at 240 °C, well below their structural phase transition temperatures. Powder X-ray diffraction shows the expected P6{sub 3}cm space group for both samples with an increase in a and a small decrease in c with Fe incorporation, consistent with an adjustment of MnO{sub 5} tilting, while XANES spectra at the Mn and Fe K edges show the oxidation state of both metals are maintained at +3 in the doped sample. High resolution TEM shows that curved stripe, annular and vortex domains can all be observed in the YMnO{sub 3} crystals, proving that the structural phase transition is not the only driving force for the occurrence of the annular and vortex domains. Furthermore, the absence of the annular and vortex domains in YMn{sub 0.9}Fe{sub 0.1}O{sub 3} indicates that the tilting state of MnO{sub 5} bipyramids plays an important role in the domain formation. Atomic resolution STEM images confirm that the ferroelectric domain walls correspond to structural antiphase boundaries similar to the crystals made via high temperature solid-state reactions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Matrix-Assisted Ionization of Molecular Uranium Species

Matrix-assisted ionization (MAI) demonstrates high sensitivity for a variety of organic compounds; however, few studies have reported the application of MAI for the detection and characterization of inorganic analytes. Trace-level uranium analysis is important in the realms of nuclear forensics, nuclear safeguards, and environmental monitoring. Traditional mass spectrometry methods employed in these fields require combinations of extensive laboratory chemistry sample preparation and destructive ionization methods. There has been recent interest in exploring ambient mass spectrometry methods that enable timely sample analysis and higher sensitivity than what is attainable by field-portable radiation detectors. Rapid characterization of uranium at nanogram levels is demonstrated in this study using MAI techniques. Mass spectra were collected on an atmospheric pressure mass spectrometer for solutions of uranyl nitrate, uranyl chloride, uranyl acetate, and uranyl oxalate utilizing 3-nibrobenzonitrile as the ionization matrix. The uranyl complexes investigated were detectable, and the chemical speciation was preserved. Sample analysis was accomplished in a matter of seconds, and limits of detection of 5 ng of uranyl nitrate, 10 ng of uranyl oxalate, 100 ng of uranyl chloride, and 200 ng of uranyl acetate were achieved. The observed gas-phase speciation was similar to negative-ion electrospray ionization of uranyl compounds with notable differences. Six matrix-derived ions were detected in all negative-ion mass spectra, and some of these ions formed adducts with the uranyl analyte. Subsequent analysis of the matrix suggests that these molecules are not matrix contaminants and are instead created during the ionization process.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

p{sup +}-doping analysis of laser fired contacts for silicon solar cells by Kelvin probe force microscopy

Local rear contacts for silicon passivated emitter and rear contact solar cells can be established by point-wise treating an Al layer with laser radiation and thereby establishing an electrical contact between Al and Si bulk through the dielectric passivation layer. In this laser fired contacts (LFC) process, Al can establish a few μm thick p{sup +}-doped Si region below the metal/Si interface and forms in this way a local back surface field which reduces carrier recombination at the contacts. In this work, the applicability of Kelvin probe force microscopy (KPFM) to the investigation of LFCs considering the p{sup +}-doping distribution is demonstrated. The method is based on atomic force microscopy and enables the evaluation of the lateral 2D Fermi-level characteristics at sub-micrometer resolution. The distribution of the electrical potential and therefore the local hole concentration in and around the laser fired region can be measured. KPFM is performed on mechanically polished cross-sections of p{sup +}-doped Si regions formed by the LFC process. The sample preparation is of great importance because the KPFM signal is very surface sensitive. Furthermore, the measurement is responsive to sample illumination and the height of the applied voltage between tip and sample. With other measurement techniques like micro-Raman spectroscopy, electrochemical capacitance-voltage, and energy dispersive X-ray analysis, a high local hole concentration in the range of 10{sup 19 }cm{sup −3} is demonstrated in the laser fired region. This provides, in combination with the high spatial resolution of the doping distribution measured by KPFM, a promising approach for microscopic understanding and further optimization of the LFC process.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Solar Flare Track Exposure Ages in Regolith Particles: A Calibration for Transmission Electron Microscope Measurements

Mineral grains in lunar and asteroidal regolith samples provide a unique record of their interaction with the space environment. Space weathering effects result from multiple processes including: exposure to the solar wind, which results in ion damage and implantation effects that are preserved in the rims of grains (typically the outermost 100 nm); cosmic ray and solar flare activity, which result in track formation; and impact processes that result in the accumulation of vapor-deposited elements, impact melts and adhering grains on particle surfaces. Determining the rate at which these effects accumulate in the grains during their space exposure is critical to studies of the surface evolution of airless bodies. Solar flare energetic particles (mainly Fe-group nuclei) have a penetration depth of a few millimeters and leave a trail of ionization damage in insulating materials that is readily observable by transmission electron microscope (TEM) imaging. The density of solar flare particle tracks is used to infer the length of time an object was at or near the regolith surface (i.e., its exposure age). Track measurements by TEM methods are routine, yet track production rate calibrations have only been determined using chemical etching techniques [e.g., 1, and references therein]. We used focused ion beam-scanning electron microscope (FIB-SEM) sample preparation techniques combined with TEM imaging to determine the track density/exposure age relations for lunar rock 64455. The 64455 sample was used earlier by [2] to determine a track production rate by chemical etching of tracks in anorthite. Here, we show that combined FIB/TEM techniques provide a more accurate determination of a track production rate and also allow us to extend the calibration to solar flare tracks in olivine.

Berger, Eve L.↗

Tuning the extent of porosity and composition of N-doped carbon materials by NaNO3 and its effect on electrochemical activity

Highlights: • One-pot method using cheap NaNO{sub 3} as etching agent was developed to tune the porous structure. • NaNO{sub 3} was added into NaCl/ZnCl{sub 2} (NaCl 80 mol%) to form ionothermal salts. • The resultant carbon possesses a 3D hierarchical structure, with more mesopores ratio than micropores. • When NaNO{sub 3} amount is 5% in the salt mixture, the optimal ORR activity was obtained. - Abstract: A facile one-pot method using NaNO{sub 3} as etching agent in a molten salt medium is developed to tune the porous structure and composition of N-doped carbon materials derived from biomass at high temperatures. SEM and TEM analyses reveal that by increasing the amount of NaNO{sub 3}, the structures of the obtained carbons become more open and graphene-like layers are formed. N{sub 2} adsorption/desorption isotherms show that the hierarchical porous structure could be efficiently tuned by adjusting the amount of NaNO{sub 3} in the salt mixture. It is observed that the specific surface area of the as-prepared N-doped carbon using NaNO{sub 3} can reach 1430.1 m{sup 2} g{sup −1}, a much higher value than that of the sample prepared in the absence of NaNO{sub 3}. The micropore ratio decreases with increased amount of NaNO{sub 3}, from 49.42% to 9.98%. Whilst the surface composition of the obtained carbon materials is affected by NaNO{sub 3}. The N content increases and O decreases respectively, by increasing the amount of NaNO{sub 3}. Analysis on the N 1s high resolution reveals that the sum of pyridinic-N and graphitic-N increased, whereas the sum of pyridinic-N oxide and NO{sub x} decreases from NC-0 to NC-0.75. It is also found that the changes of the porous structure and the oxygen-containing groups from NC-0 to NC-0.75 led to changes in hydrophilicity. When the as-prepared carbon materials are used as catalysts for the oxygen reduction reaction, high catalytic activity values are obtained, sample NC-0.5 shows the best performance due to the porous structure and doping effect of N atoms. More importantly, it is concluded that producing N-doped carbon materials from soybean dregs in molten salt medium using NaNO{sub 3} as etching agent could provide a promising approach for the synthesis of opened N-doped carbons of controlled porous structures and large specific surface areas based on biomass precursors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Interferometric measurements of refractive index and dispersion at high pressure

Abstract We describe a high precision interferometer system to measure the pressure dependence of the refractive index and its dispersion in the diamond anvil cell (DAC). The reflective Fabry–Perot fringe patterns created by both a white light and a monochromatic beam are recorded to determine both the sample thickness and its index at the laser wavelength and to characterize the dispersion in the visible range. Advances in sample preparation, optical setup, and data analysis enable us to achieve $$10^{-4}$$ 10 - 4 random uncertainty, demonstrated with an air sample, a factor of five improvement over the best previous DAC measurement. New data on $${\text{H}}_{2}\text{O}$$ H 2 O liquid water and ice VI up to 2.21 GPa at room temperature illustrate how higher precision measurements of the index and its optical dispersion open up new opportunities to reveal subtle changes in the electronic structure of water at high pressure.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

A protected annealing strategy to enhanced light emission and photostability of YAG:Ce nanoparticle-based films

A significant obstacle in the development of YAG:Ce nanoparticles as light converters in white LEDs and as biological labels is associated with the difficulty of finding preparative conditions that allow simultaneous control of structure, particle size and size distribution, while maintaining the optical properties of bulk samples. Preparation conditions frequently involve high-temperature treatments of precursors (up to 1400 C), which result in increased particle size and aggregation, and lead to oxidation of Ce(III) to Ce(IV). We report here a process that we term protected annealing, that allows the thermal treatment of preformed precursor particles at temperatures up to 1000 C while preserving their small size and state of dispersion. In a first step, pristine nanoparticles are prepared by a glycothermal reaction, leading to a mixture of YAG and boehmite crystalline phases. The preformed nanoparticles are then dispersed in a porous silica. Annealing of the composite material at 1000 C is followed by dissolution of the amorphous silica by hydrofluoric acid to recover the annealed particles as a colloidal dispersion. This simple process allows completion of YAG crystallization while preserving their small size. The redox state of Ce ions can be controlled through the annealing atmosphere. The obtained particles of YAG:Ce (60 {+-} 10 nm in size) can be dispersed as nearly transparent aqueous suspensions, with a luminescence quantum yield of 60%. Transparent YAG:Ce nanoparticle-based films of micron thickness can be deposited on glass substrates using aerosol spraying. Films formed from particles prepared by the protected annealing strategy display significantly improved photostability over particles that have not been subject to such annealing.

36 MATERIALS SCIENCE↗

Procedures for cryogenic X-ray ptychographic imaging of biological samples

Biological sample-preparation procedures have been developed for imaging human chromosomes under cryogenic conditions. A new experimental setup, developed for imaging frozen samples using beamline I13 at Diamond Light Source, is described. This manuscript describes the equipment and experimental procedures as well as the authors' first ptychographic reconstructions using X-rays.

47 OTHER INSTRUMENTATION↗