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Combustion synthesis of CdS/reduced graphene oxide composites and their photocatalytic properties

Highlights: • CdS/reduced graphene oxide composites were prepared by a combustion method. • The phase changed from hexagonal to cubic phase by increasing the added amount of GO. • The composites showed excellent visible-light photocatalytic properties. • The plausible mechanism of photodegradation was discussed. - Abstract: CdS/reduced graphene oxide composites were synthesized by a simple one-pot combustion method using cadmium nitrate, thiourea and graphite as raw materials. The structure, morphologies, and photocatalytic properties of the as-prepared samples were studied by means of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, photoluminescence and ultraviolet–visible spectrophotometry. The results show that the structure of CdS in as-prepared samples changes from hexagonal to cubic phase by increasing the added amount of graphene oxide. During combustion reaction, graphene oxide was reduced to reduced graphene oxide. As-obtained CdS/reduced graphene oxide composites show high visible-light photoactivities, attributed to the minimized recombination of photoinduced electrons and holes and the high surface area of reduced graphene oxide sheets.

36 MATERIALS SCIENCE↗

Applicability of Micro X-Ray Fluorescence Spectroscopy to Astromaterials Curation and Research

Introduction: The Astromaterials Acquisition and Curation Office at NASA’s Johnson Space Center (JSC) curates NASA’s astromaterial sample collections which includes: Apollo samples, Luna samples, Ant-arctic meteorites, cosmic dust particles, microparticle impacts into space-flown materials, Genesis solar wind atoms, Stardust comet Wild-2 particles, Stardust inter-stellar particles, Hayabusa asteroid Itokawa particles, Hayabusa 2 asteroid Ryugu particles, and future OSIRIS-Rex asteroid Bennu particles (landing in Sep-tember, 2023) [1–3]. To enhance JSC’s advanced cu-ration capabilities, we have recently installed a high-performance micro-X-ray fluorescence (µXRF) spec-trometer to assist in sample characterization through rapid, non-destructive, in-situ elemental analyses that do not require the sample preparation protocols (i.e., polishing and carbon-coating) commonly needed for electron beam analyses. With this new instrument, we are capable of detecting all elements down to carbon in a variable-pressure or He-purged chamber for anal-ysis of a wide range of sample types. Here we describe the instrumental set-up, capabilities, and applicability of µXRF analysis to astromaterials curation and re-search. Instrumentation and Methodology: The X-ray fluorescence and computed tomography lab (X-FaCT) lab at JSC is now equipped with a Bruker M4 Tornado Plus µXRF (Fig. 1). This system is an energy-dispersive x-ray spectrometer equipped with two 60 mm2 silicon drift detectors (SDD) that are able to be used simulta-neously for output count rates ~500,000 cps. New light element windows allow detecting and analyzing the entire elemental range from carbon to americium. Two x-ray tubes (micro-focus Rh with polycapillary lenses and W with collimators of 0.5, 1.0, 2.0, and 4.5 mm) with max excitation parameters of 50 kV, 30 W and 50 kV, 40 W, respectively, allow for more flexibility of the analysis of high energy lines. The motorized X-Y-Z stage has a mapping range of 190 x 160 mm and can support samples up to 7 kg (~15.5 lbs) and a height of 120 mm [4]. Analytical modes include elemental analysis (down to ~20 µm spot size) via point, line, or area of bulk materials (rock surfaces, thin sections, thick sections, etc.) as well as coating analysis (determination of thickness and composition) of samples. This system has a variable vacuum chamber (1 mbar to 1 atm) that is also equipped with a He-purge system which accommodates vacuum sensitive samples while still allowing detection of light elements at atmospheric pressure. Utility and Applicability of µXRF in Astro-materials research and exploration science (ARES): Elemental analysis using µXRF is commonly em-ployed for both terrestrial and planetary geological science disciplines [5]. It is especially useful for analy-sis of astromaterials given the limited sample prepara-tion required, which is not feasible for certain materi-als. Here we show select applications of µXRF anal-yses of astromaterials that can, have, and will be done at JSC’s X-FaCT lab. Point analysis: In-situ spot analyses (~20 µm spot size) on a cut slab of Martian meteorite NWA 10922 allowed for the discovery, qualitative elemental analy-sis and determination of different feldspar minerals [6]. These point analyses served as an effective prelim-inary step for subsequent quantitative analyses. Ana-lytical standards can be employed for more accurate quantification of µXRF spot analyses. Area analysis: This analytical mode measures all detectable elements (from C to Am) at each pixel (>5 µm pixel size) in a user-defined area. The results are shown as elemental maps which can be extracted as 16-bit TIFF’s for further data processing. In Fig. 2. we show elemental distribution maps of the high-Ti basalt 73001,531 that have been processed using ImageJ software. From these maps you can accurately and quickly (this map took ~50 mins.) identify mineral components, such as pyroxene, plagioclase, oxides, and phosphates, compositional zoning, and mineral textures. Detection of high-Z phases: µXRF techniques are es-pecially effective at analyzing trace minerals with high-atomic-number (high-Z) elements because the high-energy characteristic X-rays used (relative to SEM EDS) allow for mapping of K lines in elements up to La (typically SEM maps use L X-ray lines for elements >Zn, and these can often have interferences). Thus, µXRF is especially suited for identifying minerals like zircon, baddeleyite, REE-rich phosphates, Fe-rich met-als, oxides, sulfides, and phosphides [4]. In Fig. 3 we show elemental distribution maps for 73001,530 where we are able to correlate the original video image with, Zr, Si, Y and Hf elemental maps together identi-fying the location of a zircon. In this location you would expect lower Si compared to surrounding mate-rial, as well as higher Zr, Y, and Hf content compared to surrounding material, all of which is confirmed by our XRF ele-mental distribution maps (Figure 2.) Conclusions: The new M4 Tornado Plus µXRF within the Astromaterials Acquisition and Curation office at NASA JSC allows for rapid and non-destructive elemental analysis of astromaterials with limited or no sample preparation. µXRF analyses pro-vide crucial compositional knowledge for the prelimi-nary examination and curation of astromaterials. This instrument enhances the advanced curation capabili-ties in the X-FaCT laboratory at JSC by allowing pro-ductive, cohesive, and non-destructive multi-modal x-ray analyses on astromaterial samples, which is neces-sary for the comprehensive curation and study of our current and future astromaterial collections. Addition-ally, µXRF can provide complimentary information to researchers for studies on astromaterials. References: [1] Allen, C. et al., (2011). Chemie De Erde Geochemistry, 71, 1-20. [2] McCubbin, F. M. et al., (2016) 47th LPSC, abstract #2668 [3] Zeigler, R. A. et al., (2017) 48th LPSC, abstract #2772 [4] Bruker User Manual [5] Young et al., (2016) Appl. Geochemistry, 72, 77-87 [6] Mor-ris, R. V. et al., (2023) 54th LPSC.

E W O'Neal↗

Qualitative Characterization of the Aqueous Fraction from Hydrothermal Liquefaction of Algae Using 2D Gas Chromatography with Time-of-flight Mass Spectrometry

Two-dimensional gas chromatography coupled with time of flight mass spectrometry is a powerful tool for identifying and quantifying components in complex mixtures. It has been used to analyze gasoline, jet fuel, diesel, bio-diesel and organic fraction of bio-crude/bio-oil. In these experiments, the first dimension of separation was non-polar, followed by a polar separation. Aqueous fractions of bio-crude and other aqueous samples have been examined with similar column combinations. However, sample preparation techniques such as derivatization, solvent extraction, and solid-phase extraction were necessary prior to analysis. In this study, aqueous fraction obtained from hydrothermal liquefaction of algae was characterized by two-dimensional gas chromatography coupled with time of flight mass spectrometry without prior sample preparation techniques using a polar separation in the first dimension followed by a non-polar separation. Two-dimensional plots from this analysis were compared with those obtained from the more traditional column combination. Results from qualitative characterization aqueous fractions of algal bio-crude are discussed in detail. The advantages of using a polar separation followed by a non-polar separation for characterization of organics in aqueous samples by two-dimensional gas chromatography coupled with time of flight mass spectrometry are highlighted.

aquatic biomass↗

Effect of different sulphur precursors on morphology and band-gap on the formation of Cu{sub 2}ZnSnS{sub 4} (CZTS) particles with microwave irradiation

Cu{sub 2}ZnSnS{sub 4} (CZTS) is a promising semiconductor material for ecological cost effective thin film Photovoltaic (PV) devices. As it contains earth abundant and non-toxic elements, it has the advantages over commercially available CIGS and CdTe thin film PV devices. In the present work, the pure phase Cu{sub 2}ZnSnS{sub 4} particles were successfully synthesised with microwave irradiation. The morphology and phase study was carried out for the samples prepared with two different sulphur precursors viz. thiourea and thioacetamide (TAA). CZTS particles with thiourea as sulphur precursor are more crystalline than CZTS particles with TAA. The band gap of 1.654 eV and 1.713 eV were calculated for the samples prepared with thiourea and TAA respectively.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Characterization of the aqueous fraction from hydrothermal liquefaction of algae using 2D gas chromatography with time-of-flight mass spectrometry

Two-dimensional gas chromatography coupled with time of flight mass spectrometry is a powerful tool for identifying and quantifying components in complex mixtures. It has been used to analyze gasoline, jet fuel, diesel, bio-diesel and organic fraction of bio-crude/bio-oil. In these experiments, the first dimension of separation was non-polar, followed by a polar separation. Aqueous fractions of bio-crude and other aqueous samples have been examined with similar column combinations. However, sample preparation techniques such as derivatization, solvent extraction, and solid-phase extraction were necessary prior to analysis. In this study, aqueous fraction obtained from hydrothermal liquefaction of algae was characterized by two-dimensional gas chromatography coupled with time of flight mass spectrometry without prior sample preparation techniques using a polar separation in the first dimension followed by a non-polar separation. Two-dimensional plots from this analysis were compared with those obtained from the more traditional column combination. Results from qualitative as well as quantitative characterization of aqueous fractions of algal bio-crude are discussed in detail. The advantages of using a polar separation followed by a non-polar separation for characterization of organics in aqueous samples by two-dimensional gas chromatography coupled with time of flight mass spectrometry are highlighted.

Panisko, Ellen A.↗

Impact of Solution Chemistry on Growth and Structural Features of Mo-Substituted Spinel Iron Oxides

The effect of crystallizing solution chemistry on the chemistry of subsequently as-grown materials was investigated for Mo-substituted iron oxides prepared by thermally activated co-precipitation. In the presence of Mo ions, we find that varying the oxidation state of the iron precursor from Fe(II) to Fe(III) causes a progressive loss of atomic long-range order with the stabilization of 2-4 nm particles for the sample prepared with Fe(III). The oxidation state of the Fe precursor also affects the distribution of Fe and Mo cations within the spinel structure. Increasing the Fe precursor oxidation state gives decreased Fe-ion occupation and increased Mo-ion occupation of tetrahedral sites, as revealed by the extended X-ray absorption fine structure. The stabilization of Mo within tetrahedral sites appears to be unexpected, considering the octahedral preferred coordination number of Mo(VI). The analysis of the atomic structure of the sample prepared with Fe(III) indicates a local ordering of vacancies and that the occupation of tetrahedral sites by Mo induces a contraction of the interatomic distances within the polyhedra as compared to Fe atoms. Moreover, the occupancy of Mo into the thermodynamic site preference of a Mo dopant in Fe 2 O 3 assessed by density functional theory calculations points to a stronger preference for Mo substitution at octahedral sites. Hence, we suggest that the synthetized compound is thermodynamically metastable, that is, kinetically trapped. Such a state is suggested to be a consequence of the tetrahedral site occupation by Mo ions. The population of these sites, known to be reactive sites enabling particle growth, is concomitant with the stabilization of very small particles. Furthermore, we confirmed our hypothesis by using a blank experiment without Mo ions, further supporting the impact of tetrahedral Mo ions on the growth of iron oxide nanoparticles. Our findings provide new insights into the relationships between the Fechemistry of the crystallizing solution and the structural features of the as-grown Mo-substituted Fe-oxide materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cr-substitution effect on structural, optical and electrical properties of Cr{sub x}Ce{sub 1−x}PO{sub 4} (x = 0.00, 0.08, 0.10 and 0.20) nanorods

Graphical abstract: The Cr{sub x}Ce{sub 1−x}PO{sub 4} (x = 0.00, 0.08, 0.10 and 0.20) nanorods synthesized under hydrothermal conditions. - Highlights: • Cr{sub x}Ce{sub 1−x}PO{sub 4} (x = 0.00–0.20) nanorods were synthesized by hydrothermal method. • Mean crystallite size of the products decreases with Cr-content. • Obvious improvements of the electrical conductivity comparatively to CePO4. - Abstract: Cr{sub x}Ce{sub 1−x}PO{sub 4} (x = 0.00–0.20) nanorods were synthesized using the hydrothermal method. The as-prepared samples were characterized by X-ray diffraction (XRD), infrared absorption spectroscopy (IR) and transmission electron microscopy (TEM). The XRD results revealed the formation of a pure CePO{sub 4} hexagonal phase. TEM images confirmed the nano-size character of the as-prepared samples. Impedance spectroscopy analysis was used to analyze the electrical behavior of samples as a function of frequency at different temperatures. The increase of Cr-amount led to an increase in the total conductivities and decreased the activation energies (E{sub a} (x = 0.00) = 1.08 eV to E{sub a} (x = 0.20) = 0.80 eV). The optical properties of Cr{sub x}Ce{sub 1−x}PO{sub 4} nanomaterials were investigated using UV–vis spectroscopy. The band-gap energy values decreased with increasing Cr-content showing a red-shift trend. The improvement of the electrical conductivity and optical properties makes the Cr{sub x}Ce{sub 1−x}PO{sub 4} nanomaterials possible candidates to be used as electrolytes in solid oxide fuel cells, in photocatalytic and photovoltaic applications.

36 MATERIALS SCIENCE↗

Beyond Nanopore Sequencing in Space: Identifying the Unknown

Astronaut Kate Rubins sequenced DNA on the International Space Station (ISS) for the first time in August 2016 (Figure 1A). A 2D sequencing library containing an equal mixture of lambda bacteriophage, Escherichia coli, and Mus musculus was prepared on the ground with a SQK_MAP006 kit and sent to the ISS frozen and loaded into R7.3 flow cells. After a total of 9 on-orbit sequencing runs over 6 months, it was determined that there was no decrease in sequencing performance on-orbit compared to ground controls (1). A total of ~280,000 and ~130,000 reads generated on-orbit and on the ground, respectively, identified 90% of reads that were attributed to 30% lambda bacteriophage, 30% Escherichia coli, and 30% M. musculus (Figure 1B). Extensive bioinformatics analysis determined comparable 2D and 1D read accuracies between flight and ground runs (Figure 1C), and data collected from the ISS were able to construct directed assemblies of E.coli and lambda genomes at 100% and M. musculus mitochondrial genome at 96.7%. These findings validate sequencing as a viable option for potential on-orbit applications such as environmental microbial monitoring and disease diagnosis. Current microbial monitoring of the ISS applies culture-based techniques that provide colony forming unit (CFU) data for air, water, and surface samples. The identity of the cultured microorganisms in unknown until sample return and ground-based analysis, a process that can take up to 60 days. For sequencing to benefit ISS applications, spaceflight-compatible sample preparation techniques are required. Subsequent to the testing of the MinION on-orbit, a sample-to-sequence method was developed using miniPCR™ and basic pipetting, which was only recently proven to be effective in microgravity. The work presented here details the in- flight sample preparation process and the first application of DNA sequencing on the ISS to identify unknown ISS-derived microorganisms.

Stahl, Sarah E.↗

Laser‐ablation electrospray ionization mass spectrometry with ion mobility separation reveals metabolites in the symbiotic interactions of soybean roots and rhizobia

Summary Technologies enabling in situ metabolic profiling of living plant systems are invaluable for understanding physiological processes and could be used for rapid phenotypic screening (e.g., to produce plants with superior biological nitrogen‐fixing ability). The symbiotic interaction between legumes and nitrogen‐fixing soil bacteria results in a specialized plant organ (i.e., root nodule) where the exchange of nutrients between host and endosymbiont occurs. Laser‐ablation electrospray ionization mass spectrometry ( LAESI ‐ MS ) is a method that can be performed under ambient conditions requiring minimal sample preparation. Here, we employed LAESI ‐ MS to explore the well characterized symbiosis between soybean ( Glycine max L. Merr.) and its compatible symbiont, Bradyrhizobium japonicum . The utilization of ion mobility separation ( IMS ) improved the molecular coverage, selectivity, and identification of the detected biomolecules. Specifically, incorporation of IMS resulted in an increase of 153 differentially abundant spectral features in the nodule samples. The data presented demonstrate the advantages of using LAESI – IMS – MS for the rapid analysis of intact root nodules, uninfected root segments, and free‐living rhizobia. Untargeted pathway analysis revealed several metabolic processes within the nodule (e.g., zeatin, riboflavin, and purine synthesis). Compounds specific to the uninfected root and bacteria were also detected. Lastly, we performed depth profiling of intact nodules to reveal the location of metabolites to the cortex and inside the infected region, and lateral profiling of sectioned nodules confirmed these molecular distributions. Our results established the feasibility of LAESI – IMS – MS for the analysis and spatial mapping of plant tissues, with its specific demonstration to improve our understanding of the soybean‐rhizobial symbiosis.

Stopka, Sylwia A.↗

Comparison of Laboratory Analytical Methods for Uranium Analysis Superior Steel FUSRAP Site - 16606

The Superior Steel Site processed uranium metal in support of the Atomic Energy Commission's fuel-element development program in the 1950's, and was subsequently classified as a Formerly Utilized Sites Remedial Action Program (FUSRAP) Site. Previous investigations at the site identified uranium contamination both inside and outside the buildings associated with historic uranium metalworking activities. The U.S. Army Corps of Engineers (USACE) is currently engaged in the Remedial Investigation (RI) phase in accordance with the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) of 1980, as amended. As part of the RI, gamma spectroscopy analysis of environmental samples was performed on-site using a laboratory-grade, high-purity germanium (HPGe) spectrometer. The gamma spectroscopy analysis included isotopes of uranium and their progeny. As a quality assurance measure, a subset of samples already analyzed on-site were sent to a certified, commercial, off-site laboratory for analysis using a suite of analytical methods including gamma spectroscopy, alpha spectroscopy, and mass spectroscopy. As an element of the quality assurance program implemented for the RI, an assessment of the correlations between the various analytical methods employed by both the on-site and off-site laboratory was performed. This assessment revealed inconsistencies between on-site and off-site gamma spectroscopy analytical results, which raised concerns about the appropriateness and suitability of the analytical data. To resolve the data quality concerns and better understand the source(s) of analytical results variability, the Superior Steel RI team (USACE together with its contractor, Amec Foster Wheeler) developed a quality control test whose design objective was to control or practically eliminate sampling and sample preparation variability in order to focus more clearly on analytical variability. This paper discusses the results of this supplemental quality control test, showing the differences in the various analytical methods (both on-site and off-site). It demonstrates in a practical and real world setting how sample preparation and analytical variability, if not controlled and understood can impact data quality and data defensibility. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Micrometer to Atomic Scale Characterisation of Primitive Astromaterials Using A Novel Method, Metis-Fa: A Coordinated Atom Probe Tomography, Transmission Electron Microscopy and NanoSIMS Approach

Introduction: Presolar grains preserve isotopic, chemical and microstructural records of physical and chemical processing, and formation mechanisms within a vast range of evolved stellar systems, the interstellar medium, solar nebula and their parent bodies. These evolutionary records are preserved at the micrometric to atomic scale, requiring coordinated studies to expand our understanding of evolutionary processes occurringthroughout ours and external stellar systems [1]. NanoSIMS enabled rapid in situ identification and isotopic characterisation of presolar grains and their stellar origins using 17O/16O and 18O/16O, and 13C/12C isotopic ratios [1]. Coordination with transmission electron microscopy (TEM) revealed crystallographic and localised contextual relationships and quantitively constrained their major and minor compositions [1]. However, trace elements cannot be quantified, the most sensitive geochemical tracers of environmental conditions, essential to unravelling the chemical record of their evolutionary pathway and parent stellar systems [2-3] . Furthermore, owing to the combination of technical limitations (only 5 – 7 isotopes can be measured per NanoSIMS run) and their small grain sizes of 100 nm < 3 μm (with rare exceptions in nanodiamonds (2 nm ≤) and SiC (< 40 μm)), the number of measurable isotopes per grain volume is limited [1,3] . Through more comprehensive isotopic studies of presolar grains, NanoSIMS studies have shown the importance of the latter, identifying Fe and Mg as important indicators of nuclear synthetic processing and their stellar origins, respectively [4- 5]. Coordination of NanoSIMS and Atom Probe Tomography (APT) revealed morphological signatures, and isotopic and chemical signatures at major to trace levels without requirements for preselection of elements [6]. However, crystallographic signatures in localized contextual relationships cannot be measured. Consequently, coordination of NanoSIMS, TEM and APT is essential to gain access to almost all contextual, structural and geochemical signatures within each presolar grain.Transmission electron microscopy requires a 100 nm thin lamella which is unstable in APT and would not produce any viable data. Atom probe tomography requires a needle-shaped specimen which when measured in TEM removes the local context, impacts the quality of the TEM diffraction images due to the shank angle of the needle, and can alter the chemistry of beam sensitive materials from the higher degree of surface exposure at the tip. To address these issues, we developed METIS-Fa (Multi-technical measurements of Electron Transparent materials using an Indium Sandwich - a FIB approach). A novel method which enables coordination of NanoSIMS, TEM and APT for generalized and targeted studies of individual grains, including beam sensitive materials, without compromising sample preparation requirements for TEM and APT. This method requires only indium and a Focus Ion Beam (FIB), minimizing the movement of fragile materials while still enabling preparation of TEM lamella into APT needles. Samples: Initial experimental development and testing of the method occurred at Astromaterials Research and Exploration Science (ARES), Johnson Space Centre (JSC), NASA and APT measurements and needle preparation occurred at JdLC, Curtin University. Synthetic silicate samples were used as analogs for presolar silicates when performing a trial run of the method. Samples were extracted from a polished thin section created at JSC, NASA, comprised of 38 wt.% Si, 17 wt.% FeO, 13 wt.% MgO, 12 wt.% Al, 11 wt.% Ca based on electron microprobe analysis (EMPA) [8] . Experimental details, pressure and temperature conditions were presented in [8] and references therein. Testing of the capability to target individual grains in mineral matrices using this method for acquisition in APT, measured matrix regions in meteoritic thin sections of primitive meteorites. These meteorites and their identified presolar grains for future targeted studies are detailed in [9]. Techniques: The TEM-FIB lamella were prepared using a FIB. An e-beam assisted pt deposition was used as a protective coating for the synthetic and meteoritic samples. When targeting individual grains, a secondary e-beam assisted pt deposition button is placed over the desired grain before the protective coating to denote its location. A JEOL 2500SE field-emission TEM was used for high-resolution imaging, energy-dispersive X-ray (EDX) and electron diffraction data.TheMETIS-Fa method was experimentally designed, tested and executed using a FIB at ARES, JSCNASA. Needles for APT were prepared using the Tescan Lyra3 GM Dual Beam Focus Ion Beam (FIB) Field Emission SEM (FE-SEM) at the JdLC, Curtin University. Atom probe tomography measurements were conducted using a CAMECA Local Electrode Atom Probe, LEAP 4000X HR. Two pure indium needles were analyzed initially to constraining acquisition parameters and stability under the beam. Manual acquisition was required to maintain evaporation of specimen’s at the apex and monitor interactions with measurement parameters. Experimental Design: Indium foil is pressed onto an Al stub with a pneumatic press and mounted into the FIB adjacent to the TEM-FIB lamella of interest. Using a FIB, two indium slices (5 μm x ~300 nm x 3 μm) are extracted from indium foil and aligned with the TEM-FIB lamella before touching the TEM-FIB lamella. Each slice is then attached through cold welding to the FIB-TEM lamella. This approach eliminates the need for chemical treatments and proved effective for aligning the Indium within the region of interest for APT, holding it in place for up to 4 days during testing.Once both indium slices are attached within their pre-determined region per grain targeting requirements, they are gradually melted onto the FIB-TEM lamella.When targeting a specific grain, measurements should be taken of the pt button and its distance from edge to edge of the lamella before and after sandwiching. A secondary button should be placed over the same region after the Indium slices have been attached to improve precision when preparing APT needles. Results: Figure 1 shows two indium slices melted onto a FIB-TEM lamella, adding additional bulk for preparation into APT needles as shown in Figure 2 [7] . The latter was essential so samples could be measured in TEM and APT without compromising sample preparation requirements and consequently data quality and acquisition stability. METIS-Fa proved effective forimproving geometry. Figure 3 shows a successful APTrun of the synthetic silicate. EMPA, TEM and APTshowed no chemical alterations. During targetingtesting, a solar silicate grain was successfully identifiedand measured in TEM, and prepared into an APTneedle. However, the indium was melted too long during sample preparation, causing expansion andformation of internal porosity leading to sample loss.Conclusion: METIS-Fa greatly expands the number of isotopic and chemical signatures measured per grain volume, and enables measurements of contextual, structural, crystallographic, isotopic and geochemical signatures within individual grains. Gaining access to such a vast range of evolutionary signatures required for expanding our understanding of external stellar and planetary systems and the evolution of our solar system. This method was designed for application to a vast range of phases including being sensitive materials and thus provides a way for coordination of NanoSIMS, TEM and APT not just for the study of presolar grains and by extension primitive astromaterials, but studies in a vast range of other fields including the geosciences and material sciences.Acknowledgments: Thankyou to ARES, JSC, NASA; JdLC Curtin University and Space Science Technology Centre for the use of laboratory facilities and funding [confirm].

Nicole D Nevill↗

Enhanced Photocatalytic Property of Cu Doped Sodium Niobate

Here, we investigate the photocatalytic activity of Cu doped NaNbO 3 powder sample prepared by the modified polymer complex method. The photocatalytic activity of hydrogen evolution from methanol aqueous solution was improved by Cu 2.6 at% doping. The photocatalytic degradation of rhodamine B (RhB) under visible light irradiation was enhanced in comparison with pristine NaNbO 3 . Cu introduction improved the adsorption property of NaNbO 3 , judging from the Fourier transform infrared spectra. Moreover, the ultraviolet light excitation in Cu doped sample would accelerate the mineralized process.

36 MATERIALS SCIENCE↗

Investigation of grain-boundary geometry and pores morphology in dense and porous cubic zirconia polycrystals

Highlights: • Cubic zirconia sinters were investigated in three dimensions using dual-beam FEGSEM. • The 3D-EBSD technique was successfully applied to non-conductive ceramics. • New sample preparation approach to automated 3D-EBSD was proposed. • Grain boundary microstructures were reconstructed from inverse pole figure maps. • Pore microstructures were reconstructed from image quality maps. - Abstract: Three-dimensional electron backscatter diffraction technique was used for the visualization of grain boundary geometry and pore morphology in cubic zirconia. A set of four samples sintered under different conditions was investigated. Specimens which were characterized by energy dispersive spectroscopy and X-ray diffraction were entirely composed of cubic phase. Investigations of boundaries and pore structures were carried out in a dual-beam scanning electron microscope. For each sample, a volume of 1000 μm{sup 3} was investigated. The analysis of grain boundary networks reconstructed from inverse pole figure maps revealed a strong dependence between grain boundary density and sample preparation parameters. Sintering also affects the size and distribution of pores. The total number of grains analyzed varied from 17 to 357 and the calculated volume of cavities from 0.01% to 21%. This paper shows the application of three-dimensional crystallographic orientation analysis to characterize the microstructure of yttria stabilized zirconia ceramics.

36 MATERIALS SCIENCE↗

Impact of Rare Earth Gd{sup 3+} Ions on Structural and Magnetic Properties of Ni{sub 0.5}Zn{sub 0.5}Fe{sub 2−x}Gd{sub x}O{sub 4} Spinel Ferrite: Useful for Advanced Spintronic Technologies

In this article, we have synthesized the Gd{sup 3+}-doped Ni{sub 0.5}Zn{sub 0.5}Fe{sub 2−x}Gd{sub x}O{sub 4} (x = 0.05, 0.07, 1.0) ferrite samples using solid-state reaction route. The effects of Gd{sup 3+} doping on structural, vibrational, electrical and magnetic properties were studied. Structural and vibrational properties were characterized by x-ray diffraction (XRD), Raman, and FTIR spectroscopy. XRD data indicate that the Ni{sub 0.5}Zn{sub 0.5}Fe{sub 2−x}Gd{sub x}O{sub 4} ceramics crystallize in single-phase spinel cubic (Fd3m space group) structure. Infrared spectra show two strong absorption bands in the frequency range of 400–600 cm{sup −1} which were, respectively, attributed to tetrahedral and octahedral sites of the spinel ferrite. All the prepared samples show the typical dielectric dispersion having Maxwell–Wagner-type interfacial polarization. Decrease in dielectric constant and loss tangent has been observed with frequency and doping concentration. M − H plots reveal that all the samples exhibit ferrimagnetic nature at room temperature. A significant increase in the saturation magnetization has been observed upon the substitution of Gd{sup 3+} ions. All the as-prepared samples are isotropic and soft magnetic materials. These ferrite compounds are advantageous in advanced high-density data storage and high-frequency devices applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Microstructural Characterization of Irradiated Fuels and Materials for the United States High Performance Research Reactor Fuel Development Program and the Fuel Cycle Research and Development Program

In an effort to contribute to the development of advanced nuclear fuel for research reactors, monolithic and dispersion plate fuels will be examined to determine how irradiation parameters such as fission density, fission rate, and irradiation temperature, as well as mechanical parameters such as composition and fabrication, affect the final microstructure of the fuel, post irradiation. Electron Backscatter Detection (EBSD) analysis capabilities of irradiated materials will be developed as well as improvements on irradiated sample preparation in order to provide higher quality samples for SEM, FIB, and TEM. In addition, image analysis techniques developed at Idaho National Laboratory (INL) will be employed to examine microstructural features such as fission product precipitates and fission gas bubbles. The main goals are to further develop EBSD capabilities on irradiated material; characterize microstructure of irradiated fuel to support qualification; develop a consistent, effective process for image analysis using INL developed software; and provide repeatable, statistically-confident, critically assessed data to further modeling efforts. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Community Supported Stardust Compendia

The Stardust cometary and interstellar collections present unprecedented challenges in sample preparation and analysis. The ensemble of approx.80 tracks and dozens of foil craters from the cometary collection for which we have analyses exhibits a bewildering complexity and diversity of materials. The interstellar collection is even more challenging, because of the extremely low fluence of interstellar dust, a relatively large background of secondary ejecta from impacts on the spacecraft, and the small size of interstellar dust, approximately three orders of magnitude smaller in mass than typical cometary particles. Unlike with the other returned sample collections, characterization of these samples beyond basic photo-documentation is not generally practical at JSC. Even among the other small-particle collections, currently the cosmic dust and Hayabusa samples, SEM/EDX can provide basic chemistry. This is not possible with Stardust particles without destructive and invasive sample preparation. Furthermore, SEM/EDX requires isolating small grains from adhering aerogel. A reliable technique to carry out this task does not exist. Complete characterization of particles requires coordinated analyses using synchrotron and electron-beam microprobes, which do not exist at any one lab. Thus, it was recognized since the Stardust Preliminary Examination in 2006 that characterization of the samples would rely on the worldwide community of Stardust Investigators. Here we announce the development of community-editable, wiki-style Stardust compendia that will support this effort. Our intention is that this will facilitate sample requests by providing basic characterization of tracks. We expect that this will also support comprehensive meta-analyses (global syntheses of analyses) of the collections.

Westphal, Andrew J.↗

Comparison of Dislocation Characterization by Electron Channeling Contrast Imaging and Cross-Correlation Electron Backscattered Diffraction

The characterization and quantification of dislocations is predominately carried out using transmission electron microscopy (TEM). Nevertheless, the sample preparation necessary for TEM foils can be cumbersome and possibly introduce defects. Two other techniques for characterizing and quantifying dislocations are electron channeling contrast imaging (ECCI) and cross-correlation electron backscattered diffraction (CC-EBSD). ECCI is similar to TEM in that specific imaging (channeling or diffraction) conditions need to be established, but is carried out in a scanning electron microscope on bulk samples, resulting in less complex sample preparation. CC-EBSD measures subtle changes in orientation measured from EBSD patterns to calculate elastic strains and the Nye tensor to deduce and map the total geometrically necessary dislocation (GND) content. Furthermore, this work presented here compares the capabilities of ECCI and CC-EBSD to map dislocations generated from nanoindentation.

42 ENGINEERING↗

Advanced Characterization of Irradiated Fuels and Materials at INL

Advanced characterization of the irradiated fuels and materials is crucial to help understanding the material and fuel property changes under irradiation. Microstructural defect evolution down to nanometer scale could strongly affect the material and fuel performance on macroscale. Radiation-induced material degradation include dimensional instability, hardening and embrittlement, intergranular cracking, radiation-enhanced chemical interaction at the interfaces and breakaway swelling. To mitigate the radiation damage, advanced characterization on irradiated microstructure, microchemistry, micromechanical property and local thermal property is necessary to identify the controlling mechanisms that are responsible to the degradations. This presentation provides a summary of the advanced characterization capabilities at the Irradiation Materials Characterization Laboratory (IMCL), Materials and Fuels Complex (MFC), Idaho National Laboratory (INL). It highlights the recently established capabilities including shield sample preparation area (SSPA), shield confinement cells for two focused ion beam (FIB) systems, a shielded electron probe microanalysis (EPMA), the thermal property microscopy (TPM) along with non-shielded instruments like scanning electron microscopy (SEM), X-ray diffractometer, and transmission electron microscopy (TEM). Some examples on advanced characterizations on irradiated structural materials and fuels will be presented. It demonstrates the power of combining sample preparation of highly radioactive materials with the advanced characterization down to atomic resolutions within one facility.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗