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Investigation of structural and magnetic properties of Ni{sub 0.5}Zn{sub 0.5}Fe{sub 2}O{sub 4} nano powders prepared by self combustion method

Graphical abstract: Display Omitted Highlights: ► Ni{sub 0.5}Zn{sub 0.5}Fe{sub 2}O{sub 4} prepared by self combustion with uniform/nonuniform heating. ► Characterized using TEM, XRD, in-field Mössbauer and DC magnetometry. ► Leads to bimodal (S1) and very narrow size distribution (S2) type nano samples. ► S1 has magnetic properties of bulk Ni{sub 0.5}Zn{sub 0.5}Fe{sub 2}O{sub 4}. ► Although very even sized, S2 large magnetic anisotropy distribution. -- Abstract: Nano powders of Ni{sub 0.5}Zn{sub 0.5}Fe{sub 2}O{sub 4} have been synthesized by the self-combustion method at a relatively low temperature of 473 K under conditions of non-uniform and uniform heating. Rietveld fitting of X-ray diffractograms confirm the formation of the pure spinel phase in both samples. Transmission electron microscopy indicates that the sample prepared under non-uniform heating has a bimodal particle size distribution (average values 16 nm and 6 nm) while the one prepared under uniform heating has a very narrow particle size distribution (average size 4 nm). Low temperature, in-field Mössbauer spectroscopic studies clearly show surface spin contributions. The hyperfine fields and Curie temperature of the non-uniformly heated sample are in good agreement with those reported for the corresponding bulk samples. Despite having a very narrow particle size distribution, the uniformly heated sample has a large anisotropy distribution which is evident in the broad transition visible in the temperature dependent magnetization curve. It is also corroborated by the fact that the experimental magnetization curve at room temperature requires two Langevin functions for satisfactory reproduction.

36 MATERIALS SCIENCE↗

Qualitative Headspace GCMS Analysis of Lunar Regolith and Volatile Simulant Mixtures

Introduction: Future Artemis missions aim to return the volatile-bearing samples collected near lunar polar craters. We, as advanced curation scientists, are responsible for developing techniques and methodologies for preserving the integrity of returned samples and the science value those samples contain. The extent to which that preservation is possible, and the trade-offs preservation requires (e.g. monetary costs, sample volume limitations) all must be considered. Even less-than pristine volatile-bearing samples will be of tremendous value to the scientific community seeking to unravel the history of lunar surface volatiles and, more broadly, volatiles in the solar system. A sample collected on the lunar surface will experience at least five distinctive periods during which any changes here referred to as “alteration” will certainly occur at some scale: collection on the lunar surface; transportation back to Earth; long-term storage; curatorial processing; and allocation/distribution. The Planetary Exploration and Astromaterials Research Lab (PEARL) seeks to understand temperature and pressure effects on returned volatile samples by working with high-fidelity volatile-containing regolith simulants, setting the foundation for the future of cold curation. This abstract is focused on gas-surface interactions between LCROSS volatiles and readily available lunar regolith simulants. Experiments involved analyzing differences in headspace gas composition for various combinations of volatile and regolith simulants using gas chromatography/mass spectrometry (GC/MS). Experimental Procedure: The volatile simulants were chosen based on the molecules detected during the LCROSS mission.1 Stock solutions of condensed lunar volatile analytes were: methanol, 7 N ammonia in methanol, and 0.4% hydrogen sulfide in water. The regolith simulants used were primarily JSC-1A and NU-LHT-4M. Additional regolith simulant control studies were conducted with <150 μm sieved sand and KBr. A nested vial sample preparation approach separated the liquid stock solutions from the regolith, eliminating potential matrix effects between liquid and solid phases. Fifteen microliter aliquots of liquid volatile simulants were added to a 2 mL liquid GC vial and capped in atmosphere. An 18G needle punctured the 2 mL GC vial immediately before being transferred and sealed in a 20 mL GC vial containing 0-0.3 g of regolith simulant, see Figure 1. Separating the analytes ensures any changes observed in the total headspace gases is a result of gas-surface and/or gas-gas interactions. Equipment and Method: Initial GC/MS method development for the separation and identification of relevant headspace gases can be found in Amick, et al. 2023.2 The only hardware change is a different column: a TG-1701MS 30 m × 0.25 mm × 1.00 μm column. The vials were sampled at 10°C, room temperature (~25°C) and 50°C. Low temperature samples were kept in a chilled autosampler stage for at least 1 hour prior to sampling. High temperature samples were agitated at 50°C for 5 minutes immediately prior to injection onto the column. Headspace chromatograms were collected for each combination of temperature, regolith, and volatile simulant, including controls without one or both types of analytes, in triplicate. The chromatogram elution window for each analyte or significant atmospheric gas was identified using the peak mass spectrum cross-referenced with Figure 1.Picture of the nested vial set-up. a NIST MS library search. Each analyte peak was integrated after filtering the mass spectrum trace for the parent or most unique mass-to-charge ratio. For example, the mass-to-charge ratio used to identify, filter for, and integrate the carbon dioxide peak was centered around 44 m/z. Results: Figure 2 shows the integrated peak area for hydrogen sulfide in all combinations of regolith simulants, temperatures, and the addition of ammonia in methanol solution. Multiple repeat experiments with H2S and regolith simulants have confirmed hydrogen sulfide is removed from the headspace within 1 hour when exposed to JSC-1A, NU-LHT-4M and sand (not pictured). The consumption of H2S by lunar regolith simulants at different temperatures indicates surface chemistry will be an integral component in sample integrity and preservation. It is important to note that while the effect of surface chemistry on gaseous hydrogen sulfide is intriguing, further investigation into more chemically accurate regolith simulants is necessary and ongoing. The sulfur in hydrogen sulfide is in its most reduced state while off-the-shelf, terrestrially sourced JSC-1A and NU-LHT-4M are more oxidized than most lunar materials,3which likely leads to different oxidation-reduction reactions than would be expected in lunar regolith. Figure 3 shows the integrated peak area of carbon dioxide for each sample combination that contained ammonia in methanol solution. The addition of ammonia to the GC vials results in a consistent and reproducible decrease in carbon dioxide gas, even at 50°C. The effect became more pronounced when JSC-1A or NU-LHT-4M were present. This set of experiments demonstrated that the sample composition will affect the chemical and physical state of each component present. Future spectroscopic and microscopy experiments will be geared towards identifying the cause for the CO2(g) concentration decrease and the consumption of hydrogen sulfide. As cold and volatile curation scientists, this information provides necessary insight on how to appropriately handle and analyze volatile bearing returned samples, as well as predict the effect chemical composition has on the various sample phases we will analyze upon return to Earth. Unlike traditional curation of geologic materials, the molecules in a sample cannot be identified or processed using the naked eye or even an optical microscope. Volatile curation will require a combination of analytical techniques, including but not limited to highly sensitive gas and solid/condensed phase spectroscopy. This set of experiments has demonstrated the need for more detailed studies of volatile mixtures with mineralogically and geochemically analogous lunar regolith simulants to prepare for the curation of volatile-rich lunar samples from the south polar region of the Moon. References: [1] Colaprete, A., et al. (2010) Science, 330, (463-468). [2] Amick, C. L., et al.(2023) Houston, Texas, [3] Heiken, G. H., et al.(1991) (778-778)

Cecilia L Amick↗

Oxygen Adsorption, Subsurface Oxygen Layer Formation and Reaction with Hydrogen on Surfaces of a Pt–Rh Alloy Nanocrystal

The oxygen adsorption and its catalytic reaction with hydrogen on Pt–Rh single crystals were studied at the nanoscale by Field Emission Microscopy (FEM) and Field Ion Microscopy (FIM) techniques at 700 K. Both FEM and FIM use samples prepared as sharp tips, apexes of which mimic a single nanoparticle of catalyst considering their similar size and morphology. Oxygen adsorption on Pt-17.4 at.%Rh samples leads to the formation of subsurface oxygen, which is manifested in the field emission (FE) patterns: for O2 exposure of ~3 Langmuir (L), {113} planes appear bright in the emission pattern, while for higher oxygen doses, i.e. 84 L, the bright regions correspond to the high index planes between the {012} and {011} planes. Formation of subsurface oxygen is probably accompanied by a surface reconstruction of the nanocrystal. The subsurface oxygen can be effectively reacted off by subsequent exposure of the sample to hydrogen gas at 700 K. The hydrogenation reaction was observed as a sudden, eruptive change of the brightness seen on the FE pattern. This reaction resulted in the recovery of the initial field emission pattern characteristic of a clean tip, with {012} facets being the most visible. It was shown that the oxygen accumulation-reduction process is completely reversible. The obtained results indicate that the presence of subsurface species must be considered in the description of reactive processes on Pt–Rh catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Engineering a highly dispersed core@shell structure for efficient photocatalysis: A case study of ternary novel BiOI@MIL-88A(Fe)@g-C3N4 nanocomposite

Highlights: • Novel ternary BiOI@MIL-88A(Fe)@g-C{sub 3}N{sub 4} core@shell photocatalyst is reported. • Photocatalytic degradation mechanism of organic pollutants is investigated. • It is divulged that the photodegradation is increased by BiOI supporting. • Core@shell structure of MIL-88A(Fe)@g-C{sub 3}N{sub 4} causes high activity. • Strong visible light absorption and electron transfer improve activity. - Abstract: Ternary novel BiOI@MIL-88A(Fe)@g-C{sub 3}N{sub 4} nanocomposite with core@shell structure was successfully synthesized by hydrothermal method. Fabricated photocatalysts were characterized and results confirmed the formation of MIL-88A(Fe)@g-C{sub 3}N{sub 4} core@shell structure and subsequently BiOI decoration on the surface of MIL-88A(Fe)@g-C{sub 3}N{sub 4}. Photocatalytic performances of prepared samples were investigated for degradation of Acid Blue 92 (AB92), Rhodamine B (RhB) and phenol under visible irradiation. It is clearly demonstrated that the as-prepared ternary BiOI@MIL-88A(Fe)@g-C{sub 3}N{sub 4} composites exhibits exceptional visible-light photocatalytic activities for cationic, anionic as well as neutral pollutant molecules compared to the widely accepted outstanding g-C{sub 3}N{sub 4}. It is mainly proved that the exceptional photocatalytic efficiencies are comprehensively ascribed to the porous structure of MIL-88A(Fe)@g-C{sub 3}N{sub 4}, greatly promoted charge separation and introduced catalytic functions to the carrier-related redox reactions by decorating BiOI and coupling g-C{sub 3}N{sub 4}, to modulate holes and electrons. Additionally, studies performed using radical scavengers showed the main reactive species in the photocataytic reaction for all chemical pollutant degradation.

36 MATERIALS SCIENCE↗

The quick and ultrasensitive determination of K in NaI using inductively coupled plasma mass spectrometry

A highly sensitive, novel and quick assay method utilizing inductively coupled plasma mass spectrometry was developed for the determination of K in NaI powders and NaI(Tl) scintillator crystals for use in ultralow background applications. The determination of K (viz. 40K), as well as Th and U and their daughters, is important in ultralow background detector materials to ensure incorporation of materials of sufficiently high radiopurity. Through the use of improved instrumentation, cool plasma operating conditions, and meticulously clean sample preparations, detection limits of 11 fg natK∙g-1 (or 341 pBq 40K∙kg-1) was attained for K in pure water. Detection limits in the sample matrix (i.e., NaI) were 0.529 ng natK∙g NaI-1 (or 16.4 Bq 40K∙kg NaI -1). A number of different precursor NaI powder samples and NaI(Tl) scintillator crystals were assayed for their K content. Determinations ranged from 0.757 – 31.4 ng natK∙g NaI-1. This method allows for the screening of materials to unprecedented levels in a fraction of the time compared to gamma counting techniques, providing a useful method for a more effective screening tool of K in ultralow background detector materials.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

CO 2 –Brine Contact Angle Measurements on Navajo, Nugget, Bentheimer, Bandera Brown, Berea, and Mt. Simon Sandstones

In this study, contact angles were measured for CO 2 bubbles on six different sandstones (Navajo, Nugget, Bentheimer, Bandera Brown, Berea, and Mt. Simon) that could potentially represent properties of CO 2 storage depositional environments. The impacts of pressure and temperature were studied by focusing on the CO 2 phase behavior in three different scenarios: gaseous, liquid, and supercritical conditions. Despite controlling the sample preparation and cleanliness, CO 2 -brine equilibration conditions, and pressure and temperature, there were inconsistencies in contact angle trends that could largely be attributed to natural sample heterogeneity resulting from localized variations in topography, surface roughness, and mineral composition across the surface. Despite these variations, the analysis of 298 measurements from this study showed that 81% of the contact angles were below 40° representing strongly water-wet to (moderately) water-wet behaviors. Also, 17.3% of the measurements were between 40° and 60° (weakly water-wet) and primarily belonged to small CO 2 bubbles (< 500 μm) that were heavily impacted by localized surface heterogeneity in natural sandstone samples. Additionally, only 1.7% of the measurements had angles greater than 60° and could be classified as CO 2 -wet behavior, but these measurements occurred on extremely small bubbles (100-200 μm) that were very dependent on localized surface heterogeneity. While some of the detailed physics of the CO 2 -brine-sandstone interface is still poorly understood, from an application standpoint, the sandstones of this study were best characterized as strongly water-wet to (moderately) water-wet.

03 NATURAL GAS↗

High-fidelity and high-resolution phase mapping of granites via confocal Raman imaging

Abstract In physical sciences such as chemistry and earth sciences, specifically for characterization of minerals in a rock, automated, objective mapping methods based on elemental analysis have replaced traditional optical petrography. However, mineral phase maps obtained from these newer approaches rely on conversion of elemental compositions to mineralogical compositions and thus cannot distinguish mineral polymorphs. Secondly, these techniques often require laborious sample preparations such as sectioning, polishing, and coating which are time-consuming. Here, we develop a new Raman imaging protocol that is capable of mapping unpolished samples with an auto-focusing Z-mapping feature that allows direct fingerprinting of different polymorphs. Specifically, we report a new methodology for generating high fidelity phase maps by exploiting characteristic peak intensity ratios which can be extended to any multi-phase, heterogenous system. Collectively, these enhancements allow us to rapidly map an unpolished granite specimen (~ 2 × 2 mm) with an exceptionally high accuracy (> 97%) and an extremely fine spatial resolution (< 0.3–2 µm).

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Nanowires of Fe/multi-walled carbon nanotubes and nanometric thin films of Fe/MgO

We observed that nanowires of Fe grown in the lumens of multi-walled carbon nanotubes required four times higher magnetic field strength to reach saturation compared to planar nanometric thin films of Fe on MgO(100). Nanowires of Fe and nanometric thin films of Fe both exhibited two fold magnetic symmetries. Structural and magnetic properties of 1-dimensional nanowires and 2-dimensional nanometric films were studied by several magnetometery techniques. The θ-2θ x-ray diffraction measurements showed that a (200) peak of Fe appeared on thin film samples deposited at higher substrate temperatures. In these samples prepared at higher temperatures, lower coercive field and highly pronounced two-fold magnetic symmetry were observed. Our results show that maximum magnetocrystalline anisotropy occurred for sample deposited at 100 °C and it decreased at higher deposition temperatures.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Structural studies on the substitution of Ag, Na doped LCSMO CMR manganites

Synthesis and characterization of colossal magnetoresistance (CMR) materials has been a subject of scientific research due to the unique transport, magnetotransport, and magnetic properties. The single phase polycrystalline La{sub 0.7}Ca{sub 0.1}Sr{sub 0.1}M{sub 0.1}MnO{sub 3} (LCSMO) (M=Ag and Na) samples prepared using nitrate route method. The structural properties are studied at different dopants by X-ray diffraction. The surface morphology and elemental analysis of both samples were carried out by scanning electron microscopy (SEM) and energy dispersive X-ray technique (EDAX) respectively. The structural analysis shows that the LCSMO is crystallized in an orthorhombic perovskite structure belonging to Pnma space group. The crystal size of the sample is calculated using Scherrer formula. The SEM images show that the polycrystalline grains are observed to be near spherical shape and uniform in size. EDAX spectra taken from the surface of the synthesized powders show a nominal composition near the desired one for M=Na sample where as some vacancies are present in the A-site in the case of Ag substitution as will be discussed in this paper.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Micro-CT scouting for transmission electron microscopy of human tissue specimens

Transmission electron microscopy (TEM) provides sub-nanometre-scale details in volumetric samples. Samples such as pathology tissue specimens are often stained with a metal element to enhance contrast, which makes them opaque to optical microscopes. As a result, it can be a lengthy procedure to find the region of interest inside a sample through sectioning. Here, we describe micro-CT scouting for TEM that allows noninvasive identification of regions of interest within a block sample to guide the sectioning step. In a tissue pathology study, a bench-top micro-CT scanner with 10 m resolution was used to determine the location of patches of the mucous membrane in osmium-stained human nasal scraping samples. Furthermore, once the regions of interest were located, the sample block was sectioned to expose that location, followed by ultra-thin sectioning and TEM to inspect the internal structure of the cilia of the membrane epithelial cells with nanometre resolution. This method substantially reduced the time and labour of the search process from typically 20 sections for light microscopy to three sections with no added sample preparation. Lay description Electron microscopy provides very high levels of detail in a small area, and thus the question of where to look in an opaque sample, such as a stained tissue specimen, needs to be answered by sectioning the sample in small steps and examining the sections under a light microscope, until the region of interest is found. The search process can be lengthy and labor intensive, especially for a study involving a large number of samples. Small areas of interest can be missed in the process if not enough regions are examined. We also describe a method to directly locate the region of interest within a whole sample using micro-CT imaging, bypassing the need of blindly sectioning. Micro-CT enables locating the region within 3D space; this information provides a guide for sectioning the sample to expose that precise location for high resolution electron microscopy imaging. In a human tissue specimen study, this method considerably reduced the time and labor of the search process.

60 APPLIED LIFE SCIENCES↗

X-Ray Fingerprinting Techniques for Recognizing A Hydrological Role in the Formation of Minerals on the Surface of Mars

Previous work has demonstrated the ability of a miniaturized XRD-XRF instrument to perform in-situ analyses without sample preparation or acquisition. Deployment of this instrument on a Martian rover will allow a large number of rapid qualitative analyses, which will maximize the diversity of samples studied and selected for possible return. As a first step in designing a decision tree for recognizing minerals in complex mixtures, d spacings were plotted against intensity for several mineral groups comprising rock and soil types inferred for the surface of Mars (weathered basalt, playa and hydrothermal deposits, clay-rich soils). In all groups, d spacings cluster in a range from about 1-4 angstroms, which can under certain circumstances obscure patterns for individual phases. However, within the silicate family, minerals containing either bound OH- or molecules of H20 (clays, micas, amphiboles, zeolites) are characterized by a shift of peaks to higher d spacings. Large d spacings (greater than about 7 angstroms) thus act as a first-order filter for distinguishing hydrous from anhydrous silicates. The ability to quickly verify the presence of silicates that have interacted with water has important implications for using mineral chemistry and structure to help decipher the hydrologic and atmospheric history of Mars. This represents a beginning for developing more sophisticated methods of pattern recognition. These will combine XRD and XRF analyses with optical data to rapidly7 discern environmentally diagnostic assemblages without the necessity of identifying every peak individual mineral phase.

Metzger, Ellen P.↗

An alternative solid-state method to prepare pyrochlore-free KTaO{sub 3} at low temperature

Perovskite-type KTaO{sub 3} powder was synthesized by an alternative solid-state method at low temperature. Stoichiometric ammonium tantalum hydroxide, K{sub 2}C{sub 2}O{sub 4} and KF were mixed in water and then dried at room temperature. The crude product was formed by calcining the dried mixture at different temperatures. Pyrochlore-free KTaO{sub 3} powder was successfully synthesized after treating the crude product with water. KF plays an important role to inhibit the formation of pyrochlore K{sub 2}Ta{sub 2}O{sub 6} during the calcination process of ammonium tantalum hydroxide/K{sub 2}C{sub 2}O{sub 4}/KF mixture. X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier-transform infrared (FTIR) spectroscopy, UV-vis diffuse reflectance (UV-vis) spectroscopy and thermogravimetric (TG) analysis were used to characterize the precursor compound and as-prepared samples. XRD results show that pyrochlore-free KTaO{sub 3} powder can be obtained at 600 deg. C. SEM results reveal that the as-prepared products are agglomerated and each of the agglomerations consists of many small grains with 10-30 nm in diameter. - Graphical abstract: Pyrochlore-free KTaO{sub 3} powder was prepared at 600 deg. C using tantalum hydroxide/K{sub 2}C{sub 2}O{sub 4}/KF raw materials. Pyrochlore K{sub 2}Ta{sub 2}O{sub 6} and perovskite KTaO{sub 3} coexist at 600 deg. C using tantalum hydroxide/K{sub 2}C{sub 2}O{sub 4} raw materials. Highlights: > In-situ degradation of TaO{sub x}(OH){sub 5-x}(NH{sub 4}){sub x}, K{sub 2}C{sub 2}O{sub 4} and KF promotes the reaction. > Synthesis of KTaO{sub 3} displayed a two-step reaction path with the intermediate formation of K{sub 2}TaO{sub 3}F. > Formation of intermediate K{sub 2}TaO{sub 3}F benefits to prepare pyrochlore-free KTaO{sub 3} at low temperature. > Pyrochlore-free KTaO{sub 3} is prepared at 600 deg. C, which is the lowest temperature reported so far by hard chemistry method. > Synthetic method is a facile, rapid, low price and environment friendly route.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Boosted Critical Temperature of 166 K in Superconducting D 3 S Synthesized from Elemental Sulfur and Hydrogen

The discovery of superconductivity in H 3 S at 203 K marked an advance towards room-temperature superconductivity and demonstrated the potential of H-dominated compounds to possess a high critical temperature (T c ). There have been numerous reports of the H-S system over the last five years, but important questions remain unanswered. It is crucial to verify whether the Tc was determined correctly for samples prepared from compressed H 2 S, since they are inevitably contaminated with H-depleted byproducts. Here, we prepare stoichiometric H 3 S by direct in situ synthesis from elemental S and excess H 2 . The Im$_\bar{3}$ m phase of D 3 S samples exhibits a T c significantly higher than previously reported values (ca. 150 K), reaching a maximum T c of 166 K at 157 GPa. Furthermore, we confirm that the sharp decrease in T c below 150 GPa is accompanied by continuous rhombohedral structural distortions and demonstrate that the Cccm phase is nonmetallic, with molecular H 2 units in the crystal structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Broad spectral response photodetector based on individual tin-doped CdS nanowire

High purity and tin-doped 1D CdS micro/nano-structures were synthesized by a convenient thermal evaporation method. SEM, EDS, XRD and TEM were used to examine the morphology, composition, phase structure and crystallinity of as-prepared samples. Raman spectrum was used to confirm tin doped into CdS effectively. The effect of impurity on the photoresponse properties of photodetectors made from these as-prepared pure and tin-doped CdS micro/nano-structures under excitation of light with different wavelength was investigated. Various photoconductive parameters such as responsivity, external quantum efficiency, response time and stability were analyzed to evaluate the advantage of doped nanowires and the feasibility for photodetector application. Comparison with pure CdS nanobelt, the tin-doped CdS nanowires response to broader spectral range while keep the excellect photoconductive parameters. Both trapped state induced by tin impurity and optical whispering gallery mode microcavity effect in the doped CdS nanowires contribute to the broader spectral response. The micro-photoluminescence was used to confirm the whispering gallery mode effect and deep trapped state in the doped CdS nanowires.

36 MATERIALS SCIENCE↗

Determination of Silicon in Hydrazine

Inductively coupled plasma-mass spectrometry (ICP-MS) is a highly sensitive technique sometimes used for the trace determination of silicon at a mass-to-charge (m/z) ratio of 28, the most abundant natural isotope of silicon. Unfortunately, ICP-MS is unable to differentiate between other sources of m/z 28 and false positive results for silicon will result when other sources of m/z 28 are present. Nitrogen was a major source of m/z 28 and contributes to the m/z 28 signal when hydrazine sample or nitric acid preservative is introduced into the plasma. Accordingly, this work was performed to develop a sample preparation step coupled with an ICP-MS analysis that minimized non-silicon sources of m/z 28. In the preparatory step of this method, the hydrazine sample was first decomposed predominately to nitrogen gas and water with copper-catalyzed hydrogen peroxide. In the analysis step, ICP-MS was used without nitric acid preservative in samples or standards. Glass, a potential source of silicon contamination, was also avoided where possible. The method was sensitive, accurate, and reliable for the determination of silicon in monopropellant grade hydrazine (MPH) in AF-E-332 elastomer leaching tests. Results for silicon in MPH were comparable to those reported in the literature for other studies.

McClure, Mark B.↗

Effect Of Neodymium Substitution In Structural Characteristics Of Magnesium Ferrite

The effect of Nd{sup 3+} substitution on the structural properties of Magnesium ferrite was studied in the series MgNd{sub x}Fe{sub 2-x}O{sub 4}, where x = 0 to 0.3 in steps of 0.05. The series was prepared by sol-gel technique which is one of the novel technique to prepare nanosized samples. Structural characterization was done using X-ray diffractometer and Fourier Transform Infrared Spectrometer. XRD analysis reveals the prepared samples are single phasic till x = 0.2. From x0 = .25, a secondary phase of iron neodymium oxide appears along with the spinel phase. Particle size calculation shows the prepared samples are in the 9nm to 11 nm regime. Lattice parameter was found to increase with concentration of Nd. XRD and FTIR analysis confirmed spinel structure of the prepared samples. XRF result shows the expected composition of prepared samples. The frequency dependence of the dielectric constant in the range 100 Hz--120MHz was also studied

36 MATERIALS SCIENCE↗

In-Lab Rapid Analytical Detection of Lunar Volatiles By Universal Gas Analyzer With Comparison to GC-MS System

Introduction: The curation of permanently shadowed regions (PSRs) [1] on the lunar surface is centered around studies based upon the observed volatiles from the LCROSS mission [2]. The rapid detection of important volatile gases and vapors present in planetary bodies and Astromaterials by a standalone analytical device is an area of intense research interest in our group and Planetary Exploration & Astromaterials Research Laboratory (PEARL) facility and this work is relevant to the future preparation of viable lunar simulants for testing curation efforts down the road. The groundbreaking results obtained from the LCROSS Mission [2] open the requirements for the direct detection of volatiles present in regolith materials collected from the lunar surface. The mass spectrometry of volatile chemicals is a general technique that utilizes a set of instruments that creates charged ions from a gaseous chemical species and measures the intensities vs. mass-to-charge ratio (m/z) [3]. In this context, we discuss in-lab experimental results and procedures for rapid qualitative analysis of main LCROSS volatiles (water, H2S, NH3, CO2, and CH3OH) by a Universal Gas Analyzer (UGA) instrument. Additionally, the instrument performance was evaluated by measuring the isotopic abundance ratio of atmospheric Ar-40 to Ar-36 present in room air since, argon is a relevant gas in planetary studies as it can provide an insight and reference point to isotope studies [4]. Additional, cross comparisons were attempted and made between the two instruments to develop a robust analytical technique by comparing mass spectral data for H2S headspace samples with a Trace-1310/ ISQ 7000 (ThermoFisher Scientific.) GC-MS system. Background: The benchtop UGA System is equipped with an SRS UGA 300 quadrupole mass spectrometer designed and built by Stanford Research Systems [5]. This system can be configured for several types of gaseous chemical analysis. The inlet line continuously samples gases at low flow rates (several milliliters per minute) through a capillary limiting the intake pressure making the instrument ideal for online analysis of select gases and/or room atmosphere. Moreover, in our current UGA system, a change in composition at the inlet can be detected in about 200 milliseconds and a complete spectrum is acquired (for a range of 1-100 amu) in under 45 sec with masses measured at rates up to 25 msec per point [5]. This system provides a quick upstream analytical data that we can then compare to results obtained by our GC-MS system. Sample Preparation: Small volume (2-4 mL) of analyte sample was taken in a 10 mL glass vial and sealed with a crimped cap and purged with pure Ar or N2 gas to displace air from the top. The headspace sample was scanned by the UGA instrument at analog, histogram, and pressure vs. time modes. The isotopic abundance ratio for 40Ar-to-36Ar was estimated by measuring partial pressure vs. time scans and setting the mass at 40 and 36 respectively. Results and Discussions: In this work, we have investigated the applicability of the UGA system by qualitative analysis of a series of LCROSS volatiles measured individually. Fig. 1 demonstrates a set of vertically offset spectra for the partial pressures measured as a function of mass-to-charge (m/z) ratios. The average acquisition time for each spectrum was less than a minute suggesting that the UGA system is ideal for quick analysis of geochemical volatiles. For the cross-comparison, we analyzed an H2S headspace sample by a Trace-1310/ISQ-7000 system and compared mass spectral data with previously measured UGA histogram scan data (Fig. 2). In both cases, major peak positions are the same, however, the intensities of fragment ions ([1H132S]+ and [32S]+) are higher for UGA suggesting that the fragment ionization process is stronger in UGA compared to that of GC-MS. To investigate how the integrated area under each chromatogram varies with the headspace sample volume, a set of five H2S headspace samples with increasing volumes was analyzed by the GC-MS system (Fig. 3, inset). A small volume (e.g., 200 to 1000 µL) of H2S/H2O vapor was withdrawn from a 20 mL stock sample vial containing ~5 mL of 0.4% H2S in water by a gas-tight syringe and added to another 20 mL vial filled with argon and analyzed by the GC-MS system. Finally, the UGA detector sensitivity was evaluated by calculating the atmospheric 40Ar-to-36Ar isotopic abundance ratio in room air by running a partial pressure vs. time scan with setting the atomic mass at 40, and 36. Fig. 4(a) shows a ~25 min duration “P vs. time” scan for 40Ar (plot for 36Ar is not shown). The partial pressure values (~100 points) were corrected by subtracting the corresponding background pressure value for 37Ar and utilized to calculate 40Ar-to-36Ar isotopic abundance ratios as shown by Fig. 4b. The average isotopic abundance ratio is ~306 with a 2*STDEV ~13. This abundance ratio is significantly close to the previously reported value of 298.56 [6] and the ratio obtained by our GC-MS system (303 for a UHP grade Ar sample). Conclusions: Our study strongly evidenced that the benchtop UGA system is a valuable analytical tool for the detection of major LCROSS volatiles. The rapid scanning capability, the inexpensiveness of the whole system, and impressive detection sensitivity prove its worthiness as an essential device for advanced geochemical applications. Moreover, cross comparisons with the GC-MS provide important bridges into advanced curatorial efforts into the future. References: [1] Bickel, V.T., et al. (2021) Nat Commun 12, 5607. [2] Colaprete, A., et al. (2010) Science, 330, 463-468. [3] Glavin, D. P. et al. (2012) 2012 IEEE Aerospace Conference, 1-11. [4] Willett, C. D., et al. (2022) Geochimica et Cosmochimica Acta 329, 119-134. [5] Operation Manual and Programming Reference. (2018) Universal gas Analyzers, Stanford Research Systems. [6] Lee, J. Y., et al. (2006) Geochimica et Cosmochimica Acta 70, 4507–4512. Notes: (4 figures are attached with text as shown by the attached file)

Curation↗

No 182 W excess in the Ontong Java Plateau source

We report that small-scale W isotope variations in ancient and modern terrestrial rocks provide insights into Earth's accretion and early differentiation history as well as the long-term evolution of the Earth's mantle. Tungsten isotope studies on such rocks have exploited advances in mass spectrometry, both NTIMS and MC-ICPMS, which now permit the determination of W isotope ratios at unprecedented precision. While W isotope studies performed in different labs by MC-ICPMS and NTIMS generally exhibit excellent agreement, obtaining accurate W isotope data at this level of precision remains analytically challenging. For example, a recent NTIMS study reported a relatively large, +24 ppm excess in 182 W/ 184 W for a Phanerozoic sample from the Ontong Java Plateau (OJP), but no such 182 W/ 184 W anomaly was found in another study by MC-ICPMS. The present study aims to resolve the discrepancy between these two previous studies, and more generally to evaluate the agreement between different recent W isotope studies by NTIMS and MC-ICPMS. To this end, we report new W isotope data for OJP drill core samples obtained by MC-ICPMS. Additionally, the OJP samples analyzed here exhibit no resolvable 182 W/ 184 W excess relative to the standards and most terrestrial rocks. Moreover, the OJP samples as well as the terrestrial rock standards analyzed here exhibit small but variable W isotope variations for ratios involving 183 W, producing coupled variations in both ‘radiogenic’ (i.e., 182 W/ 183 W) and ‘non-radiogenic’ (i.e., 183 W/ 184 W) ratios. These W isotope variations are analytical in origin, induced during sample preparation, and very likely caused by a nuclear field shift isotope fractionation affecting primarily the odd isotope ( 183 W). The recently reported 182 W excess for an OJP sample may result from this nuclear field shift effect, as the NTIMS analyses had to rely on a double normalization involving the 183 W/ 184 W ratio. More generally, these results demonstrate that using 183 W data from any MC-ICPMS or NTIMS study requires a careful quantification of any potential analytical 183 W effect. Nevertheless, once such effects are taken into account, then both 182 W/ 184 W and 183 W/ 184 W can accurately be determined to a very high level of precision.

07 ISOTOPE AND RADIATION SOURCES↗