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At least 163 records · Page 9

WO 3 /CuWO 4 Ratio Controls Open-Circuit Photovoltage and Photocurrent in Type II Heterojunction Solar Fuel Photoelectrodes

WO 3 /CuWO 4 photoelectrodes for the oxygen evolution reaction benefit from a type II heterojunction for charge separation. However, the impact of the WO 3 /CuWO 4 ratio on the photocurrent and the photovoltage is not clear. To probe the effect of composition, Cu x W 1-x O y thin films with variable W:Cu ratio were prepared on FTO by reactive magnetron co-sputtering of W and Cu, followed by air annealing at 500ºC. EDS, XRD, Rietveld refinement, and Raman spectroscopy confirm the presence of crystalline WO 3 and CuWO 4 in the W rich films and increasing amounts of amorphous copper oxides in the Cu rich films. Bandgaps were determined by optical absorption spectroscopy, surface photovoltage spectroscopy (SPS), and photoaction spectra and are found to decrease from 2.7 eV to 1.2 eV with increasing copper oxide content. SPS reveals n-type semiconductor photoanode behavior for WO 3 /CuWO 4 samples and p-type photocathode behavior for CuO x rich films. Photoelectrochemical experiments confirm stable water oxidation with Faraday efficiency near unity for all W rich films and photocurrents that are increasing with CuWO 4 content. Optimal performance is seen for WO 3 /CuWO 4 mixed phases containing 47-75 mass% CuWO 4 . These compositions maximize charge separation at the type II heterojunction interface between the two materials. Additionally, according to incident photon to current efficiency (IPCE) data, the WO 3 improves photon conversion below 350 nm, while CuWO 4 improves conversion at 450-525 nm. Overall, this work shows for the first time how the WO 3 /CuWO 4 ratio controls the photovoltage and the photocurrent in type II heterojunction solar fuel photoelectrodes, and how copper oxides in the copper rich films severely degrade the performance. Furthermore, these results are useful in the context of bulk-heterojunction electrodes for the conversion of solar energy into fuels.

CuWO4↗

Detection of Br and I as atomic anions using liquid sampling – atmospheric pressure glow discharge/Orbitrap mass spectrometry

The quantification and determination of halogen isotope composition is essential in many fields including geochemistry and nuclear forensics. Detection of the halogen elements is commonly attempted with inductively coupled plasma mass spectrometry (ICP-MS) however, there are multiple challenges faced. Most significantly this includes very poor ionization efficiency and the potential for isobaric interferences from either matrix or plasma species. Thus, sensitivity and accuracy are often limiting issues. Here a liquid sampling-atmospheric pressure glow discharge (LS-APGD) ionization source is coupled with an ultrahigh resolution Orbitrap MS to perform halogen detection of bromine and iodine as initial analytes. This facilitates simple and sensitive detection of these elements as atomic anions from simple aqueous salt solutions. Collision-induced dissociation (CID) and higher-energy collisional dissociation (HCD) energies were optimized to produce the maximum response of Br − and I − . The LS-APGD conditions were optimized using a design of experiments (DOE) approach for Br − and I − concurrently. Response curves for Br − and I − solutions determined limit of detection (LOD) values of 50 pg and 5 pg, respectively, in 20 μL aliquots. The curves indicated response factors of 0.67 for 79 Br − and 0.90 for 127 I − . Br isotope ratios were determined with precision between 0.7 and 7.3% RSD, with the isotope ratios determined with precision 0.8% RSD at concentrations above the limit of quantification. Preliminary tests were conducted to evaluate the effect of different cations (Na + , K + , and Mg 2+ ) on Br − responses, with no discernible impacts observed on the halogen signal responses. This study demonstrates the potential use of the LS-APGD-Orbitrap-MS for the detection of multiple halogens while avoiding interferences, minimizing sample preparation, and overcoming ionization barriers.

Lang, Dehlia A. [Clemson University, SC (United St↗

How to avoid multiple scattering in strongly scattering SANS and USANS samples

Small Angle Neutron Scattering (SANS) and Ultra Small Angle Neutron Scattering (USANS) are the only available experimental techniques to provide seamless non-destructive measurements of the geometry of the accessible and inaccessible pore structure of rocks from sub-nanopore size to the scale of macropores. They have therefore become the measurement of choice for tight reservoir rocks such as organic rich shales. A simplifying assumption in the analysis is, however, that during the path of neutrons through the sample each neutron is only scattered once. Shales are samples with a high scattering power and Multiple Scattering (MS) may occur which requires special modelling for deconvolution of the results. The approach to avoid MS is to simply reduce the sample thickness to <0.15–0.5 mm. Here, in this work, we present a systematic method on wavelength selection and preparation of samples to optimise extraction of microstructural data and minimise parasitic errors. Experimentally measured SAS transmission (TSAS) values are used as a practical criterion for estimation of the extent of MS. Generous beamtime allocations allowed robust testing revealing that sample thicknesses can be twice as thick as predicted using the standard protocol. Analysing thicker samples is particularly beneficial for statistically relevant characterisation of heterogeneous samples making the new protocol the method of choice for such samples.

(U)SANS↗

Etching sharp tips from thin metallic wires for tuning-fork-based scanning probe microscopy

Sharp tips are critical for obtaining high resolution images in scanning probe microscopy (SPM), particularly in samples with large variations in topography. For tuning-fork-based SPM, such tips are commonly obtained by electrochemical etching of metallic wires (e.g., tungsten). Electrochemical etching of metallic wires is the preferred means of preparing tips for scanning tunneling microscopy (STM), and techniques for obtaining sharp tips have been investigated extensively. However, the requirements for STM and tuning-fork-based SPM are different. In particular, the wires used in STM are typically 250-500 μ m in diameter, while the wires used for tuning-fork-based SPM are usually an order of magnitude narrower in order to minimize loading of the tuning fork: 25-50 μ m and sometimes down to a few micrometers in diameter. Consequently, many of the recipes developed for etching thicker metallic wires for STM tips do not give optimal results for smaller diameter wires. The authors describe here a modification of the etching circuit of Ibe et al . that significantly improves the reproducibility and reliability of the etching process for thin wires, and discuss the parameters that affect the aspect ratio of produced tips.

42 ENGINEERING↗

Understanding the effects of fabrication process on BaZr 0.9 Y 0.1 O 3– δ grain-boundary chemistry using atom probe tomography

Proton-conducting oxides, such as BaZr 0.9 Y 0.1 O 3–δ (BZY10), are receiving significant scientific attention for application in a variety of electrochemical applications. It has been shown that the synthesis route has a significant effect on the ionic behavior of these materials, especially the grain boundaries (GB). In this study, laser-pulsed atom probe tomography (APT) is used to characterize the GB chemistry of BZY10 samples prepared by four different methods: (1) spark plasma sintering (SPS), (2) conventional sintering followed by high-temperature annealing (HT), (3) conventional sintering with NiO used as a sintering aid (SSR-Ni), and (4) solid-state reactive sintering of oxide precursor powders with NiO as a reactive sintering aid (SSRS-Ni). Oxygen depletion (corresponding to oxygen vacancy accumulation) was observed at every GB in this study, consistent with the positive space-charge GB region commonly assigned to these materials. In contrast to the consistent trends associated with oxygen depletion, cation constituents showed varying segregation/depletion behaviors. The samples that used NiO revealed Ni preferentially segregating to the GB. The most common impurities in BZY10 are Al, Fe, Mg, Si, and Sr, all of which generally accumulate at GBs. In order to quantify these chemical trends, the APT method was optimized for this material supplemented with understanding from density functional theory (DFT). Finally, this APT study reveals the complexity of BZY10 GB chemistry and shows that even adjacent GBs in the same material can sometimes show surprisingly different GB chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Production of Carbon Nanomaterials and Sorbents from Domestic U.S. Coal (Final Report)

The main goal of this project was to produce high-value carbon nanomaterials and carbon sorbents from domestic coal resources in a cost-effective manner. Four types of domestic coal samples were processed through a combination of deashing, devolatilization, oxidation, reduction, and activation treatments to produce graphene oxide (GO), reduced graphene oxide (RGO), and activated carbon (AC). The precursors and developed materials were extensively characterized by various methods to investigate the impact of the coal feedstock type on the yield and quality of each product. A commercial graphite-based GO sample was included in the experimental work as the baseline material for comparison with the coal-based materials developed in this work. The performed work also included a technoeconomic analysis and cost estimation for a plant processing 20 tons/day coal, a market evaluation for the graphene materials, and a technology gap analysis. A simple process by concentrated nitric acid oxidation is used to oxidize coal precursors for the production of GO. Fine oxidized coal particles that were separated from larger oxidized coal particles had significantly higher oxygen contents and were identified as coal-based GO samples. Coarse oxidized coal particles were used as precursors for production of AC. Based on the Raman spectroscopy results, coal-based GO samples exhibited G and D bands similar to those of graphite-based GO samples. X-ray photoelectron spectroscopy revealed that coal-based GO samples had surface oxygen contents of ~26-35% that were higher than the oxygen contents of graphite-based GO samples. Larger particles of oxidized coal samples were activated under different conditions to produce high surface area functionalized AC. Prepared materials had surface areas exceeding 1,500 m 2 /g and pore volumes more than 1 cm 3 /g with different pore size distributions. Reduced graphene oxide samples were prepared by thermal reduction of both coal-based and graphite-based GO samples at 170-2800 ºC. Coal-based and graphite-based RGO samples exhibited similar carbon contents, Raman spectra, and XRD profiles. Heat treatment above 1500 ºC shifted RGO to synthetic graphite. Among anthracite, bituminous, subbituminous, and lignite coals tested, anthracite was the best precursor to produce carbon nanomaterials exhibiting properties similar to those of graphite-based materials. Anthracite-based carbon nanomaterials also had the highest production yields. Technoeconomic analysis estimated the production cost of GO and RGO for anthracite-based samples at about 2,600 and 4,200 $/ton, respectively, which is about two orders of magnitude lower than the current estimated price of graphite-based materials. Several gaps to further develop the proposed technology were identified and discussed that include process and equipment optimization, process integration, need for additional bench- and pilot-scale experiments, and other items to reduce the scale up risk. Market analysis reports suggested a compound annual growth rate of 40% for graphene and related materials. Short-term applications include composites, inks, and coatings. However, energy storage applications appear to be the dominant potential long-term applications. Different applications of coal-based GO and RGO need to be explored and clear metrics and standards for each application need to be developed.

01 COAL, LIGNITE, AND PEAT↗

Additive Manufacturing of Porous Ceramics With Foaming Agent

The macro-porous ceramics has promising durability and thermal insulation performance. As porous ceramics find more and more applications across many industries, a cost-effective and scalable additive manufacturing technique for fabricating macro-porous ceramics is highly desirable. Herein, we reported a facile additive manufacturing approach to fabricate porous ceramics and control the printed porosity. Several printable ceramic inks were prepared, and the foaming agent was added to generate gaseous bubbles in the ink, followed by the direct ink writing and the ambient-pressure and room-temperature drying to create the three-dimensional geometries. In this work, a set of experimental studies were performed to optimize the printing quality. The results revealed the optimal process parameters for printing the foamed ceramic ink with a high spatial resolution and fine surface quality. Varying the concentration of the foaming agent enables the controllability of the structural porosity. The maximum porosity can reach 85%, with a crack-free internal porous structure. The tensile tests showed that the printed macro-porous ceramics possessed enhanced durability with the addition of fiber. With a high-fidelity three-dimensional (3D) printing process and the precise controllability of the porosity, we showed that the printed samples exhibited a remarkably low thermal conductivity and durable mechanical strength.

36 MATERIALS SCIENCE↗

Rapid macrovoid characterization in membranes prepared via nonsolvent-induced phase separation: A comparison between 2D and 3D techniques

Optimizing the performance of asymmetric membranes prepared via nonsolvent-induced phase separation (NIPS) requires a quantitative understanding of how processing variables influence membrane morphology. Presently, the most useful structural quantification techniques require 3D visualization of the membrane structure and are best suited for studies seeking detailed information on small datasets. This study proposes and validates a rapid and accurate technique for quantifying macroporosity (i.e., D m ), a simple descriptor of sublayer macrovoid content in asymmetric membranes D m . values measured from segmented cross-sectional imaging performed via X-ray computed tomography (XCT) and scanning electron microscopy (SEM) are presented and compared for three asymmetric membranes prepared from commercial polymers. Importantly, analyses of 3D XCT membrane reconstructions reveal that D m is described by a single, centralized mean, which demonstrates that macrovoid content is spatially homogenous. Thus, D m can be approximated from limited sampling of the 2D cross-sectional membrane structure via SEM. A proposed 2D SEM sampling method provides D m estimates within ±6% of corresponding 3D XCT values with 30 independent measurements for the three membranes. Further sensitivity is achieved using complementary descriptors such as macrovoid count density (i.e., C m ). This technique is thus a useful tool for characterizing macroporosity from a broad selection of membrane samples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of annealing temperature on the magnetic properties of highly crystalline biphase iron oxide nanorods

We report on the effects of annealing temperatures ranging from 225 °C to 325 °C on the magnetic properties of high aspect ratio iron oxide nanorods consisting of a ferrimagnetic Fe 3 O 4 phase and an antiferromagnetic α-Fe 2 O 3 phase in an as-prepared state. Annealing at the aforementioned temperatures under a constant flow of O 2 for 3 h leads to an increment of the volume fraction of the antiferromagnetic α-Fe 2 O 3 phase and concomitant enhancement of the crystallinity of the ferrimagnetic Fe 3 O 4 phase. These opposing effects compete with each other, resulting in a decrease in global magnetization with increasing the annealing temperature. The desirable magnetic properties are achieved for the sample annealed at 250 °C. For all samples investigated, we observed an increase in low field magnetization at low temperatures after the sample is field cooled in the presence of a 1T magnetic field, which we attribute to the ordering of macro-spins of the weakly ordered antiferromagnetic α-Fe 2 O 3 phase in the presence of the cooling field. Our study will pave the way for determining the optimal conditions to enhance the magnetic characteristics in iron oxide nanorods, which will enable its use in spintronics and biomedical applications.

36 MATERIALS SCIENCE↗

Non-Gaussian photonic state engineering with the quantum frequency processor

Non-Gaussian quantum states of light are critical resources for optical quantum information processing, but methods to generate them efficiently remain challenging to implement. Here we introduce a generic approach for non-Gaussian state production from input states populating discrete frequency bins. Based on controllable unitary operations with a quantum frequency processor, followed by photon-number-resolved detection of ancilla modes, our method combines recent developments in both frequency-based quantum information and non-Gaussian state preparation. Leveraging and refining the K-function representation of quantum states in the coherent basis, we develop a theoretical model amenable to numerical optimization and, as specific examples, design quantum frequency processor circuits for the production of Schrödinger cat states, exploring the performance tradeoffs for several combinations of ancilla modes and circuit depth. Our scheme provides a valuable framework for producing complex quantum states in frequency bins, paving the way for single-spatial-mode, fiber-optic-compatible non-Gaussian resources.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Scalable Surface Micro-Texturing of LLZO Solid Electrolytes for Battery Applications

A challenge for lithium lanthanum zirconate (LLZO)-based solid-state batteries is to increase the critical current density (CCD) to enable high current cycling. A promising strategy is to modify the LLZO surface morphology to provide a larger contact area with the Li metal. Here, a surface-textured thin LLZO electrolyte was prepared through an easily scalable process. The texturing process is a simple pressing of green LLZO tapes between micro-textured substrates. A variety of textures can be produced, depending on the type of substrate, and texturing can be on either one side or both sides. For this work, after pressing and sintering, several micro-patterns are formed on thin LLZO (~118 μm thick). The properties of the various samples were characterized to investigate the impact of surface texturing, and the most promising ones were selected for electrochemical testing in symmetrical lithium cells and full cells. Li symmetric cells using a coarse ridge-textured LLZO exhibit ~2.5 times increased CCD compared to planar non-textured LLZO, and a solid-state full cell shows stable cycling and improved rate performance. Finally, we believe this process offers a favorable trade-off of processing complexity vs structural optimization to maximize CCD.

25 ENERGY STORAGE↗

Report of the NASA Science Definition Team for the Mars Science Orbiter (MSO)

NASA is considering that its Mars Exploration Program (MEP) will launch an orbiter to Mars in the 2013 launch opportunity. To further explore this opportunity, NASA has formed a Science Definition Team (SDT) for this orbiter mission, provisionally called the Mars Science Orbiter (MSO). Membership and leadership of the SDT are given in Appendix 1. Dr. Michael D. Smith chaired the SDT. The purpose of the SDT was to define the: 1) Scientific objectives of an MSO mission to be launched to Mars no earlier than the 2013 launch opportunity, building on the findings for Plan A [Atmospheric Signatures and Near-Surface Change] of the Mars Exploration Program Analysis Group (MEPAG) Second Science Analysis Group (SAG-2); 2) Science requirements of instruments that are most likely to make high priority measurements from the MSO platform, giving due consideration to the likely mission, spacecraft and programmatic constraints. The possibilities and opportunities for international partners to provide the needed instrumentation should be considered; 3) Desired orbits and mission profile for optimal scientific return in support of the scientific objectives, and the likely practical capabilities and the potential constraints defined by the science requirements; and 4) Potential science synergies with, or support for, future missions, such as a Mars Sample Return. This shall include imaging for evaluation and certification of future landing sites. As a starting point, the SDT was charged to assume spacecraft capabilities similar to those of the Mars Reconnaissance Orbiter (MRO). The SDT was further charged to assume that MSO would be scoped to support telecommunications relay of data from, and commands to, landed assets, over a 10 Earth year period following orbit insertion. Missions supported by MSO may include planned international missions such as EXOMARS. The MSO SDT study was conducted during October - December 2007. The SDT was directed to complete its work by December 15, 2007. This rapid turn-around was required in order to allow time to prepare an Announcement of Opportunity (AO) for science investigations, to be released in early 2008.

Smith, Michael↗

Combined Imaging and RNA-Seq on a Microfluidic Platform for Viral Infection Studies

The goal of this work was to pioneer a novel, low-overhead protocol for simultaneously assaying cell-surface markers and intracellular gene expression in a single mammalian cell. The purpose of developing such a method is to be able to understand the mechanisms by which pathogens engage with individual mammalian cells, depending on their cell surface proteins, and how both host and pathogen gene expression changes are reflective of these mechanisms. The knowledge gained from such analyses of single cells will ultimately lead to more robust pathogen detection and countermeasures. Our method was aimed at streamlining both the upstream cell sample preparation using microfluidic methods, as well as the actual library making protocol. Specifically, we wanted to implement a random hexamer-based reverse transcription of all RNA within a single cell (as opposed to oligo dT-based which would only capture polyadenylated transcripts), and then use a CRISPR-based method called scDash to deplete ribosomal DNAs (since ribosomal RNAs make up the majority of the RNA in a mammalian cell). After significant troubleshooting, we demonstrate that we are able to prepare cDNA from RNA using the random hexamer primer, and perform the rDNA depletion. We also show that we can visualize individually stained cells, setting up the pipeline for connecting surface markers to RNA-sequencing profiles. Finally, we test a number of devices for various parts of the pipeline, including bead generation, optical barcoding and cell dispensing, and demonstrate that while some of these have potential, more work is needed to optimize this part of the pipeline.

59 BASIC BIOLOGICAL SCIENCES↗

Characterization of Kariya ( Hildegardia barteri (Mast.) Kosterm) Seed Oil Fatty Acid Methyl Ester Prepared from Basic Catalytic Transesterification

The rising global energy demand, alongside concerns regarding environmental deterioration due to the use of fossil fuels, has spurred extensive investigation into renewable energy alternatives. Biomass-derived biodiesel, especially from lesser-known oil sources, emerges as a promising option. This research focuses on analyzing the fatty acid methyl esters (FAMEs) derived from Kariya (Hildegardia barteri (Mast.) Kosterm) seed oil through basic catalytic transesterification using gas chromatography–flame ionization detector (GC–FID) analysis, assessing its potential as a biodiesel feedstock. Oil extraction from Kariya seeds was carried out using three solvents (n-hexane, ethanol, and a 1:1 blend of hexane and ethanol), followed by transesterification with methanol. Gas chromatography–mass spectrometry (GC–MS) and GC–FID analyses were utilized to identify and quantify FAMEs in the resulting biodiesel. The results revealed various FAMEs, including methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl linoleate, and methyl linolenate. Significant differences in FAME composition were observed among the samples, with hexane–ethanol Kariya oil biodiesel (HE-KOB) showing the highest FAME content (76.1%). This combination of solvents exhibited synergistic effects on the composition of HE-KOB, suggesting potential optimization strategies for biodiesel production. Fourier transform infrared spectroscopy (FTIR) provided additional insights into the molecular composition of the biodiesel samples, confirming their biodiesel nature through the identified functional groups such as methyl, methylene, hydrocarbon, ester, aldehyde, and alkene. Thermogravimetric analysis (TGA) for thermal decomposition also gave an insight into FAME composition and its contribution to the degree of conversion of biodiesel to energy. These findings highlight the feasibility of utilizing Kariya seed oil as a biodiesel feedstock, emphasizing the importance of solvent selection and transesterification conditions in optimizing FAME yield and composition. This research contributes to the exploration of underutilized oil sources for sustainable biodiesel production, aligning with the global shift towards cleaner and renewable energy sources.

09 BIOMASS FUELS↗

Microstructural Evolution and Mechanical Properties of LP-DED NASA HR-1 – A Hydrogen Resistant AM Superalloy for Space Propulsion Applications

The National Aeronautics and Space Administration (NASA) has actively pursued metal additive manufacturing (AM) technologies for spaceflight applications since the late 2000s. AM offers transformative advantages in cost, schedule, part consolidation, and design flexibility. Among the various AM techniques, laser powder directed energy deposition (LP-DED) is particularly well suited for fabricating complex geometries with fine feature resolution. In propulsion systems that utilize high-pressure gaseous hydrogen—such as liquid hydrogen rocket engines—hydrogen environment embrittlement (HEE) presents a serious threat to material performance 1,2 . Mechanical property degradation under these conditions can compromise component reliability, especially under cyclic loading. To address this challenge, NASA developed NASA HR-1 (Hydrogen Resistant-1) as a solution for liquid rocket engine components operating in hydrogen-rich environments, using the LP-DED technique 3-9 . A key component in a liquid rocket engine is the exhaust nozzle, which is typically regeneratively cooled (regen) due to the high heat flux. NASA HR-1 was specifically developed for regen nozzle applications using hydrogen as a propellant, providing resistance to HEE, a critical issue for many materials. The AM version of NASA HR-1 was also formulated to achieve high ultimate tensile strength, along with high yield strength and ductility in this environment 5,6 . Low-cycle fatigue (LCF) is another important consideration in nozzle design, as components are expected to endure multiple starts and missions. Additionally, the LP-DED version of the alloy exhibits improved thermal conductivity compared to its wrought counterpart, which benefits nozzle cooling. Overall, NASA HR-1 offers an excellent balance of high strength, HEE resistance, LCF performance, thermal conductivity, and ductility to meet the demanding requirements of channel-cooled nozzles and other components used with hydrogen and other propellants. The LP-DED–processed NASA HR-1 requires several post-processing heat treatment steps to achieve the material properties desirable for its intended application 6 . These steps include stress relief, homogenization, solution annealing, and aging for precipitation hardening. The stress relief treatment mitigates residual stresses accumulated during the LP-DED process and minimizes the potential for distortion. Homogenization, a common step for AM materials, reduces elemental segregation and promotes recrystallization to develop a more equiaxed grain structure. The subsequent solution annealing treatment heats the part to a solid solution temperature to dissolve the undesirable η-phase that forms during cooling from homogenization, followed by rapid cooling to retain an η-phase–free microstructure. Finally, aging promotes precipitation of the strengthening γ′ phase in the alloy. The integration of compositional design and optimized thermal processing enables high-quality LP-DED NASA HR-1 components with excellent microstructural and mechanical stability. Improved chemical and microstructure homogeneity enhances ductility and fatigue resistance—both critical for safe and reliable operation in high-pressure hydrogen environments. NASA has successfully fabricated and hot-fire tested multiple subscale and full-scale channel wall nozzles using LP-DED NASA HR-1 5,6, 9-14 . These efforts included process refinements to support thin-wall construction and various channel geometries. Throughout development, several key observations emerged. After homogenization, the as-built columnar grain structure transforms into a fully equiaxed microstructure. However, subsequent treatments—such as solution annealing and aging—result in changes that are more difficult to track. The grain structure remains largely unchanged, and the γ′ precipitates, typically 5–10 nm in diameter, are beyond the resolution of scanning electron microscopy (SEM). While transmission electron microscopy (TEM) can resolve these fine precipitates, TEM sample preparation is time-consuming and difficult for LP-DED material. As an alternative, differential scanning calorimetry (DSC) offers a useful, qualitative approach to monitor precipitate evolution throughout different stages of heat treatment. The overall goal is to improve the understanding of how heat treatment affects the microstructure and mechanical performance of LP-DED NASA HR-1. This paper presents heat treatment design considerations, microstructural characterization, mechanical testing – including tensile and LCF testing in both air and hydrogen environments.

Superalloy↗

Linker-Free Magnetite-Decorated Gold Nanoparticles (Fe3O4-Au): Synthesis, Characterization, and Application for Electrochemical Detection of Arsenic (III)

Linker-free magnetite nanoparticles (Fe3O4NPs)-decorated gold nanoparticles (AuNPs) were grown using a new protocol that can be used as a new platform for synthesis of other intact metal–metal oxide nanocomposites without the need for linkers. This minimizes the distance between the metal and metal oxide nanoparticles and ensures the optimum combined effects between the two material interfaces. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy confirmed the successful synthesis of the Fe3O4-Au nanocomposite, without any change in the magnetite phase. Characterization, using transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectroscopy, revealed the composite to consist of AuNPs of 70 ± 10 nm diameter decorated with tiny 10 ± 3 nm diameter Fe3O4NPs in Au:Fe mass ratio of 5:1. The prepared Fe3O4-Au nanocomposite was embedded in ionic liquid (IL) and applied for the modification of glassy carbon electrode (GCE) for the electrochemical detection of As(III) in water. By combining the excellent catalytic properties of the AuNPs with the high adsorption capacity of the tiny Fe3O4NPs towards As(III), as well as the good conductivity of IL, the Fe3O4-Au-IL nanocomposite showed excellent performance in the square wave anodic stripping voltammetry detection of As(III). Under the optimized conditions, a linear range of 1 to 100 μg/L was achieved with a detection limit of 0.22 μg/L (S/N = 3), and no interference from 100-fold higher concentrations of a wide variety of cations and anions found in water. A very low residual standard deviation of 1.16% confirmed the high precision/reproducibility of As(III) analysis and the reliability of the Fe3O4-Au-IL sensing interface. Finally, this proposed sensing interface was successfully applied to analyzing synthetic river and wastewater samples with a 95–101% recovery, demonstrating excellent accuracy, even in complex synthetic river and wastewater samples containing high concentrations of humic acid without any sample pretreatments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analysis of persistent contaminants and personal care products by dispersive liquid-liquid microextraction using hydrophobic magnetic deep eutectic solvents

Here, in this work, hydrophobic magnetic deep eutectic solvents (HMDESs) were used in the development of a simple and rapid dispersive liquid-liquid microextraction (DLLME) approach coupled to high performance liquid chromatography with UV detection (HPLC-UV) for the determination of ten organic contaminants including five polycyclic aromatic hydrocarbons, four UV filters, and a pesticide from water at trace levels. The HMDESs were prepared by mixing a hydrogen bond acceptor, metal halide salt, and hydrogen bond donor in suitable molar ratios. Two HMDESs, 2 tetraoctylammonium bromide ([N 8888 + ][Br - ]): cobalt chloride (CoCl 2 ): 4 octanoic acid (OA) and 3 trioctylphosphine oxide (TOPO): neodymium chloride (NdCl 3 ): 3 OA, offered the highest analyte extraction efficiency overall and were chosen as suitable solvents for validation of the microextraction method. Under optimized extraction conditions, the method required 30 µL of HMDES as extraction solvent, acetone (87.5 µL) as disperser solvent, a NaCl concentration of 30% (w/v), and an extraction time of 120 s at 20°C. Enrichment factors of the analytes ranged from 44.6 for 3-(4-methylbenzylindene) camphor to 66.0 for 2-ethylhexyl-4-(dimethyl)aminobenzoate. The method provided low limits of detection (LODs) ranging from 0.5 to 4.5 µg L -1 , and acceptable precision, with RSD values lower than 9.6%. Furthermore, the validated method was successfully applied for tap and lake water analysis, resulting in relative recoveries of spiked samples ranging between 94.7 and 119.2%.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗