Electron Microprobe Research Articles

Analytical Techniques for Detecting Rare Earth Elements in Geological Ores: Laser-Induced Breakdown Spectroscopy (LIBS), MFA-LIBS, Thermal LIBS, Laser Ablation Time-of-Flight Mass Spectrometry, Energy-Dispersive X-ray Spectroscopy, Energy-Dispersive X-ray Fluorescence Spectrometer, and Inductively Coupled Plasma Optical Emission Spectroscopy

Rare earth elements (REEs) hold significant industrial, scientific, and modern technological worth. This study focused on detecting and quantifying REEs in various geological ore samples. These samples were collected from different REE-bearing locations recommended by geological experts. The analysis was conducted using laser-induced breakdown spectroscopy (LIBS) and laser ablation time-of-flight mass spectrometry (LA-TOF-MS). In this work, LIBS methodology was employed using three different configurations: standard LIBS, LIBS with an applied magnetic field, and LIBS with both an applied magnetic field and target sample heating within an optimal temperature range. Elements from the REE group, specifically lanthanum (La), cerium (Ce), and neodymium (Nd), were identified and quantified. To detect, quantify, and validate the results from LIBS and LA-TOF-MS, we utilized an array of analytical techniques—Energy-Dispersive X-ray Spectroscopy (EDX), Energy-Dispersive X-ray Fluorescence Spectrometer (ED-XRF), and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Interestingly, the quantitative results for REEs (La, Ce, and Nd) in the ore samples obtained using the LIBS technique with various configurations were found to be in agreement with those from LA-TOF-MS, EDX, XRF, and ICP-OES. In addition, LIBS enables detailed microchemical imaging, allowing the map of the spatial distribution of elements within the mineral–ore matrix. The high-resolution microscale elemental mapping of REEs was accomplished using the emission lines Ce (II) at 446.0 nm, La (II) at 492.1 nm, and Nd (II) at 388.8 nm. By integrating multiple analytical techniques, our study enabled the construction of a complete elemental distribution map, providing new insights into the geochemical processes and mineral composition of rare earth ores, while advancing geochemistry and contributing valuable data for rare earth resource exploration.

Electrochemical behavior and microstructure of diffusion welding of zirconium alloy and super duplex stainless steel

In this study, the effect of welding temperature on interface microstructure, mechanical properties, and electrochemical behavior of diffusion welded joints (DWJs) of zirconium alloy (ZrA, Zr702 grade) and super duplex stainless steel (2205 duplex stainless steel grade) were investigated. Alloys were welded in a vacuum atmosphere at four different temperatures (800, 850, 900, and 925 °C) for 75min under 4MPa compressive pressure. The optical, scanning electron microscopy, electron probe micro-analyzer, and X-ray diffraction techniques were used to characterize the interfacial microstructure of the DWJs. Layers of intermetallics were formed along the welded interface at 850 °C and above welding temperatures. At 850 °C, a single reaction layer (phase mixture of ZrFe2+ZrCr2) was observed; however, bilayers (ZrFe2+ZrCr2 and Fe2Zr+FeZr3 phase mixtures), and triple layers (ZrFe2+ZrCr2, Fe2Zr+FeZr3, and β-Zr+FeZr3 phase mixtures) were observed at the welded interface of the joints processed at 900 and 925 °C, respectively. Width of the reaction layer (phase mixtures) increases with an increase in the welding temperature. The DWJs processed at 900 °C reach the maximum joint strength of ~312MPa along with ~6.4% ductility. For corrosion analysis, studies of the base alloys and DWJs in 0.1mol/L HCl and 0.1mol/L NaOH solutions separately using electrochemical techniques, such as open circuit potential, electrochemical impedance spectroscopy, and potentiodynamic polarization were undertaken.

Anomalous tellurium enrichment associated with gold mineralization: A mineralogical and isotopic study of the Yongxin Te-Au deposit, northeast China

The Yongxin tellurium-gold (Te-Au) deposit, a large epithermal deposit in the Duobaoshan polymetallic metallogenic belt (DPMB) within eastern section of the Central Asian Orogenic Belt (CAOB), is mainly hosted by syenogranite and mylonite. However, the Te-Au occurrence, precipitation mechanism and genesis in this deposit remain elusive. In this study, pyrite, the primary host of Te-Au mineralization, was studied utilizing multiparametric techniques such as scanning electron microscope (SEM), electron probe microanalysis (EPMA), in-situ laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) and femtosecond laser ablation coupled multi-collector inductively coupled plasma mass spectrometry (fs LA-MC-ICP-MS). The results show that there are three generations of pyrite termed here as Py1, Py2 and Py3. The coarse euhedral Py1 and fine vein Py2 contain negligible to low contents of Te and Au, whereas the anhedral aggregated Py3 with porosity and grain boundary (GB) shows the highest concentrations of Te and Au. Representative LA-ICP-MS profiles show that Te-Au occurs either as solid solution in the Py1 and Py2 or submicroscopic Au-Ag-Te-Bi inclusions, electrum and native gold in Py3. Thermodynamic data of telluride and sulfide show that the Te-Au was deposited under relatively oxidizing conditions with values of log f Te2 ranging from −15.2 to −11.2 and log f S2 from −16.7 to −12.1. at 200 °C. We infer that fluid mixing and fluid-rock interaction were the dominant mechanisms that triggered the precipitation of Te-Au in the Yongxin Te-Au deposit. Geochemical and geochronological data indicate that the likely source of Te is Te-rich oceanic sediments originating from the Western Pacific Plate. Pyrite and telluride from the gold deposits can be potential targets for Te exploration in the DPMB.

Coloring Multilayer Zirconia May Affect Its Optical and Mechanical Properties

The coloring process of monolithic dental zirconia caused considerable debate on the possible effects of different coloring methods. The main objective of this study was to investigate the influence of pigments in 3 multilayer 5-mol% yttria partially stabilized zirconia (5Y-PSZ) disks (Lava Esthetic A2 [Zr-AGG_A2] and Bleach [Zr-AGG_BL], both 3M Oral Care, and Katana STML A2 [Zr-NoAGG], Kuraray Noritake). The influence of pigment addition on the translucency parameter (TP00), fracture toughness, Vickers hardness, biaxial strength, and hydrothermal stability was assessed and correlated with the microstructure and phase composition. The pigment composition and distribution were evaluated by light and fluorescence microscopy, electron probe microanalysis, and nano–scanning electron microscopy. The chemical and phase composition and aging behavior were assessed using X-ray fluorescence and X-ray diffraction, respectively, while the aging sensitivity of the pigments was evaluated using micro-Raman spectroscopy. In contrast to Zr-NoAGG, possessing a typical 5Y-PSZ microstructure, the pigment additions in both Zr-AGG_A2/BL zirconia resulted in large yellow and blue fluorescent Er-, Hf-, and Al-containing agglomerates composed of small grains (0.57 µm and 0.38 µm, respectively, vs. 0.92 µm for the surrounding grains) with lower Y2O3 content. Zr-AGG_A2 had the lowest aging resistance, with transformation degradation occurring exclusively within the pigment agglomerates. All zirconia grades had a high Y2O3 content (4.2%–5.7 mol%) tetragonal ZrO2 phase and a high (42%–55 wt%) cubic ZrO2 phase content. Although no statistical differences were measured for hardness and toughness, Zr-NoAGG had a significantly higher TP00, higher flexural strength, and lower mechanical reliability compared to both Zr-AGG_A2/BL zirconia. The rare-earth oxide-containing zirconia agglomerates that were added as pigments to the multilayered monolithic Zr-AGG_A2/BL zirconia are the cause for their lower optical and mechanical properties and reduced aging resistance.

Fluid inclusion and pyrite geochemistry of the Jiapigou gold deposit, North China Craton: Implication for origin of orogenic gold deposit?

The Jiapigou auriferous belt in Jilin province has been recognized as substantial gold-producers in the North China Craton (NCC). Gold mineralization in this district mainly occurs in mineralized quartz veins and alteration zones, characterized by silicification, pyritization, and argillitization. The quartz veins contain three generations of mineralized quartz, namely, qtz1 (probably oldest), qtz2 (slightly younger), and qtz3 (probably youngest) were identified using SEM-CL. The fluid inclusions in all three generations of quartz are broadly of three types, viz., bi-phase Ia (H2O-CO2), tri-phase Ib (H2O-CO2-NaCl ± CH4), and II (H2O-NaCl).The micro-thermometric analysis of the type Ia and Ib fluid inclusion in qtz1 & qtz2 have aqueous-carbonic composition and exhibit a similar salinity of 1.1 to 7.8 wt% NaCl equivalent, whereas the homogenization temperature (Th) range varies from ∼237 to ∼350 °C. These ore-related fluid inclusions are of low to moderate salinity, and show mixture of CO2 and CH4. On the other hand, Type II fluid inclusions are dominant in qtz3. They have salinity of 3.2 to 12.7 wt% NaCl equivalent and homogenization temperature varying between 180 °C and 210 °C. These data indicate that the ore-forming fluid evolved from a CO2–H2O–NaCl ± CH4 system during the mineralization period.The X-ray elemental maps of pyrite acquired using electron microprobe analysis (EPMA) show irregular zones of Co and Ni indicating two generations of pyrite. The early-stage pyrite which occupies core portion shows high Co and Ni, whereas the later-stage pyrite occupying rim has lower Co and Ni. The laser ablation-inductively coupled plasma-mass spectrometer (LA-ICPMS) analyses of pyrite has indicated that pyrite-1 is rich in Au + Ag + Se + Cu + Co + Ni, whereas, pyrite-2 has lower concentration of these elements. A positive correlation between Fe and other chalcophile elements reported here (i.e. Au + Ag + Se + Cu + Co + Ni), might be due to fluid-rock interaction resulting into a saturated fluid that subsequently precipitated along the microfractures within earlier-formed pyrite and quartz. The in-situ δ34S values in pyrite from Jiapigou deposits overlap in the range of +4.5 to +9.6 ‰, which is consistent with the ore-forming fluids of the crustal origin input during fluid-rock interaction. The systematic pyrite compositional observations and fluid inclusions study documented here to provide new insight into the process of ore formation for the Au enrichment in the Jiapigou deposit

Ti- and Ba-rich phlogopitic micas in alkaline basic and upper mantle igneous rocks; stoichiometry, stability, and Fe valence estimation reassessed and rationalised

Ti- and Ba-rich tri-octahedral micas occur in fractionated basic igneous rocks, metasomatized mantle peridotites, metamorphosed pelites/carbonates, and hydrothermally altered mineral deposits. Electron microprobe analyses (EMP), with all iron reported as FeO, were widely used in the 1970/80s to interpret Ti and Ba substitution mechanisms, based on 22 O2– unit cell calculations, implying that cation vacancies occur in octahedral and/or intersheet sites. In 1996 EMP with chemical and physical analyses for ferric and total Fe, H2O, (OH), and element-specific Fe X-ray Absorption Spectroscopy (both K and L-edges) established valence states for Fe and Ti and cation site occupancies, that ∼50 % O replaces (OH) molecules, and that 24 anion cell formulae show the absence of cation vacancies. Cell formula calculation protocol for phlogopitic micas is refined here and results tested against the stoichiometric formula for vacancy-free phlogopite, XIIK2VIMg6IV[Si6Al2]O20(OH)4. Hypothetical sheet silicate compositions, calculated with fixed contents of vacancies linked to particular mixed-valence element substitutions, confirm that reliable unit cell formulae for natural mica solids require that each stoichiometric vacancy must be accounted for. If reliable estimates for ‘excess O’ (denoted WO2−) are assigned to EMP analyses, the proportion of the oxy-mica component in a mica solid solution can be defined. This approach is tested using published analyses for Ti- and Ba-rich biotites from fractionated basic and ultramafic volcanic igneous rocks (oxymica range 2.5–45 %; TiO2 up to 14 %; BaO up to 23 %), upper mantle peridotites (equivalent values 7–18 %; 6 %; 0.7 %), and metasomatised upper mantle (2–37 %; 9 %; 23 %). Enrichments of Ti and Ba in micas are clearly linked to the extra oxygen charge required to neutralise the more highly charged Ba2+ and Ti4+ replacing K+ and Mg2+.Substitution mechanisms involving Ba, Ti, and Fe3+ in ideal phlogopite involve coupled inter-site / inter-valence interactions so both site-ordering and valence-balance between the different cation sites must be accounted for. The cation exchange 2XIIK+ + 4VI(Mg2+ + Fe2+) + 4IVSi4+ ↔ XIIBa2+ + 3VITi4+ + 4(Altotal + Fe3+ + Crtotal)3+ is used here so that valence and site order can be considered together. Compositional variations show well-defined trends towards high-oxymica content and vacancy-free Ti and Ba mica end-members, rather than to oxy-free end-members with essential vacancies. Average compositions for different source rock micas are used to assess compositional trends; molecular WO2− values are refined by relating initial estimates directly to the wt.% TiO2 contents; and refined WO2− and stoichiometrically calculated Fe3+/Fetotal ratios ranging ∼0.1–0.5) are correlated with possible primary magmatic values.

Insights into the North Patagonian Massif Lower Crust: Petrology and Microstructure of Granulite Xenoliths

Abstract The continental lower crust constitutes a key zone for understanding the mantle–crust magmatic and mechanical transfers, but its study is hampered by the paucity of lower crust samples. Here, we characterise the petrological, geochemical and petrophysical processes structuring the lower crust of the North Patagonian Massif (NPM; Argentina) using a suite of representative mafic granulite and websterite xenoliths. These xenoliths were entrained by alkaline lavas from five volcanic centres that erupted between the Oligocene and Pleistocene. Electron microprobe and Laser Ablation Inductively Coupled Plasma Mass Spectrometer (LA-ICPMS) were used to obtain in situ geochemical data on the minerals, while microstructural data were obtained by Electron BackScatter Diffraction (EBSD). Both granulites and websterites display a granoblastic texture and sometimes a weak inherited magmatic layering. Mafic granulite xenoliths show a plagioclase + clinopyroxene ± orthopyroxene assemblage commonly associated with spinel or titanomagnetite. Websterite xenoliths show an association of clinopyroxene + orthopyroxene + spinel, along with accessory plagioclase. Mafic granulites and websterites have SiO2 contents ranging from 44 to 53 wt %, while their Mg# varies from 53 to 79. Clinopyroxenes are characterised by weak convex upward chondrite-normalised Rare Earth Elements - REE patterns (Light-REE </<< Mid-REE > Heavy-REE) which are similar to clinopyroxene phenocrysts and megacrysts from intra-plate basalts. Calculated liquid in equilibrium with clinopyroxene have similar REE patterns to those found in Cenozoic basalts from the NPM, suggesting that the xenolith suite represents evidence for underplating processes, possibly related to one of the magmatic events that have occurred in the NPM since the Permo-Trias. Mafic granulites and websterites show a weak mineral shape preferred orientation and an associated weak Crystal Preferred Orientation (CPO) related to the magmatic layering. Recorded plastic deformation is associated with the activation of both (100)[001] and (001)[100] slip systems in clinopyroxene, (100)[001] in orthopyroxene and (010)[001] in plagioclase. However, the activation of slip systems is generally not correlated with CPO in granulites, suggesting that the lower crust underwent subsolidus equilibration and weak plastic deformation in an inactive tectonic context, thereby preserving an inherited magmatic layering. Two-pyroxene (Fe–Mg) thermometer and pseudosection calculations define P–T conditions of the main paragenesis at 760°C to 1120°C and 7.2 to 10.3 kbar, which allows to define the Cenozoic geotherm of the NPM crust at 30°C/km and to reconsider the petrologic Moho depth at ca. 40 km.

Investigating the efficacy of Palladium Doped Ceria for the Photodegradation of Azo Dyes

Ceria (CeO2) was prepared by microwave assisted precipitation method while sonothermal method was utilized for the synthesis of palladium doped ceria (Pd-CeO2) photocatalyst. HR-TEM analysis confirms the face centered cubic geometry (FCC) of CeO2. The particle size of Pd-CeO2 calculated from HR-TEM analysis (7.6±2.18 nm) is in close relation with XRD (8.25±0.25 nm). The SAED pattern of Pd-CeO2 shows the poly crystallinity where the d-spacing was 0.31 and 0.30 nm which corresponds to CeO2 and Pd crystal facets 111 and 100 respectively. The amount of dopant and existence of Pd, Ce and O was confirmed from EDX spectra and elemental mapping. BET surface area analysis of CeO2 (64.45 m2/g), Pd-CeO2 (60.20 m²/g) revealed that the decrease in the surface area of CeO2 due to Pd loading which is confirmed by pore volume (0.079 cm³/g) for CeO2 and pore volume for Pd-CeO2 (0.073 cm³/g). The photocatalytic activity of Pd-CeO2 was screened against a model azo dye Acid red-4 (AR-4). The fluctuation of the rate of photodegradation (PD) of AR-4 was observed under different reaction conditions. Therefore, the reaction parameters were optimized to achieve best catalytic activity up to PD; 98%. The kinetic study suggests that the PD of AR-4 follows 1st order kinetics with regression coefficient (R2=0.973) and rate constant (k=0.024/min). Recycling study revealed the prolong use of catalyst without significant loss of activity. DFT study and experiments revealed the synergism of Pd on the photo response of CeO2. Perhaps this synergistic effect due to metal support interaction, causes redistribution of charges and Fermi energy levels. The synthesized catalyst showed potential application for the treatment of textile industrial effluents.

Cydonia oblonga extract mediated biosynthesis of gold nanoparticles: Analysis of its anti-oral cancer and antioxidant properties

Here, using natural and biological macromolecules derived from Cydonia oblonga extract, we have developed a green protocol for the biogenic made Au NPs. Under ultrasonic activated conditions, the Cydonia oblonga phytomolecules were employed as an efficient green reducing agent for the Au3+ ions to the Au0 NPs. Additionally, by encapsulating or capping, they allowed the Au NPs to stabilize on their own. Several physicochemical techniques, such as elemental mapping, TEM, FE-SEM, UV–Vis spectroscopy, EDS, and ICP-OES, were used to analyze the structure of the Au NPs/Cydonia oblonga bio-nanocomposite. The field of medicinal therapeutics pertaining to human health includes cancer treatment as a major component. Subsequently, the as prepared Au NPs/Cydonia oblonga bio-nanocomposite was investigated for antioxidant and human anti-oral cancer assays. In such studies a number of cell lines, viz., HSC-3, HSC-2, and Ca9-22 were used in determining the cytotoxicity. Notably, Au NPs/Cydonia oblonga exhibit significant anti-oral cancer properties against HSC-3, HSC-2, and Ca9-22 cancer cell lines following time and dose-dependent manner. The corresponding IC50 values were determined as 201, 192, and 246 µg/mL respectively. DPPH radical scavenging method was used to determine the antioxidant activity of Au NPs/Cydonia oblonga bio-nanocomposite. The significant IC50 value suggested the material having very good antioxidant potential. The anti-human oral cancer effect of our material is believed to be due to its antioxidant effects.

Proton conductive 2D MXene-derived potassium titanate nanoribbons fabricated electrochemical platform for trace detection of enrofloxacin

In recent years, due to exceptional properties like broad interlayered spacing and low working potential, MXene-derived titanate nanoribbons have been established as promising electrode materials. Herein, the electrocatalytic activity of MXene-derived potassium titanate nanoribbon was employed to develop a voltammetric sensor for the detection of enrofloxacin. The sensor's significance is to provide a sustainable solution to quantify the presence of enrofloxacin regarding food safety and environmental monitoring. Moreover, to achieve the United Nations' Sustainable Development Goals by preventing antimicrobial resistance to accomplish the One Health approach. Potassium titanate nanoribbons were synthesized using 2D Ti3C2 MXene as an active precursor material, while X-ray diffraction spectroscopy, field emission scanning electron microscopy, high-resolution transmission electron microscopy, selected area electron diffraction pattern, elemental mapping, and energy-dispersive X-ray spectroscopy were used to characterize the crystallinity, surface and layered morphology of synthesized nanoribbons. The Brunauer-Emmett-Teller (BET) technique was applied to calculate the specific surface area of the synthesized materials. The materials underwent electrochemical characterization using cyclic voltammetry (CV), differential pulse voltammetry (DPV), and electrochemical impedance spectroscopy (EIS). Later on, the nanoribbons were fabricated on the surface of a glassy carbon electrode, and the electro-oxidative behaviour of enrofloxacin was studied by CV, DPV, square wave voltammetry (SWV) in 0.1 M phosphate buffer (optimized pH 8). The developed sensor depicts a significantly lower limit of quantification of 0.007 μM (≈2.5 μg/L), and an upper limit of quantification of 18 μM (≈6.5 mg/L) along with a limit of detection (LOD) of 0.00279, 0.00803, 0.00881 μM obtained from CV, DPV, and SWV respectively. Furthermore, the developed electrodes show a reliable selectivity to be examined in real complex matrices, i.e. marine water, river water, agricultural soil, organic fertilizer, milk, honey, and poultry egg.

Supported Au NPs over magnetic chitosan-gelatin nanocomposite: Investigation of its catalytic activity for one-pot synthesis of tetrazoles, study of antioxidant activity and anti-uterine cancer performances

This paper reports the synthesis of a novel class of Fe3O4@CS-Gl/Au core-shell pattern nanoparticles by employing Au NPs and chitosan-gelatin composite. The biogenic synthesis was mediated by dual composite hydrogel of chitosan and gelatin as a green reducing as well as stabilizing agent under ambient conditions. Physicochemical features the so obtained nanomaterial was assessed by using FT-IR, TEM, FE-SEM, EDX, elemental mapping, VSM and XRD. Click synthesis of 5-substituted-1H-tetrazoles utilizing aryl halides was our aim in catalytic investigation. The Fe3O4@CS-Gl/Au catalyst, which is highly effective and reusable, was used to catalyze the [3+ 2]-cycloaddition of benzonitriles with NaN3, leading to the solvent-free synthesis of corresponding tetrazole derivatives at 120 °C. This method was carried out using K4[Fe(CN)6] as a non-hazardous cyanide precursor. Following a 12-hour process, the different substrates produced yields ranging from 70 to 96%. Hot filtration, leaching and reusability studies were conducted 12 times in a succession, all of which confirmed the catalyst's resilience. Furthermore, in the biological studies % cell viability of Fe3O4@CS-Gl/Au NPs was found very low against common human uterine cell lines i.e. AN3-CA and HEC-1-A, devoid of any cytotoxicity on normal cell lines like HUVEC. The best anti-uterine effect was observed against the AN3-CA cell line. For investigating the antioxidant properties of nanobio-composite, the DPPH assay was used. Fe3O4@CS-Gl/Au NPs inhibited half of the DPPH molecules in the concentration of 139 µg/mL. The antioxidant activity of the NPs is significantly related to its anti-uterine cancer potentials. Based on the above findings, the Fe3O4@CS-Gl/Au NPs could be administered in restricting diverse human cancers.

Photocatalytic activity of molybdenum-doped LOS- zeolite for efficient dye degradation and hydrogen production

This research investigates the synthesis and application of Losod-zeolite (LOS-Z), a crystalline hydrated sodium aluminosilicate (Na12Al12Si12O48.xH2O) as a potential photocatalyst for dye degradation and H2 production from dye-degraded water. The photocatalytic properties are enhanced by impregnating molybdenum (Mo) into LOS-Z (Mo@LOS-Z). XRD, FTIR, SEM, EDX, and elemental mapping were used to study the physicochemical properties of synthesized materials while UV–vis and PL were employed to explore the optoelectronic properties. The photocatalytic activities for dye degradation and H2 production were evaluated using methylene blue (MB) under visible light irradiation. An enhancement in the efficiency of dye degradation (56%–82%) and H2 production rate was demonstrated due to the competitive photocatalytic performance of 10% Mo@LOS-Z compared to the pristine LOS-Z and CFA-BFA blend. It exhibited 2.5 times higher (∼1200 μmol g−1h−1) H2 production than the LOS-Z (∼480 μmol g−1h−1) due to the synergistic effects of narrowed band gap and recombination rate. This study could pave the way forward into the synthesis of waste-derived photocatalysts for efficient dye degradation and H2 production.

Hydrothermal synthesis and characterization of samarium molybdate nanosheets modified multi-walled carbon nanotubes: real-time analysis of dimetridazole in environmental and biological samples

Dimetridazole (DMZ) is commonly used as a veterinary drug, resulting in high emissions and environmental pollution and DMZ residues are carcinogenic, genotoxic, and mutagenic to humans. Therefore, it is essential to construct a fast, sensitive and simple sensor to monitor DMZ. In this study, samarium molybdate nanosheets modified multi-walled carbon nanotube composites (SmM/MWCNT) were synthesized to modify GCE for detecting DMZ. The SmM/MWCNT material was also characterized by various analytical and spectroscopic techniques, such as FE-SEM, HRTEM, FT-IR, Raman spectroscopy, XRD, elemental mapping and XPS, to demonstrate the successful synthesis of the composite. Besides, the electrochemical behavior of SmM/MWCNT /GCE for DMZ was also investigated using CV and DPV, and the modified electrode showed good electrochemical sensing performance for DMZ with a low detection limit (0.08 μM), a wide linear range (0.1∼1000 μM), and excellent selectivity. Finally, the SmM/MWCNT/GCE was successfully applied to detect DMZ in environmental and biological samples, and satisfactory recoveries (95%∼105%) were obtained. To the best of our knowledge, the synthesis of SmM/MWCNT and its application in electrochemical sensors are reported for the first time, which demonstrates that it can provide a new route for real-time monitoring of environmental pollutants.

Investigation into graphene nano-platelet reinforced aluminum coating on mild steel substrate

Pure Aluminum (Al) and composite coating of Al with the reinforcement of carboxyl functionalized graphene nano-platelet (fGNP) were successfully electrodeposited on mild steel. The chloroaluminate ionic liquid melt was used for electrodeposition under ambient conditions. Electron probe microanalyzer analysis and Raman spectroscopy revealed the existence of fGNP in the composite coating. 3D optical profilometry of both coatings depicted the changes in the surface because of the presence of fGNP in the composite coatings. The micro-hardness test demonstrated enhancement in hardness, which can be ascribed to the existence of fGNP in the composite coating.

Iron redox shuttling and uptake by silicate minerals on the Namibian mud belt

Anoxic marine sediments represent an important source of bioavailable iron (Fe) to the ocean. The highest sedimentary Fe fluxes are observed in open-marine oxygen minimum zones where anoxic bottom waters are in contact with ferruginous surface sediments. Here, sedimentary Fe release, transport and re-deposition (i.e., Fe shuttling) may generate a lateral pattern of sedimentary Fe enrichment and depletion, which can be used to trace redox-related Fe mobility in the paleo-record. However, depending on the balance between terrigenous and authigenic (i.e., shuttle-related) Fe flux, the stability of bottom water redox conditions as well as post-depositional processes of mineral alteration, the sedimentary fingerprint of an Fe redox shuttle may be obscured and difficult to identify.We investigated sedimentary Fe cycling along two transects across the Namibian mud belt with variable terrigenous sedimentation (23°S < 25°S) and during two seasons with opposing bottom water redox conditions (oxic in austral winter versus anoxic to sulfidic in austral summer). On both transects, substantial benthic Fe fluxes up to −50 µmol m−2 d−1 were inferred based on pore water profiles. The magnitude of these fluxes is comparable to those reported for other open-marine oxygen minimum zones. On the transect at 23°S, Fe source areas with ferruginous surface sediments were clearly separated from Fe sink areas with highly sulfidic surface sediments. Therefore, Fe redox shuttling was reflected by a lateral pattern of reactive Fe depletion and enrichment relative to the terrigenous background sedimentation. By contrast, on the transect at 25°S, benthic Fe fluxes were temporally and spatially more variable and surface sediments were ferruginous or only weakly sulfidic. Therefore, sedimentary Fe depletion and enrichment was less pronounced at 25°S. In the Fe sink area at 23°S, hydrogen sulfide was present at the sediment surface during both sampling campaigns and solid phase data suggest that Fe sulfide minerals represented the main burial phase of reactive Fe. By contrast, at 25°S excess Fe was associated with potassium (K) rather than reduced sulfur. While a differing sediment provenance cannot be ruled out entirely, combined evidence from pore water silica profiles, K to Fe stoichiometric relationships and electron microprobe images suggest that laterally derived excess Fe was incorporated into pre-existing and/or authigenic clay minerals during early diagenesis. Iron uptake by clay minerals may be supported by frequent redox oscillations and sediment mixing preventing preservation of Fe sulfide minerals and promoting Fe and K fixation in clay minerals. The burial fluxes of excess Fe associated with sulfide minerals at 23°S and silicate minerals at 25°S were similar. Our findings thus underscore that neoformation or alteration of silicate minerals can be important processes within the low-temperature marine Fe cycle.

Semi-quantitative μLIBS mapping of germanium diffusion between metal and silicate during planetary core–mantle segregation

Understanding the distribution of elements between the cores and mantles of planetary bodies is essential for elucidating the geological and geochemical processes operating during their formation. Because the semi-metallic element Ge shows complex siderophile, chalcophile, and lithophile properties, it is particularly significant for investigating core–mantle segregation and ore deposit formation. Recent advancements in in situ microanalysis techniques, such as μLIBS, have enabled high-resolution elemental mapping of Ge and other trace elements.This study explores the application of μLIBS imaging to investigate the high-temperature/high-pressure distribution of Ge between metallic and silicate matrices analogous to planetary cores and mantles. By cross-calibrating the μLIBS intensities with electron microprobe profile analyses carried out on piston cylinder experimental samples, we produced semi-quantitative Ge maps from which we extracted Ge concentration profiles to assess Ge diffusion from the silicate to the metal. We determined, for the first time, the diffusion coefficient of Ge between metal and silicate to be D(Ge)metal = 4.03E−13 ± 3.6E−14 m2/s at 1 GPa and 1350 °C. Our results demonstrate the capability and efficiency of μLIBS for providing detailed, high-resolution (15 μm) trace element concentration data at few ppm levels, offering a time- and cost-effective alternative to conventional techniques.These findings bring insights on planetesimal differentiation and on chemical exchanges between metal and silicate phases in a magma ocean and between two different metal phases occurring at the bottom of the magma ocean during planetesimal formation.

Effect of nanoparticles reinforcement of silicon dioxide derived from prosopis juliflora on Silver-Grey magnesium nanocomposite: utilization of silicon dioxide mechanical and tribological properties

Abstract The automotive and aviation industries require lightweight materials to enhance working efficiency. Composites combine materials such as aluminium, magnesium, titanium, steel, and copper with various forms of reinforcements to offer lightweight alternatives for a range of applications. The present investigation aims to fabricate a Silver-Grey Magnesium (Mg-25%Si) alloy-based nanocomposite with silicon dioxide (SiO2) nano reinforcement at weight % of 0, 3.25, 6.5 and 9.75 utilizing the two step stir casting method. Prosopis juliflora is utilized in the production of different weight percentages of SiO2 nano reinforcements. The microhardness, tensile, wear, and impact tests are performed on the Silver-Grey Magnesium nanocomposites (Mg-25%Si/SiO2) utilizing a computerized tensometer testing machine, a Vicker’s hardness tester, a pin-on-disc tribometer, and an Izod impact, respectively. The x-ray diffraction (XRD), Field Emission Scanning Electron Microscope (FESEM), and Energy-dispersive x-ray spectroscopy (EDAX) with elemental mapping microstructure were employed to scrutinize the tensile specimen fracture, EDAX, elemental mapping microstructure, wear, CoF, and worn surface characterization and impact strength analysis. When compared to the Silver-Grey Magnesium (Mg-25%Si) base alloy, the results of the Mg-25%Si/SiO2 nanocomposites demonstrated an increase in SiO2 nano reinforcements that significantly increased microhardness, tensile strength, wear resistance, and impact strength. The corresponding values are 113.36 VHN, yield and ultimate tensile strength of 603.25 MPa and 665.84 MPa, 0.00478 mm3 m−1, CoF of 0.38421 and 400 J m−1.

Assembly of Fe@Zn-Coordination Polymer Composite: Iron Doping Foster the Luminescent Detection for Tetracycline, Uric Acid and Cr2O72− and Crystal Violet Degradation Efficiency

Coordination polymers exhibit a diverse array of applications across various fields, and through the development of composite materials, their utility and versatility are further enhanced, broadening their impact on our world. In this work We synthesized the first coordination polymer (CP) based on Zn and doped with Fe composites (Fe@Zn-CP Composite), which exhibit enhanced photocatalytic activity triggered by visible light. Using mixed ligands orotic acid potassium salt, 1,3 di (4-pyridyl) propane (dpp), and FeSO4 in a simple method at ambient temperature, the Zn-CP [Zn8(Or)8(dpp)4(H2O)8] was resynthesized here to form the Fe@Zn-CP composites. Zn-CP and Fe@Zn-CP Composite were both characterized by powder X-ray diffraction, FT-IR spectra analysis, and SEM-EDX analysis and elemental mapping analysis. It has been observed that Fe@Zn-CP Composite is as multi-functional luminescence sensor for MnO4−, Cr2O72− and Tetracycline with high sensitivity. In-depth research has also been done on the recyclable nature, and photocatalytic efficiency of Zn-CP and Fe@Zn-CP Composite for the decomposition of organic dyes Crystal Violet and Rose Bengal (RB) in contaminated water under the sunlight irradiation.

Impact of atmospheric plasma spraying parameters on microstructure, mechanical properties and thermal cycling performance of YSZ coatings

Yttria-stabilized zirconia (YSZ) coatings are widely utilized thermal protective layers for metal and superalloy surfaces. These coatings are employed as thermal barrier coating (TBCs) to insulate metallic parts from higher thermal energy, thereby minimizing the cooling need for the topcoat ceramic layer. The choice of material is 7 wt% YSZ due to its exceptional capability to withstand challenging conditions characterized by extremely high temperatures and pressures, typically employed by the atmospheric plasma spraying (APS) in gas turbines, effectively extending their lifespan and improving performance. The deposition process of TBCs is significantly influenced by various spraying parameters, including gas flow rate and current (amp). These key parameters mutually play a significant role in controlling thermal stability, phase composition, and improved mechanical and microstructure properties. The aim of this research is to evaluate and contrast the impact of various spraying parameters on YSZ TBC performance. Accordingly, the influence of Hydrogen (H2), Argon (Ar) flow rate, and Current (amp) was investigated. Microstructure and elemental mapping studying was conducted using Field Emission Scanning Electron Microscopy FESEM/EDS and phase studying was examined with X-ray diffraction (XRD). Porosity was measured by IMAGE J software while hardness measurement was calculated by Vickers hardness tester. Additionally, thermal cycling tests were conducted between 700 °C and 1200 °C. The porous coatings exhibited poor performance, delaminating early during the tests. In contrast, dense coatings performed significantly better, enduring up to 140 cycles before failure.

Co–Ni nanoparticle supported on heteroatom-doped carbon derived from garlic powder and eutectic solvent: Its application in Nitroarenes reduction

This paper presents the synthesis of a novel heterogeneous catalyst, PSN-C600-Co2:Ni1, designed for the hydrogenation of nitroaromatic compounds. The catalyst is a porous carbon substrate triply doped with nitrogen, sulfur, and phosphorus, incorporating bimetallic Co and Ni nanoparticles. A natural precursor, garlic biochar, and a biodegradable eutectic solvent were used in the synthesis. Various characterization techniques, including Scanning Electron Microscope (SEM), X-Ray Energy Diffraction Spectroscopy (EDX), Elemental Mapping Measurements (MAP), Thermogravimetric Analysis (TGA), X-Ray Diffraction (XRD), Infrared Spectrometer (FTIR), Transmission Electron Microscope (TEM), Raman Spectroscopy, and Nitrogen Adsorption and Desorption Pattern (N2 adsorption-desorption isotherm), were utilized to examine the features and properties of the synthesized PSN-C600-Co2:Ni1 catalyst.