Microscopy-energy Dispersive X-ray Spectroscopy Research Articles

Performance evaluation of a hyphenated laser spectroscopy system with conventional methods for microplastic analysis

Microplastics are one of the concerning environmental pollutants because of their ubiquity. Their capability to adsorb other environmental pollutants increases the risk even further. Existing identification approaches for microplastic characterization for polymer class and their surface-adsorbed heavy metal detection require the utilization of multiple resources and expertise. The article discusses the applicability of a custom-made hyphenated Laser Induced Breakdown Spectroscopy (LIBS)—Raman spectroscopic system in characterizing microplastics by comparing the analytical performance with conventional methods such as Attenuated Total Reflectance- Fourier Transform Infrared (ATR-FTIR) spectroscopy, confocal Raman spectroscopy, and Scanning Electron Microscopy–Energy Dispersive X-ray Spectroscopy (SEM–EDS). Raman analysis identified polyethylene (PE), polypropylene (PP), and polyethylene terephthalate (PET) plastics, which is confirmed by confocal Raman and FTIR study of the same. LIBS study of microplastics detected heavy metals such as Al, Ni, Co, and Zn, along with Ca and Mg trace elements. The cross-examination with EDS validates these trace elements' presence on the microplastics' surface. The results of the reported LIBS-Raman analysis and its validity evaluated using conventional gold-standard methods show the applicability of the proposed methodology in characterizing microplastics from environmental resources with less or no sample preparation in short time.

Characterization and ohmic contact properties of indium tin-oxide films prepared on p-type GaN using electron-cyclotron-resonance plasma-sputter deposition

The optical and electrical properties of indium tin oxide (ITO) films deposited using electron cyclotron resonance (ECR) plasma-sputter deposition and the ohmic contact properties between the ITO films and p-type gallium nitride (p-GaN) were evaluated. The electrical properties of the ITO films were evaluated in terms of the dependence on the tin (IV) oxide (SnO2) content of the ITO target and radio frequency (RF) power. The ohmic contact properties between the ITO films and p-GaN were also characterized by varying the top-surface Mg concentration of the p-GaN substrate. An ohmic contact was achieved without post-annealing treatment by depositing the film on a p-GaN high-dope substrate with a top-surface Mg concentration of 2.0 × 1020 cm−3 under low RF-power deposition using an ITO sputter target with 10 wt.% SnO2. The interface between the ITO films and p-GaN that achieved an ohmic contact was observed using scanning transmission electron microscopy (STEM) and was very smooth with no crystal disorder. This indicates that the crystallinity of the ITO films and p-GaN surface is a factor affecting ohmic-contact properties. The inter-diffusion between the ITO films and p-GaN surface was also evaluated using transmission electron microscopy energy dispersive X-ray spectroscopy (TEM-EDS), and no inter-diffusion was observed.

Temperature-induced variations in the structural, morphological and optical features of cobalt oxide nanoparticles synthesized via hydrothermal method

Cobalt oxide is a promising material that attracts the researchers to find its application in various fields like catalysts, dielectric applications, gas sensors and electronics devices, etc. In this work, we investigated the effect of temperature in the structural, elemental, morphological and optical properties of Co3O4 nanoparticles synthesized by hydrothermal method. The as-prepared and annealed samples were observed for their structural and optical properties. The structural analysis and micro-strain effects of Co3O4 nanoparticles with cubic spinel structure were carried out through X-ray diffraction (XRD) studies. The crystallite size of as-prepared and annealed samples were around 27 nm and 29 nm, respectively. Raman spectrum showed the lattice vibrations of both oxidation states of cobalt oxide nanoparticles. Elemental analysis were observed through X-ray photoelectron spectroscopy (XPS). The morphology and chemical composition of the samples were determined from the field emission scanning electron microscope (FESEM) image and energy dispersive X-ray spectroscopy (EDAX). Moreover, the internal structure of both samples were compared through transmission electron microscopic (TEM) studies. The optical studies were done using the absorption spectrum and photoluminescence spectroscopy. Two direct band gaps (1.8 and 3.2 eV) were observed in the as-prepared, which got red-shifted on annealing (1.7 and 2.5 eV) due to size effects. The charge transfer process in two oxidation states of cobalt oxide could be identified from these bandgaps. Emission peaks in the photoluminescence spectrum of samples are due to the recombination of free-excitons and point defects in the crystal lattice.

Novel starch–tungsten (VI) oxide biocomposites: Preparation, characterization, and comparisons between experimental and theoretical photon attenuation coefficients

This study synthesized biocomposites containing starch and WO3 at varying ratios of 10 %, 20 %, 30 %, 40 %, and 50 % and assessed their thermal and radiation-shielding properties. These biocomposites were characterized using Fourier-transform infrared spectroscopy, X-ray diffraction (XRD) analysis, particle-size distribution assessments, scanning electron microscopy–energy dispersive X-ray spectroscopy, and thermogravimetric analysis–differential thermogravimetry measurements. Furthermore, the linear attenuation coefficients of the biocomposites were experimentally measured using an NaI(Tl) gamma spectrometry system and theoretically computed using XCOM and GAMOS simulations for comparisons. The XRD and particle-size distribution profiles of the WO3.2H2O powder, respectively, demonstrated evident diffraction peaks and favorable pore-size distributions. Morphological characterizations revealed that the WO3 particles were homogeneously dispersed throughout the starch matrix without any agglomeration. Comparisons of the thermal degradation rates revealed that the pure starch and starch +50%WO3 biocomposite began decomposing at approximately 200°Cand 300 °C, respectively, indicating that increasing WO3 proportions enhanced thermal stability. Furthermore, the starch +50%WO3 biocomposite demonstrated the highest experimental linear attenuation coefficient, with a value of 0.2510 ± 0.0848 cm−1 at a gamma energy of 662 keV. Meanwhile, XCOM and GAMOS simulations revealed theoretical attenuation coefficients of 0.1229 and 0.1213 cm−1 for pure starch and 0.2202 cm−1 and 0.2178 cm−1 for the starch +50%WO3 biocomposite at 662 keV, respectively.

Characterization of an advanced bone graft material with a nanocrystalline hydroxycarbanoapatite surface and dual phase composition.

The bone formation response of ceramic bone graft materials can be improved by modifying the material's surface and composition. A unique dual-phase ceramic bone graft material with a nanocrystalline, hydroxycarbanoapatite (HCA) surface and a calcium carbonate core (TrelCor®-Biogennix, Irvine, CA) was characterized through a variety of analytical methods. Scanning electron microscopy (SEM) of the TrelCor surface (magnification 100-100,000X) clearly demonstrated a nanosized crystalline structure covering the entire surface. The surface morphology showed a hierarchical structure that included micron-sized spherulites fully covered by plate-like nanocrystals (<60 nm in thickness). Chemical and physical characterization of the material using X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), and Scanning Electron Microscopy Energy Dispersive X-ray Spectroscopy (SEM-EDX) showed a surface composed of HCA. Analysis of fractured samples confirmed the dual-phase composition with the presence of a calcium carbonate core and HCA surface. An in vitro bioactivity study was conducted to evaluate whether TrelCor would form a bioactive layer when immersed in simulated body fluid. This response was compared to a known bioactive material (45S5 bioactive glass - Bioglass). Following 14-days of immersion, surface and cross-sectional analysis via SEM-EDX showed that the TrelCor material elicited a bioactive response with the formation of a bioactive layer that was qualitatively thicker than the layer that formed on Bioglass. An in vivo sheep muscle pouch model was also conducted to evaluate the ability of the material to stimulate an ectopic, cellular bone formation response. Results were compared against Bioglass and a first-generation calcium phosphate ceramic that lacked a nanocrystalline surface. Histology and histomorphometric analysis (HMA) confirmed that the TrelCor nanocrystalline HCA surface stimulated a bone formation response in muscle (avg. 11% bone area) that was significantly greater than Bioglass (3%) and the smooth surface calcium phosphate ceramic (0%).

Atomic-level investigation of structure and formation process of Y3Al5O12 with super-high content of Ce emitting anomalous orange-red emissions

Ce-doped yttrium aluminum garnet (YAG:Ce, Y3Al5O12:Ce) is the most commonly used yellow phosphor in white light-emitting diodes. Recently, we found that (Y1–xCex)3Al5O12:Ce with a super-high content of Ce (x = 0.11–0.21) can be prepared by a polymerized complex method and exhibits anomalous orange–red emission. To understand the nature of this anomalous behavior from the atomic level, we applied high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and scanning transmission electron microscopy–energy dispersive X-ray spectroscopy (STEM-EDS), a state-of-the-art technique that enables analysis of the atomic-level elemental distributions of Al, Y, and Ce. STEM-EDS images on the atomic level were successfully obtained for YAG:Ce. It was found that Ce in Y site has spatially uneven for few nanometers. Ce–K edge extended X-ray absorption fine structure (EXAFS) analysis was also conducted, which revealed a high level of asymmetry around Ce. By combining the STEM-EDS and EXAFS results, a dynamic model for the red emission was proposed. STEM-EDS also revealed that CeO2 nanocrystals were firstly formed with low-temperature annealing and that the reaction of Y with the CeO2 nanocrystals subsequently yielded YAG:Ce, unlike in the conventional one-step high-temperature synthesis.

Influence of TiO2 Nanoparticles on the Physical, Mechanical, and Structural Characteristics of Cementitious Composites with Recycled Aggregates.

The aim of this study is to analyze the effect of the addition of TiO2 nanoparticles (NTs) on the physical and mechanical properties, as well as the microstructural changes, of cementitious composites containing partially substituted natural aggregates (NAs) with aggregates derived from the following four recycled materials: glass (RGA), brick (RGB), blast-furnace slag (GBA), and recycled textolite waste with WEEE (waste from electrical and electronic equipment) as the primary source (RTA), in line with sustainable construction practices. The research methodology included the following phases: selection and characterization of raw materials, formulation design, experimental preparation and testing of specimens using standardized methods specific to cementitious composite mortars (including determination of apparent density in the hardened state, mechanical strength in compression, flexure, and abrasion, and water absorption by capillarity), and structural analysis using specialized techniques (scanning electron microscopy (SEM) images and energy dispersive X-ray spectroscopy (EDS)). The analysis and interpretation of the results focused primarily on identifying the effects of NT addition on the composites. Results show a decrease in density resulting from replacing NAs with recycled aggregates, particularly in the case of RGB and RTA. Conversely, the introduction of TiO2 nanoparticles resulted in a slight increase in density, ranging from 0.2% for RTA to 7.4% for samples containing NAs. Additionally, the introduction of TiO2 contributes to improved compressive strength, especially in samples containing RTA, while flexural strength benefits from a 3-4% TiO2 addition in all composites. The compressive strength ranged from 35.19 to 70.13 N/mm2, while the flexural strength ranged from 8.4 to 10.47 N/mm2. The abrasion loss varied between 2.4% and 5.71%, and the water absorption coefficient varied between 0.03 and 0.37 kg/m2m0.5, the variations being influenced by both the nature of the aggregates and the amount of NTs added. Scanning electron microscopy (SEM) images and energy dispersive X-ray spectroscopy (EDS) analysis showed that TiO2 nanoparticles are uniformly distributed in the cementitious composites, mainly forming CSH gel. TiO2 nanoparticles act as nucleating agents during early hydration, as confirmed by EDS spectra after curing.

On dry machining of AZ31B magnesium alloy using textured cutting tool inserts

Magnesium alloys have many advantages as lightweight materials for engineering applications, especially in the fields of automotive and aerospace. They undergo extensive cutting or machining while making products out of them. Dry cutting, a sustainable machining method, causes more friction and adhesion at the tool-chip interface. One of the promising solutions to this problem is cutting tool surface texturing, which can reduce tool wear and friction in dry cutting and improve machining performance. This paper aims to investigate the impact of dimple textures (made on the flank face of cutting inserts) on tool wear and chip morphology in the dry machining of AZ31B magnesium alloy. The results show that the cutting speed was the most significant factor affecting tool flank wear, followed by feed rate and cutting depth. The tool wear mechanism was examined using scanning electron microscope (SEM) images and energy dispersive X-ray spectroscopy (EDS) analysis reports, which showed that at low cutting speed, the main wear mechanism was abrasion, while at high speed, it was adhesion. The chips are discontinuous at low cutting speeds, while continuous at high cutting speeds. The dimple textured flank face cutting tools facilitate the dry machining of AZ31B magnesium alloy and contribute to ecological benefits.

Synthesis and Characterization of Carbonate Hydroxyapatite from Pokea Clam Shells (&lt;i&gt;Batissa Violacea Var. Celebensis&lt;/i&gt;) by Precipitation and Hydrothermal Methods

Hydroxyapatite Carbonate (CHA) is a material that is found to have a composition more similar to bone, with a higher bioactivity than Hydroxyapatite (HA). CHA was synthesized using precipitation and hydrothermal methods using (NH4)2HPO4 as a phosphate source, NH4HCO3 as a carbonate source, and Pokea shells as a calcium source. In this study, the Pokea shells were crushed, calcined, and characterized based on physicochemical tests. CaO from Pokea shell contains 74.33% calcium. CHA was successfully produced by precipitation method at room temperature and hydrothermal at 120 C for 8 h. Sample characterization was carried out using X-Ray Diffraction (XRD), Fourier Transform Infrared (FTIR), and Scanning Electron Microscope Energy Dispersive X-Ray Spectroscopy (SEM-EDX). Based on XRD data, there are differences in the crystal size of CHA produced via precipitation and hydrothermal methods, where the crystal sizes of Precipitation CHA-1 and Hydrothermal CHA-2 are 6.388 nm and 25.969 nm. The FTIR results of both CHA show the functional groups typical of CHA, namely OH-, CO, CaO, PO43-, and CO32-. From the Ca/P EDX data results, Precipitation CHA-1 and Hydrothermal CHA-2 do not differ much, namely 1.71 and 1.69, and this value indicates that CHA has been formed.

Characterization of Mn5Ge3 Contacts on a Shallow Ge/SiGe Heterostructure.

Mn5Ge3 is a ferromagnetic phase of the Mn-Ge system that is a potential contact material for efficient spin injection and detection. Here, we investigate the creation of Mn5Ge3-based contacts on a Ge/SiGe quantum well heterostructure via solid-state synthesis. X-ray diffraction spectra fitting indicates the formation of Mn5Ge3-based contacts on bulk Ge and Ge/SiGe. High-resolution scanning transmission electron microscopy imaging and energy dispersive X-ray spectroscopy verify the correct Mn5Ge3-based phase formation. Schottky diode measurements, transmission line measurements, and Hall measurements reveal that Mn5Ge3-based contacts serve as good p-type contacts for Ge/SiGe quantum well heterostructures due to having a low Schottky barrier height of 0.10eV (extracted from a Mn5Ge3/n-Ge analogue) and a contact resistance in the order of 1 kΩ. Furthermore, we show that these electrical characteristics have a gate-voltage dependence, thereby providing tunability.

Long-term corrosion of copper alloys in the soil: new aspects of corrosion morphology in archaeological vessels from south-western Iran

A group of copper-based objects excavated at Deh Dumen cemetery, in south-western Iran, was studied and analysed to examine the long-term corrosion morphology and mechanism in the soil burial environment. For this purpose, twenty-two samples from twenty-one copper-based vessels were studied and analysed using X-ray diffraction, scanning electron microscopy—energy dispersive X-ray spectroscopy, micro-Raman spectroscopy and metallography techniques. The results of the analyses showed that the majority of vessels are made of tin bronze, along with two arsenical copper samples. The extent of corrosion observed ranges from very thin corrosion crusts to thick crusts and entirely corroded structures. These three identified corrosion morphologies display a multi-layered corrosion stratigraphy as well as the preserved limit of the original surface. The corrosion crusts include internal tin-rich and external copper-rich layers, and the main corrosion mechanism for the formation of multi-layered corrosion crusts is decuprification or selective dissolution of copper during the long-term burial time in a moderately Cl-contaminated soil. The three identified corrosion morphologies are similar to the previously published morphologies, but some clear deviations are apparent and are discussed here.

Selective recovery of rare earth elements by smelting of magnets

Rare earth elements (REEs) play a crucial role in many technologies from daily appliances in cell phones to more advanced wind turbines and electric cars. Permanent magnets account for a quarter of total global REEs production and have high recycling value. In this study, smelting process was used to selectively oxidize REEs in the permanent magnets by adding Fe2O3. This separates REEs into a slag phase from an iron-rich metallic phase. B2O3 was also added to the system as a flux to lower the slag melting temperature. This minimizes REEs loss to the metallic phase and allows a more efficient phase separation. The effect of flux and oxidizing agent addition was investigated on both regular and cerium-rich NdFeB (NdCeFeB) magnets. At 1350 °C and for 1 h, the slag phase was successfully separated from the metallic phase with the addition of 0.8 stoichiometric amount of Fe2O3 and 40 wt% of B2O3. Scanning electron microscopy–energy dispersive X-ray spectroscopy (SEM-EDX) analysis reveals that REEs in the magnet do not migrate to the metal phase while the REE-rich slag phase contains almost no iron. After the selective removal of iron into the metallic phase, REEs are recovered from the slag phase through an acid leaching process allowing >99% of REEs recovery. Boron in the magnet can also be recovered as useful boric acid by evaporation and crystallisation technique. The proposed process in this study is reagent and energy-efficient with almost complete valorisation of both NdCeFeB and NdFeB magnets.

Analysis of Pigments Unearthed from the Yungang Grottoes Archaeological Excavations

The Yungang Grottoes, excavated during the 5th to 6th centuries AD, stand as a pinnacle of Buddhist sculpture, representing a precious world cultural heritage. Since their excavation, the grottoes have undergone multiple phases of painting, with a significant amount of pigment still present on the surfaces of the stone carvings. Since the 1990s, two large-scale archaeological excavations have been conducted on both the front ground and the summit of Yungang Grottoes. During these excavations, various artifacts with accompanying pigments were unearthed, encompassing stone carvings, grinding tools, architectural components, fragments of murals, and remnants of clay sculptures, spanning the historical periods of the Northern Wei, Liao-Jin, and Ming-Qing dynasties. Using portable X-ray fluorescence spectrometry, portable microscopy, polarizing microscopy, scanning electron microscopy–energy dispersive X-ray spectroscopy, and confocal Raman microscopy, we conducted a comprehensive analysis of these painted elements. The investigation revealed the presence of hematite, vermilion, goethite, malachite, calcium carbonate, lead white, and ivory black pigments in the Northern Wei samples. The Liao-Jin samples exhibited hematite, while the Ming-Qing samples contained vermilion, minium, atacamite, lead white, and Prussian blue.

Characterization of Chilean hot spring-origin Staphylococcus sp. BSP3 produced exopolysaccharide as biological additive

A type of high molecular weight bioactive polymers called exopolysaccharides (EPS) are produced by thermophiles, the extremophilic microbes that thrive in acidic environmental conditions of hot springs with excessively warm temperatures. Over time, EPS became important as natural biotechnological additives because of their noncytotoxic, emulsifying, antioxidant, or immunostimulant activities. In this article, we unravelled a new EPS produced by Staphylococcus sp. BSP3 from an acidic (pH 6.03) San Pedro hot spring (38.1 °C) located in the central Andean mountains in Chile. Several physicochemical techniques were performed to characterize the EPS structure including Scanning electron microscopy–energy dispersive X-ray spectroscopy (SEM–EDS), Atomic Force Microscopy (AFM), High-Performance Liquid Chromatography (HPLC), Gel permeation chromatography (GPC), Fourier Transform Infrared Spectroscopy (FTIR), 1D Nuclear Magnetic Resonance (NMR), and Thermogravimetric analysis (TGA). It was confirmed that the amorphous surface of the BSP3 EPS, composed of rough pillar-like nanostructures, is evenly distributed. The main EPS monosaccharide constituents were mannose (72%), glucose (24%) and galactose (4%). Also, it is a medium molecular weight (43.7 kDa) heteropolysaccharide. NMR spectroscopy demonstrated the presence of a [→ 6)-⍺-d-Manp-(1 → 6)-⍺-d-Manp-(1 →] backbone 2-O substituted with 1-⍺-d-Manp. A high thermal stability of EPS (287 °C) was confirmed by TGA analysis. Emulsification, antioxidant, flocculation, water-holding (WHC), and oil-holding (OHC) capacities are also studied for biotechnological industry applications. The results demonstrated that BSP3 EPS could be used as a biodegradable material for different purposes, like flocculation and natural additives in product formulation.Graphical

Synthesis of TiO2/Fe2O3 Nanocomposites as Photocatalyst for Methyl Orange Degradation

Fe2O3/TiO2 composites were successfully synthesized using the sol-gel method. The photocatalytic performance of prepared nanocomposites to degrade methyl orange under UV light irradiation was systematically investigated. The Fe2O3 added and calcination temperature were varied to study their effect on psychochemical properties. Further, to study the effect of psychochemical properties of the prepared nanocomposites on photocatalytic activity, X-ray diffraction (XRD), and scanning electron microscope Energy Dispersive X-ray spectroscopy (SEM-EDS) characterization were conducted. The visible light active Fe2O3 photocatalyst managed to decrease the bandgap energy of the prepared composites from 3.32 eV to 1.95 eV. This decrease in the band gap energy led to the composite being more active under visible light and less active under UV light irradiation. A composite with 6% Fe2O3 content exhibits the smallest degradation efficiency of 14% in 180 min, while the pure TiO2 nanoparticles are 94%. The results in this study provided important implications for further research on the preparation of composite TiO2 with Fe2O3 co-catalyst showing a promising route for improving the visible light activity of photocatalysts.

Thermodynamic behavior and kinetic analysis of carbothermal reduction process of low-grade oxysulfur lead–zinc ore

During the exploitation of sphalerite resources, a considerable amount of low-grade oxysulfur Pb–Zn deposits is generated, which poses a significant threat to the environment and soil and water conservation in mining areas. Therefore, low-grade Pb–Zn resources urgently require source emission reduction and appropriate utilization. This study applied a mineral technology and conducted X-ray diffraction and scanning electron microscopy–energy dispersive X-ray spectroscopy to investigate the phase transformation and the mechanism underlying the volatilization of Pb and Zn at different times and temperatures. The Pb–Zn volatilization kinetics of a low-grade oxysulfur Pb–Zn ore by a one-step pyrometallurgical process in an argon atmosphere was studied, and the effects of different temperature conditions on the Zn volatilization process were investigated. The results showed that the Zn-containing phase in the raw material was decomposed to ZnO and ZnS upon heating. Moreover, ZnO was reduced via carbothermal reduction, whereas ZnS was reduced via a CaO-assisted carbothermal reaction and volatilized in the form of gaseous Zn. In the Pb-containing phase, PbSO4 generated PbO, Pb, and PbS in the presence of Fe, FeS, and CaO. PbO was volatilized in the form of gaseous Pb through carbothermal reduction and interactions between PbS and PbO. The Pb–Zn volatilization reaction conformed to the shrinking core model with a constant size, and the volatilization-based removal of Pb and Zn process was controlled by internal diffusion. A macroscopic kinetic model of the reaction was established on the basis of experimental data. The apparent activation energy of Pb and Zn volatilization was 163.90 and 328.19 kJ/mol, respectively. This study promotes the utilization of the low-grade oxysulfur Pb–Zn ore through a pyrometallurgical method to provide theoretical support for large-scale industrial treatments.

Glass/steel/clay interactions in a simulated radioactive waste geological disposal system

Deep geological storage is the accepted solution for the final disposal of high-level radioactive waste therefore, it is necessary to study the host rock of the planned Hungarian waste repository and the materials involved in the engineered barriers. The main goal was to understand the characteristics and stability of the glass/steel/claystone system, from the structural properties of the vitrified waste (borosilicate glasses) to the clay response in the repository. Repository conditions were applied during the experiments to understand the chemical evolution of the system. A triplicate setup was kept at 80 °C for 3, 7 and 12 months and post-mortem characterization was performed. No alteration products were observed with scanning electron microscopy energy dispersive X-ray spectroscopy measurements on the surface of the glass and Fe or in the clay after the end of the experimental period. Based on the elemental analysis of the liquid phase, the released amount of B, K, Si and Na increased, while that of Ca and Mg decreased compared to the baseline. The concentrations of Cl− and SO42− did not change significantly. Ca- and Mg-silicate precipitation was observed by X-ray photoelectron spectroscopy at the surface range of the borosilicate glasses because of the synthetic porewater treatment.

Micro-mechanical behavior of nanosilica-treated high-sulfate soils

The addition of calcium (Ca)-based stabilizers to sulfate-rich expansive soils is associated with the formation of ettringite, a deleterious reactant that can cause moderate-to-severe swell-related damage to overlying lightweight infrastructures. This research study was conducted to understand the effects of combining nanosilica admixtures with a traditional Ca-based stabilizer to effectively treat high-sulfate soils with an intent to suppress the ettringite formation. Engineering and microstructural studies were thus performed to gain a comprehensive understanding of the behavior of sulfate-bearing soils treated with lime in the presence of amorphous nanosilica. The engineering studies on treated and untreated soils included strength tests before and after capillary soaking, free swell strain tests, and resilient moduli studies that were performed to study and understand the macrostructural behavior of these soils at different curing periods. Supplemental studies using scanning electron microscope imaging and energy dispersive X-ray spectroscopy, thermal analyses using differential scanning calorimetry, and X-ray diffraction studies were also conducted to determine the microstructural changes that occur within these sulfate-rich soils. The results showed that additional silica phases furnished from nanosilica suppressed the precipitation of ettringite and correspondingly increased the formation of cementitious phases. This study also provided ample evidence that the application of amorphous siliceous nanomaterials positively impacts chemical treatments and reduces the precipitation of ettringite in sulfate-rich soils, thus enhancing their engineering performance.

Chemical composition-dependent hygroscopic behavior of individual ambient aerosol particles collected at a coastal site

Abstract. This study investigated the hygroscopic behavior of individual ambient aerosol particles collected at a coastal site of Jeju Island, South Korea. The size of the particles changes along with the phase transitions during humidification and dehydration processes, and the chemical compositions of the particles were determined by optical microscopy and scanning electron microscopy–energy dispersive X-ray spectroscopy (SEM-EDX), respectively. Of the 39 particles analyzed, 24 were aged sea spray aerosols (SSAs), with diverse mixing ratios of Cl− and NO3-. The ambient SSAs exhibited multiple deliquescence and efflorescence transitions that were dominantly influenced by NaCl, NaNO3, MgCl2, Mg(NO3)2, and organic species covering the surface of the aged SSAs. For Cl-rich SSAs with X(Na,Mg)Cl&gt;0.4, although some particles showed very slow water uptake at low relative humidity levels (RH ≃30 %), two major transitions were observed during the humidification process. The first was at RH ≃63.8 %, regardless of their chemical compositions, which is the mutual deliquescence relative humidity (MDRH) level; and the second was at RH 67.5 % to 73.5 %, depending on their chemical compositions, which are the final deliquescence relative humidity (DRH) levels. During the dehydration process, the Cl-rich SSAs showed single-stage efflorescence at RH 33.0 % to 50.5 %, due to simultaneous heterogeneous crystallization of inorganic salts. For Cl-depleted SSAs with X(Na,Mg)Cl&lt;0.4, two prompt deliquescence transitions were observed during the humidification process. The first was at MDRH 63.8 %, and the second was at RH 65.4 % to 72.9 %. The mutual deliquescence transition was more distinguishable for Cl-depleted SSAs. During the dehydration process, step-wise transitions were observed at efflorescence RH levels (ERH 24.6 % to 46.0 % and 17.9 % to 30.5 %), depending on their chemical compositions. Additionally, aged mineral particles showed partial or complete phase changes with varying RH due to the presence of SSAs and/or NO3- species. In contrast, non-reacted mineral and Fe-rich particles maintained their size during the entire hygroscopic process. The mixture particles of organic and ammonium sulfate (AS) exhibited lower deliquescence and efflorescence RH levels compared to pure AS salt, highlighting the impact of organic species on the hygroscopic behavior of AS. These findings emphasize the complexity of atmospheric aerosols and the importance of considering their composition and mixing state when modeling their hygroscopic behavior and subsequent atmospheric impacts.

WO3 dispersed on a titanium porous clay heterostructure as a highly efficient visible light-active photocatalyst

Nanocomposites of WO3-dispersed titanium-porous clay heterostructures (W/Ti-PCH) from montmorillonite raw clay were synthesized and reported for the first time in this paper. The nanocomposite was prepared by impregnating tungstophosphoric acid into the titanium-porous clay heterostructure (Ti-PCH). The physicochemical features of the nanocomposite were characterized by using X-ray diffraction (XRD), scanning electron microscopy energy dispersive X-ray spectroscopy (SEM-EDS), high-resolution transmission electron microscopy (HRTEM), UV–visible diffuse reflectance UV–visible spectroscopy (UV-DRS), X-ray photoelectron spectroscopy (XPS) and gas sorption analyses. Identification using XRD and XPS revealed that the dispersion of WO3 anchored on the Ti-PCH surface led to an increase in the band gap energy of the material from 3.1 eV in Ti-PCH to 3.22 eV in W/Ti-PCH. The improved characteristics support the excellent photocatalytic activity for RhB degradation, as 99.99 % removal was achieved after 15 min of treatment.