Chemical Composition Distribution Research Articles

Multicore@shell nanoparticle synthesis from a single multicomponent target by gas aggregation source

Synthesis of multifunctional nanomaterials is known as a critical challenge in advanced nanoscience. Multicore@shell nanostructures are generated here via a gas phase synthesis approach. To achieve this objective, we used conventional DC magnetron sputtering in conjunction with a gas aggregation chamber. We employed a customized Au-Ti target to produce metal-metal oxide multicore@shell nanoparticles (NPs) with tunable properties. The deposited NPs were characterized with regard to their chemical composition, morphology, structural status, NP size distribution and optical properties. The obtained data clearly confirms that the crystalline Au cores are encapsulated in a TiOx matrix in each individual NP. Furthermore, the chemical composition and size distribution of the NPs can be affected by the operating pressure. Our approach provides a versatile route with many different possibilities to synthesize multicore@shell NPs from a variety of composite targets for well-desired applications including environmental, optical/plasmonic, and energy.

Numerical Optimization of Functionally Graded Ti-HAP Material for Tibial Bone Fixation System.

Functionally graded materials (FGMs) are heterogeneous composites characterized by outstanding properties. They are built from two or more components with a gradient distribution of chemical composition along a given direction. A promising graded material for biomedical engineering as an implant could be a FGM made of titanium (Ti) and hydroxyapatite (HAP). It would allow us to counteract the difference between the stiffness modulus of pure titanium and bone tissue. Moreover, it can be a good solution to the problem of stress shielding for bone fixation plates made of conventional titanium or steel. The presented paper aims to perform micromechanical modeling and optimization of a functionally Ti-HAP graded plate, followed by numerical analysis of a fractured tibia stabilization system under specific boundary conditions. Finite element analysis was performed using ANSYS Workbench 2021 software. The models of the FGM plate and tibial fixation system were made using the Space Claim tool. The ANSYS software allowed the optimization of the model considered and the selection of the appropriate structural parameters of the FGM Ti-HAP material. In general, the results proved that the osteosynthesis plate built of graded Ti-HAP material resulted in lower bone stress compared to titanium and steel plates. The results obtained confirmed the validity of the design and the possibility to use functionally graded Ti-HAP bone fixation plates.

Evaluation of Clayey Raw Materials and Ceramic Masses from Ceramic Building Material Companies Located in Northeastern Brazil

The challenge of improving the quality of ceramic products is faced worldwide, especially in areas where artisanal production is common and the need for in-depth knowledge about raw materials, together with inefficient production processes, limits the advancement of the ceramic industry. Scientifically, detailed investigation of ceramic masses’ physical, chemical and mechanical properties can provide essential insights to optimize production, contribute to developing more advanced and sustainable techniques, and increase competitiveness. This study evaluated raw clay materials and ceramic masses obtained from northeastern Brazilian, focusing on their chemical composition, mineralogical phases, thermal behavior, and particle size distribution. Rectangular samples (80 mm × 20 mm × 7 mm) prepared using uniaxial pressing (25 MPa by 30 s) were fired at different temperatures (950 and 1050 °C) and linear shrinkage, flexural strength, water absorption, and apparent porosity measurements were taken. The results showed that the companies still need to improve the production process to meet the minimum strength requirement of 1.5 MPa according to the Brazilian standard NBR 15270.

Spectral and optic-metric methods of monitoring parameters of plasma channels caused by discharge currents between metals granules in working liquids

Introduction. Spark-erosion processing of metals and alloys granules in working liquids is the basis of a several technological processes. Efficiency of energy use in them and parameters of the resulting product largely depend on the accuracy of stabilization and regulation of pulse power in each plasma channel between the granules. To achieve this, until now only the voltage and current of the discharge pulses in the entire layer of granules have been controlled. Problem. The measurement methods, which are used, are not effective enough for monitoring the parameters of individual plasma channels and predicting the size distribution of eroded metals particles at the stage of their formation. The aim of the work is to develop a method for determining the volumes of components of plasma channels in layers of metals granules during their spark-erosion treatment to predict the size distribution of eroded metal particles at the stage of their formation, as well as to simplify the method of spectrometric analysis of the elemental composition of substances surrounding plasma channels for the operational prediction of the chemical composition of resulting products. Methodology. A series of experiments were carried out on spark-erosion processing of Al and Ag granules layers in distilled water. Using a digital camera, images of the plasma channels in them were obtained. Based on the theory of pulsed electrical breakdown of liquid dielectrics, an analysis of the components of plasma channels was carried out. Using the specialized ToupView program, the volumes of equivalent ellipsoids of rotation were determined, approximating the halos of colored radiation likely arising from streamers, as well as the spark cores of plasma channels emitting white light. The shades of the resulting radiation were studied for several metals and working liquids. The obtained data were compared with the known results of spectrometric studies for the same elements excited by similar mechanisms. Results. The theory of discharge-pulse systems for spark-erosion processing of granular conductive media has been developed in the direction of new methods for monitoring the parameters of discharge pulses and predicting the chemical composition and size distribution parameters of eroded metal particles at the stage of their production. An optic-metric method has been developed for determining the volumes of halos and cores of plasma channels. A simplified spectral method for determining the chemical composition of erosion particles based on the shade of the resulting radiation was proposed. Originality. The developed new optic-metric method makes it possible to obtain information about almost every plasma channel, which refines predictions of the size distribution of erosion particles. To implement the method, general-purpose hardware and specialized software that is freely available are used. The developed method of simplified spectral analysis of excited atoms makes it possible to make preliminary predictions of the chemical composition of the obtained erosion particles already at the stage of their formation without the use of expensive specialized equipment. Practical significance. The ratio of the volumes of halos and cores of plasma channels between Al and Ag granules in distilled water was measured. An analysis of the emission spectra of plasma channel halos between Al, Ag and Cu granules in distilled water, Fe in ethyl alcohol, Ni-Mn-Ga and Ti-Zr-Ni alloys in liquid nitrogen, and Ti-Zr-Ni in liquid argon was carried out. Based on spectrometry data, the resulting shades of these radiations were substantiated and their description in the RGB system is given. References 56, table 1, figures 4.

Modeling, assessment and characterization of soiling on PV Technologies. Toward a Better understanding of the Relation between dust deposition and performance losses

Soiling is a critical, site-specific challenge that affects the performance and economic viability of photovoltaic power plants. This study evaluates the effectiveness of an outdoor microscopy method under the specific climatic conditions and dust composition of the Mid-south region of Morocco. Semi-empirical models were developed to correlate the Soiling Coverage Index with losses in optical and electrical performance. Additionally, a comprehensive analysis of local dust, encompassing its chemical composition, morphology, and size distribution, was conducted. Results indicate quartz as the predominant mineral in Benguerir city’s dust particles, with diameters ranging from 0 μm to 26 μm. Additionally, following a 2-week exposure with no rainfall, a dust density of 2.5 g/m2 accumulated on the deployed glass coupons, resulting in a soiling ratio of 6.9 % and a relative transmittance loss of 15.19 %. The surface coverage index, as calculated by the outdoor microscope, was 9.16 %. Furthermore, the evaluation of this metric revealed strong positive correlations (r2 = 0.95 to 0.99) with key soiling indicators such as dust density, soiling ratio, and transmittance loss. These findings underscore the efficacy of the outdoor microscope as a fast, low-cost, and reliable soiling monitoring sensor, offering valuable insights for future monitoring and mitigation efforts.

Regulating Anode-Electrolyte Interphasial Reactions by Zwitterionic Binder Chemistry in Lithium-Ion Batteries with High-Nickel Layered Oxide Cathodes and Silicon-Graphite Anodes.

The practical application of silicon (Si)-based anodes faces challenges due to severe structural and interphasial degradations. These challenges are exacerbated in lithium-ion batteries (LIBs) employing Si-based anodes with high-nickel layered oxide cathodes, as significant transition-metal crossover catalyzes serious parasitic side reactions, leading to faster cell failure. While enhancing the mechanical properties of polymer binders has been acknowledged as an effective means of improving solid-electrolyte interphase (SEI) stability on Si-based anodes, an in-depth understanding of how the binder chemistry influences the SEI is lacking. Herein, a zwitterionic binder with an ability to manipulate the chemical composition and spatial distribution of the SEI layer is designed for Si-based anodes. It is evidenced that the electrically charged microenvironment created by the zwitterionic species alters the solvation environment on the Si-based anode, featuring rich anions and weakened Li+-solvent interactions. Such a binder-regulated solvation environment induces a thin, uniform, robust SEI on Si-based anodes, which is found to be the key to withstanding transition-metal deposition and minimizing their detrimental impact on catalyzing electrolyte decomposition and devitalizing bulk Si. As a result, albeit possessing comparable mechanical properties to those of commercial binders, the zwitterionic binder enables superior cycling performances in high-energy-density LIBs under demanding operating conditions.

Microstructure and mechanical properties of Ti60–Ti2AlNb functionally graded materials fabricated by laser directed energy deposition

The increasing demands for materials that service under high temperature environments in advanced aero-engines with high thrust-to-weight ratios have led to the exploration of functionally graded materials, which can offer unique advantages for addressing these challenges, such as the ability to achieve multiple properties at different positions of the components. In this study, Ti60–Ti2AlNb functionally graded materials were fabricated via laser directed energy deposition (L-DED) with 20% compositional step and various step widths in the transition zone. The distribution of chemical composition, microstructure, and microhardness in the transition zone of functionally graded materials with different compositional paths along the deposition direction were investigated. Meanwhile, the mechanical properties and fracture mechanisms were also evaluated. Smooth composition transition has been achieved in the joint zone between Ti60 and Ti2AlNb. By decreasing the width of each composition zone in the transition area or removing the Ti60-60% Ti2AlNb zone, the precipitation of the hard and brittle α2 phase can be effectively suppressed, thereby enhancing the tensile strength of the graded material. Through this approach, Ti60–Ti2AlNb functionally graded material with a tensile strength of 1030.9 MPa and elongation of 2.0% was fabricated.

Mg Exosphere of Mercury Observed by PHEBUS Onboard BepiColombo During Its Second and Third Swing‐Bys

AbstractMercury's exosphere is an important target for understanding the dynamics of coupled systems in space environments, tenuous planetary atmospheres, and planetary surfaces. Magnesium (Mg) is especially crucial for establishing methods for estimating the surface chemical composition distribution through observations of the exosphere because its distribution in the exosphere and on the surface is strongly correlated. However, owing to its low radiance, the Hermean Mg exosphere has only been detected by the Mercury Atmospheric and Surface Composition Spectrometer (MASCS) onboard the Mercury Surface, Space Environment, Geochemistry, and Ranging (MESSENGER) spacecraft. Thus, we have few observation data for areas other than low latitude regions in addition to few detection cases of short‐term or sporadic fluctuations, resulting in a poor understanding of ejection and transportation mechanisms of the Mg exosphere. In this study, we analyzed the distribution of the Hermean Mg exosphere by the Probing of Hermean Exosphere by Ultraviolet Spectroscopy (PHEBUS) onboard the Mercury Planetary Orbiter of the BepiColombo mission during its second and third Mercury swing‐bys (MSBs). First, we constructed a calibration method including background subtraction and calibration using stellar observations. Mg light curves at two true anomaly angles were obtained, which were in agreement with the Chamberlain model and a three‐dimensional numerical calculation. Comparing the Mg and calcium (Ca) radiances obtained by PHEBUS during the MSBs, the exospheric Mg atoms have a lower energy than the exospheric Ca atoms. This is consistent with the lower energy necessary for producing the Mg atoms produced by molecular photodissociation than for Ca atoms.

Effect of cultivation and geographical location on chemical composition and enantiomeric distribution in linalool-rich Origanum dubium Boiss. essential oils obtained at different growth stages

ABSTRACT The current study is objected to investigate the essential oil yields, chemical compositions, and enantiomeric distribution of wild and cultivated linalool rich Origanum dubium Boiss. essential oils obtained at pre-flowering, initial flowering, and post-flowering growth stages. Wild plant materials are collected from Mediterranean region of Turkey. Samples were also cultivated in Mediterranean and Aegean coastlines of Turkey in the experimental fields of Ministry of Agriculture and Forestry of Turkey. O. dubium samples yielded between 6.7 and 9.7% (mL/100 g) of essential oils. The compositions were dominated by oxygenated monoterpenes (98.2–98.9%). Linalool was detected as the major compound in all essential oils (97.0–97.6%). The dominant enantiomer was discovered as (R)-(-)-linalool with a 99.3–99.4% enantiomeric purity. The essential oil yields, chemical compositions and enantiomeric distributions were found to be constant regardless of cultivation, geographical locations or different growth stages. The result of this manuscript indicates that by culturing linalool chemotype of O. dubium, the industrial need for (R)-(-)-linalool could be met at more affordable costs.

Regulating Anode‐Electrolyte Interphasial Reactions by Zwitterionic Binder Chemistry in Lithium‐Ion Batteries with High‐Nickel Layered Oxide Cathodes and Silicon‐Graphite Anodes

AbstractThe practical application of silicon (Si)‐based anodes faces challenges due to severe structural and interphasial degradations. These challenges are exacerbated in lithium‐ion batteries (LIBs) employing Si‐based anodes with high‐nickel layered oxide cathodes, as significant transition‐metal crossover catalyzes serious parasitic side reactions, leading to faster cell failure. While enhancing the mechanical properties of polymer binders has been acknowledged as an effective means of improving solid‐electrolyte interphase (SEI) stability on Si‐based anodes, an in‐depth understanding of how the binder chemistry influences the SEI is lacking. Herein, a zwitterionic binder with an ability to manipulate the chemical composition and spatial distribution of the SEI layer is designed for Si‐based anodes. It is evidenced that the electrically charged microenvironment created by the zwitterionic species alters the solvation environment on the Si‐based anode, featuring rich anions and weakened Li+‐solvent interactions. Such a binder‐regulated solvation environment induces a thin, uniform, robust SEI on Si‐based anodes, which is found to be the key to withstanding transition‐metal deposition and minimizing their detrimental impact on catalyzing electrolyte decomposition and devitalizing bulk Si. As a result, albeit possessing comparable mechanical properties to those of commercial binders, the zwitterionic binder enables superior cycling performances in high‐energy‐density LIBs under demanding operating conditions.

Employment of MQ gas sensors for the classification of Cistus ladanifer essential oils

The chemical composition of essential oils (EOs) from Cistus ladanifer has a huge variability throughout the year, impacting the oil quality. Nowadays, EO analytic chemistry techniques, which are expensive and destroy the sample, are utilized to measure the chemical composition. In the paper, we propose a combination of low-cost sensors and machine learning based system. As low-cost sensors, seven gas sensors are combined to obtain up to 36 features. Regarding machine learning, 31 multiclass classification algorithms are applied. Data from sensors were collected for 33 samples of EO from Cistus ladanifer. The generated dataset was split into training and test datasets, with 75 % of the data for training. The datasets were created to ensure a homogeneous chemical composition distribution on both training and test datasets. There were three target chemical compounds: Alpha-pinene and Viridiflorol as individual compounds and Terpenic Hydrocarbons as a group of chemical compounds. The value of the percentage of each targeted compound is converted into a categoric variable with 5 possible values, 1 being the lowest concentration and 5 being the maximum one. The data of the MQ-sensors were included as the input for the models, and each one of the targeted chemical compounds was selected as an output for different models. The input features were ranged using different algorithms for the feature selection process. The results indicate that there is no valid classification model for Viridiflorol, and limited accuracy is achieved for Alpha-pinene. Meanwhile, for Terpenic Hydrocarbons, an accuracy of 91.6 % is achieved. It is important to highlight that these accuracies were attained when a reduced number of features were included, ranging the number of features from 11 to 13. This is the first case in which MQ-based gas sensors, or other metal oxide sensors, are used to correctly determine the concentration of a chemical compounds in a complex matrix formed by dozens of compounds. This system will provide a cheap method to determine the quality of EOs and confirm the benefits of combining low-cost sensors with machine learning.

Chemically Resolved Respiratory Deposition of Ultrafine Particles Characterized by Number Concentration in the Urban Atmosphere.

Ultrafine particles (UFPs) dominate the atmospheric particles in number concentration, impacting human health and climate change. However, existing studies primarily rely on mass-based approaches, leading to a restricted understanding of the number-based and chemically resolved health effects of atmospheric UFPs. In this study, we utilized a high-mass-resolution single-particle aerosol mass spectrometer to investigate the online chemical composition and number size distribution of ultrafine, fine, and coarse particles during the summertime in urban Shenzhen, China. Human respiratory deposition dose assessments of particles with varying chemical compositions were further conducted by a respiratory deposition model. The results showed that during our observation, particles containing elemental carbon (EC) were the dominant components in UFPs (0.05-0.1 μm). Compared to fine and coarse particles, UFPs can deposit more deeply into the respiratory tract with a daily dose of ∼2.08 ± 0.67 billion particles. Among the deposited UFPs, EC-cluster particles constituted ∼85.7% in number fraction, accounting for a daily number dose of ∼1.78 billion particles, which poses a greater impact on human health. Simultaneously, we found discrepancies in the chemically resolved particle depositions among number-, surface area-, and mass-based approaches, emphasizing the importance of an appropriate metric for particle health-risk evaluation.

Processing and microstructure development of reactive sintered (Ti-Zr-Nb-Hf-Ta)B2 + (Ti-Zr-Nb-Hf-Ta)C high-entropy ceramics

A novel dual-phase (Ti-Zr-Nb-Hf-Ta)B2 + (Ti-Zr-Nb-Hf-Ta)C high-entropy, compositionally complex composite was synthesized by reactive spark plasma sintering using commercial ZrB2, NbB2, HfB2, TaB2 and TiC powders as starting materials. The composite with high density, consists predominantly of boride (∼39.7 vol%) and carbide (∼56.4 vol%) phases and with residual amount of (Hf-Zr)O2. The microstructure is homogenous and relatively fine due to the reaction and solid solution coupling effect with average grain sizes of 3.4 μm and 2.2 μm of the boride and carbide phases, respectively. Large-area SEM analyses confirmed no microcracks or micropore formation and no presence of large grains or clusters. Investigation from micro to nano and atomic level, focused on local chemical composition and spatial distribution of constituent elements, revealed that Ti preferentially dissolves into the boride and all other elements to the carbide phase creating a (Ti0.82Zr0.04Nb0.08Hf0.03Ta0.03)B2 + (Ti0.49Zr0.12Nb0.13Hf0.11Ta0.15)C system. The analysis of grain and phase boundary interfaces revealed a continuous, <1.5 nm wide, segregation of impurity atoms of Fe and Co. Continuous (>20 nm) and atomically flat basal interfacial termination planes (001) decorated with monoatomic Zr enriched layer in the boride phase were observed. Triple points at grain and phase boundaries exhibit metal-rich composition due to impurities from the starting raw powders.

Effect of Zr content on the microstructure, mechanical properties, electrochemical behavior, and biocompatibility of Mg–3Zn–xZr alloy using powder metallurgy

Abstract In this study, Mg–3Zn–xZr (x = 0, 0.5, 1, 2 and 3) alloy were produced using powder metallurgy incorporating high-energy ball milling. Scanning electron microscope (SEM), energy dispersive X-ray (EDX) analyzer and X-ray diffraction (XRD) have been used to investigate the microstructure, chemical composition and phase distribution of the samples. XRD results show that the Mg solid solution wholly formed, and the milled powders were single phase, and no secondary phase was observed. While the secondary phases were formed after sintering. Hardness of Mg–Zn–xZr sample increased from 58.8 Hv (for Zr = 0) to 87.81 Hv with addition of 3 wt.% Zr. The result shows that the corrosion potential of Mg–Zn–Zr alloy was more positive than Mg–3Zn. However, the Mg–3Zn–Zr alloy exhibited higher corrosion current than Mg–3Zn due to galvanic effect of Zr rich area. All of Mg–3Zn–Zr alloys showed better antibacterial and biocompatibility properties than Mg–3Zn alloy due to the presence of Zr as additive. According to the mechanical, corrosion, and biological evaluations in this study, it can be concluded that the Mg–3Zn–1Zr alloy can be used as a suitable biomaterial for the use of orthopedic implants.

Spatiotemporal Active Phase Evolution for CO2 Electrocatalysis

Transition-metal-based solid-state electrocatalysts undergo dynamic phase transformation governed by the local electrochemical environment during operation, e.g., oxygen evolution/reduction(1,2), hydrogen evolution(3), and carbon dioxide reduction(4). Electrochemical active species, often hidden before operation, can become evolved due to the applied electrochemical potential and/or surrounding chemicals. These species are stabilized under the local environment dynamically generated by the reaction product, e.g., proton (H+) or hydroxyl (OH-) group(5,6).Active species often account for a small fraction (i.e., minor motif) of the entire catalyst volume, and the nanoscale morphology and chemical composition of the electrocatalyst are inhomogeneous and continuously change during the electrochemical reaction. Thus, capturing the active species remains a major challenge. Spatiotemporal observation of the structural/chemical changes of the electrocatalyst and the correlation with the local electrochemical environment may reveal the active species and elucidate the governing step toward their formation. Furthermore, identification of the key intermediate step of catalyst phase transformation allows the redirection of low- to high-active catalysts; however, this remains challenging.During electrochemical CO2 reduction (ECR), (hydr)oxide-derived Cu electrocatalysts experience significant phase transformation and show high activity and selectivity for carbon dimerization (C–C coupling)(7,8,9). The location and chemical composition of the active species evolving during electrochemical phase transformation may be strongly heterogeneous; however, these species have not been clearly determined. Recent studies have employed operando characterization techniques, e.g., fluorescence hard/soft X-ray(4,10), X-ray photoelectron(11), and Raman spectroscopy(6), to elucidate the active species responsible for high C–C coupling activity. However, although these techniques could track the changes in chemical composition of the electrocatalysts during operation, they did not reveal the spatiotemporal evolution of the active species or existence of minor motifs, owing to their inefficient chemical sensitivity. Thus, it is imperative to develop an operando analysis technique that can probe the nanoscopic chemical composition with high spatial/temporal resolution and sufficient detection limit.By observing the chemical and morphological evolution of highly efficient ECR catalysts during operation, we identified the key intermediate species toward highly active surfaces and significantly enhanced the C–C coupling activity. Operando transmission soft X-ray microscopy(1,12,13), which visualizes the nanoscale chemical composition distribution of Cu-based catalysts during ECR, revealed that partially evolved Cu+ phases and surface Cu2+ phases are responsible for the dynamic dissolution–redeposition process(4,8) and improvement of C–C coupling activity, respectively. We further demonstrated that the dissolution–redeposition process is electrochemically triggered by inducing Cu+ phases, which are redirected to copper-carbonate-hydroxide species(6,14,15) even under high cathodic potentials. DFT calculations suggest that these cationic Cu species potentially serve as active species and/or assistive sites for enhancing C–C coupling activity.(1) Mefford, J. T., et al. Nature 593(7857), 67-73 (2021)(2) Kreider, M. E., et al. ACS Applied Materials & Interfaces 11(30), 26863-26871 (2019)(3) Zhai, L., et al. ACS Energy Letters 5(8), 2483-2491 (2020)(4) De Luna, P., et al. Nature Catalysis 1(2), 103-110 (2018)(5) Wang, Y., et al. Nature Catalysis 3(2), 98-106 (2020)(6) Henckel, D. A., et al. ACS Catalysis 11(1), 255-263 (2021)(7) Lee, S. Y., et al. Journal of the American Chemical Society 140(28), 8681-8689 (2018)(8) Zhong, D., et al. Angewandte Chemie International Edition 60(9), 4879-4885 (2021)(9) Lei, Q., et al. Journal of the American Chemical Society 142(9), 4213-4222 (2020)(10) Eilert, A., et al. The Journal of Physical Chemistry Letters 7(8), 1466-1470 (2016)(11) Arán-Ais, R. M., et al. Nature Energy 5(4), 317-325 (2020)(12) Lim, J. et al. Science 353, 566–571 (2016)(13) de Smit, E., et al. Nature 456(7219), 222-225 (2008)(14) Spodaryk, M., et al. Electrochimica Acta 297, 55-60 (2019)(15) Jiang, S., et al. ChemSusChem 15(8), e202102506 (2022) Figure 1

Muscular and Edible Organ Meat Chemical Composition, Macro and Micro-Elements Distribution and Subcutaneous Fat Properties of Camel and Beef Cattle Calves.

Muscular and Edible Organ Meat Chemical Composition, Macro and Micro-Elements Distribution and Subcutaneous Fat Properties of Camel and Beef Cattle Calves.

Effect of MgO/ZnO ratio on the formation process of MgxZn1-xO ceramics

The structural characteristics, chemical composition, and element spatial distribution in MgxZn1-xO ceramics were investigated using X-ray diffraction, scanning electron microscopy, Auger electron spectroscopy, energy-dispersive X-ray spectroscopy, and cathodoluminescence techniques. The study revealed that the morphology of the ceramic samples, as well as the mechanism of solid solution formation, depend on the relative contribution of both oxides in the charge. It was discovered that hexagonal and cubic phases of the solid solution were found to form simultaneously. An increase in the MgO content in the charge results in the magnesium content rise in the hexagonal grains continuously, reaching approximately 13 at.%. It was discovered an enrichment of grain boundaries with zinc and magnesium playing a significant role in doping ZnO and MgO grains. Obtained results allowed to propose two mechanisms involved in the formation of solid solution ceramics: i) diffusion of Mg and Zn along grain boundaries, followed by their incorporation into ZnO or MgO grains, respectively, and ii) interdiffusion of Mg into ZnO and Zn into MgO due to direct contact of ZnO and MgO grains. The second mechanism appears to dominate when both ZnO and MgO contribute comparably, increasing the probability of their direct contact. This study significantly advances the understanding of the process of the formation of MgxZn1-xO ceramics under thermodynamic conditions. These insights are crucial for optimizing the doping process and improving the material properties, thereby promoting innovations in the ceramics industry.

Anthropogenic and biogenic pollutants in a forested environment: SPRUCE-22 campaign overview

The SPRUCE-22 field campaign was conducted during July 2022 on a remote mountainous forested site in Greece to assess interactions of biogenic and anthropogenic pollutants in the Eastern Mediterranean. Particle chemical composition and size distributions along with concentrations of organic and inorganic gases were measured at high temporal resolution, while samples were collected and analyzed off-line. PM1 had a surprisingly high average concentration of 13 μg m−3 consisting primarily of organics (57%), followed by sulfate (30%), ammonium (9%), and black carbon (2%). Nitrates (both inorganic and organic) were less than 1% of the PM1 despite the relatively high NOx emissions in the Balkans. The PM2.5 concentrations at this remote site were similar and even higher than those in major cities across Greece including Athens, indicating the importance of regional transport for summertime pollution in the Eastern Mediterranean. The relatively constant average diurnal profiles of major anthropogenic pollutants are consistent with only minimal effects from local sources. Sulfates are not any more the dominant component of fine PM in Greece due to the reduction of SO2 emissions of coal-burning powerplants. The organic aerosol (OA) was quite oxidized with an average oxygen to carbon ratio (O:C) equal to 0.83. The average concentration of isoprene was 0.6 ppb, of monoterpenes 0.5 ppb, while the biogenic secondary organic aerosol factor (obtained through source apportionment analysis) was estimated to contribute 22% of the OA. Additional biogenic secondary organic aerosol (SOA) may be part of the two oxygenated OA (OOA) factors that were also identified. Radiocarbon analysis indicated that the non-fossil carbon was approximately equal to the sum of the biogenic and the more oxidized oxygenated OA, implying that the less oxidized OOA in this study was mostly associated to anthropogenic fossil fuel combustion. The biogenic SOA was quite aged (O:C equal to 0.63) and was also mostly transported to the site. Nearby new particle formation events occurred during 20 % of the days, with an average SO2 concentration of 0.3 ppb. The oxidative potential of the PM per unit of mass was quite high. The source attribution of the fine PM and the interactions among its anthropogenic and biogenic components are also discussed.

Effect of solvent type on chemical composition distribution analysis of polyolefins using crystallization elution fractionation (CEF)

For microstructure characterization of polyolefin by separation-based techniques with infrared detector, either 1,2-dichlorobenzene (o-DCB) or 1,2,4-trichlorobenzene (TCB) is commonly selected as a dissolution solvent and mobile phase. Herein, we studied the effects of o-DCB and TCB on the comonomer detection and chemical composition distribution (CCD) by crystallization elution fractionation (CEF) with a filter-based IR detector. We first compared the detector sensitivity on methyl group content or short chain branching (SCB) in polyethylene-co-butene with varied sample concentrations in o-DCB and TCB. TCB demonstrated superior comonomer detection in the IR detector with a single linear calibration across a wide range of sample concentrations. In contrast, o-DCB displayed stronger concentration dependent methyl group response, requiring a more complex equation in the calibration. Furthermore, o-DCB provided better separation of comonomer distribution with less peak broadening and co-crystallization effects, as observed with various polyolefins, including high density polyethylene (HDPE), linear low-density polyethylene (LLDPE), polypropylene (PP), and ethylene-propylene copolymer (EP).

Functionality-type and chemical-composition separation of poly(lactide-co-glycolide) using gradient elution normal-phase liquid chromatography with basic and acidic additives

End groups of poly(Lactide-co-glycolide) (PLGA) play an important role in determining the properties of polymers for use in drug delivery systems. For instance, it has been reported that the encapsulation efficiency in PLGA microspheres varies significantly between ester-terminated and acid-terminated PLGA. More importantly, the in-vivo degradation time of such polymer excipients is influenced by the functional end-group of the copolymer used.The end group distribution in PLGA polymers has been studied using electrospray and matrix-assisted laser-desorption/ionization – high-resolution mass spectrometry. In both cases, the application of these methods is typically limited to PLGA having a molecular weight of up to 4 kDa. 13Carbon-nuclear-magnetic-resonance has also been reported as a method to differentiate and quantify PLGA end groups with a molecular weight up to 136 kDa. However, reported NMR methods take over 12 h per sample, limiting throughput.Cryoprobe NMR can reduce the time required for the process, however such NMR equipment is costly, which makes it unsuitable for the quality control of PLGA.Here, we present a normal-phase liquid chromatography method capable of resolving functionality type distribution (FTD) and, partially, chemical composition distribution (CCD) in commercial PLGA polymers obtained from ring opening polymerization. This method can separate PLGA polymers with a molecular weight of up to 183.0 kDa while also enabling the simultaneous separation of the difference of Lactic acid (LA)/Glycolic acid (GA) ratios.To achieve this, a cross-linked diol column was used with a ternary gradient from HEX to 0.1 % v/v TEA in EA to 0.1 % v/v FA in THF to allow first for the elution of mono-ester terminated PLGA, followed by the di-acid terminated. In addition, a separation of ester-terminated PLGA in the difference of the LA/GA ratio was achieved.This method is expected to aid in understanding the correlation between PLGA's FTD, CCD, and physical properties, facilitating product development and quality control.