A Brief Review of MoO3 and MoO3-Based Materials and Recent Technological Applications in Gas Sensors, Lithium-Ion Batteries, Adsorption, and Photocatalysis.

Molybdenum trioxide is an abundant natural, low-cost, and environmentally friendly material that has gained considerable attention from many researchers in a variety of high-impact applications. It is an attractive inorganic oxide that has been widely studied because of its layered structure, which results in intercalation ability through tetrahedral/octahedral holes and extension channels and leads to superior charge transfer. Shape-related properties such as high specific capacities, the presence of exposed active sites on the oxygen-rich structure, and its natural tendency to oxygen vacancy that leads to a high ionic conductivity are also attractive to technological applications. Due to its chemistry with multiple valence states, high thermal and chemical stability, high reduction potential, and electrochemical activity, many studies have focused on the development of molybdenum oxide-based systems in the last few years. Thus, this article aims to briefly review the latest advances in technological applications of MoO3 and MoO3-based materials in gas sensors, lithium-ion batteries, and water pollution treatment using adsorption and photocatalysis techniques, presenting the most relevant and new information on heterostructures, metal doping, and non-stoichiometric MoO3-x.

Role of Nitrogen and Yttrium Contents in Manufacturing (Cr, Y)Nx Film Nanostructures.

The high-power impulse magnetron sputtering (HiPIMS) technique was applied to deposit multilayer-like (Cr, Y)Nx coatings on AISI 304L stainless steel, using pendular substrate oscillation and a Cr-Y target and varying the nitrogen flow rate from 10 to 50 sccm. The microstructure, mechanical and tribological properties were investigated by scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, instrumented nano-hardness, and wear tests. The columnar grain structure became highly segmented and nanosized due to pendular substrate oscillation and the addition of yttrium. The deposition rate increased continuously with the growing nitrogen flow rate. The increase in nitrogen flow from 10 to 50 sccm increased the hardness of the coatings (Cr, Y)Nx, with a maximum hardness value of 32.7 GPa for the coating (Cr, Y)Nx with a nitrogen flow of 50 sccm, which greatly surpasses the hardness of CrN films with multilayer-like (Cr, Y)Nx coatings architecture. The best mechanical and tribological performance was achieved for a nitrogen flow rate of 50 sccm. This was enabled by more elevated compressive stresses and impact energies of the impinging ions during film growth, owing to an increase of HiPIMS peak voltage with a rising N2/Ar ratio.

On Improving Wear Resistance of Cr-Al-N Coatings Using Dynamic Glancing Angle DC Magnetron Sputtering.

The development of alternatives for wear protection in surface engineering can be responsible for a significant decrease in energy waste as a large amount of the energy produced in the world is lost due to tribological contact. Dynamic Glancing Angle Deposition has been recently evaluated as a route to produce coatings with improved wear performance. In this technique, the substrate oscillates along with a determined range in front of the sputtering target during the growth of the film. In this study, five oscillatory ranges (0, ±5°, ±10°, ±15°, ±20°) were probed to manufacture nanostructured Cr-Al-N coatings using direct current magnetron sputtering, and their impact was investigated on the grain morphology, phase formation, chemical composition, and performance of the coatings. FEG-SEM revealed the formation of multilayer-like architecture across the grains of the coatings. The deposition rate and hardness improved, and a more than 2-fold decrease in the material loss was observed in a comparison between the stationary-deposited conventional coating and the sample produced under ±10° oscillatory range. This indicated the potential use of this technique in future surface engineering applications.

Solution Blow Spun Silica Nanofibers: Influence of Polymeric Additives on the Physical Properties and Dye Adsorption Capacity.

The physical properties of porous silica nanofibers are an important factor that impacts their performance in various applications. In this study, porous silica nanofibers were produced via solution blow spinning (SBS) from a silica precursor/polymer solution. Two polyvinylpyrrolidone (PVP, Mw = 360,000 and 1,300,000) were chosen as spinning aids in order to create different pore properties. The effect of their physical properties on the adsorption of methylene blue (MB) in an aqueous solution was explored. After forming, the nanofibers were calcined to remove the organic phase and create pores. The calcined nanofibers had a large amount of micro and mesopores without the use of additional surfactants. The molecular weight of the PVP impacted the growth of silica particles and consequently the pore size. High Mw PVP inhibited the growth of silica particles, resulting in a large volume of micropores. On the other hand, silica nanofibers with a high fraction of mesopores were obtained using the lower Mw PVP. These results demonstrate a simple method of producing blow spun silica nanofibers with defined variations of pore sizes by varying only the molecular weight of the PVP. In the adsorption process, the accessible mesopores improved the adsorption performance of large MB molecules.

Adsorption of Anionic Dye on the Acid-Functionalized Bentonite.

The efficiency of acid treatment on natural calcium bentonite (natural bentonite) for anionic dye adsorption was investigated using methyl orange (MO) as a probe. Additionally, adsorption experiments were accomplished between the natural bentonite, acidified bentonite, and a cationic dye (methylene blue, MB). Acid functionalization in natural bentonite (RF) was carried out with HCl and H2SO4 acids (RF1 and RF2, respectively). The samples were characterized by chemical analysis, mineralogy, particle size, and thermal behavior with the associated mass losses. The adsorption efficiency of MO and MB dyes was investigated by the effects of the initial concentration of adsorbate (Ci) and the contact time (tc). The acid treatment was efficient for increasing the adsorption capacity of the anionic dye, and the Qmaxexp values measured were 2.2 mg/g, 67.4 mg/g e 47.8 mg/g to RF, RF1 e RF2, respectively. On the other hand, the acid functionalization of bentonite did not significantly modify the MB dye adsorption. The Sips equation was the best fit for the adsorption isotherms. Thus, we found that the acid-functionalized bentonite increases the anionic dye adsorption by up to 8000%. The increased adsorptive capacity of acidified bentonite was explained in terms of electrostatic attraction between the clay surface and the dye molecule.

Development of Scheelite Tailings-Based Ceramic Formulations with the Potential to Manufacture Porcelain Tiles, Semi-Stoneware and Stoneware.

New ceramic formulations based on scheelite tailing were developed, and their potential in the ceramic industry was evaluated. Green bodies with different contents of scheelite tailing (0-8 wt%) were sintered (1150 °C, 1200 °C, and 1250 °C) and characterized in terms of the main mineralogical phases, microstructure, and physico-mechanical properties. The mullite was the main phase identified in all sintered temperatures. This result was also ratified with the aid of scanning electron microscope (SEM) images, in which small needles of the mullite were detected. The presence of mullite is required because it contributes to increasing the mechanical resistance of the material. The physico-mechanical properties measured (water absorption, linear shrinkage, apparent porosity, and flexural strength) were compared to the ISO 13006, and the samples sintered at 1150 °C presented potential to be used as semi-stoneware, while those sintered at 1200 °C and 1250 °C can be employed stoneware and porcelain tiles, respectively.

Development and characterization of a babassu nut oil-based moisturizing cosmetic emulsion with a high sun protection factor.

A stable moisturizing cosmetic emulsion was developed from babassu nut oil and high concentrations of sunscreens. Babassu nut oil was chosen because within the laboratory time-scale, this vegetable oil showed stable physicochemical properties (relative density, acidity index, and refracted index) and a good ratio between lauric and myristic fatty acids. The presence of these saturated fatty acids can confer specific activities to the cosmetic emulsion, such as antiviral, bactericidal, and anti-inflammatory activity. The prepared cosmetic emulsion, even after the centrifugation test (3000 rpm for 15 min), showed a creamy appearance with stable light-yellow coloration and the typical odor of babassu nut oil-based products. In the accelerated stability assays (pH, viscosity, and globule homogeneity), the cosmetic emulsion was kept at different temperatures (2.0 ± 0.2 °C (T G), 25 ± 2 °C (T A), and 40 ± 2 °C (T E)) and time durations (24 hours (t 0), 7 days (t 7), 15 days (t 15), and 30 days (t 30)). Finally, developed the cosmetic emulsion was investigated for occlusive properties and in vitro sun protection factor (SPF). Both were measured at room temperature and did not change significantly under the experimental conditions employed. The maximum experimental value measured in the in vitro occlusive test was equal to 34.2 ± 2.8, and the SPF was 39 ± 1.6 (t 0) and 38 ± 2.9 (t 30). In agreement with European and Brazilian legislations, the obtained babassu oil-based cosmetic emulsion is classified to have a high sun protection factor.

Nitrogen-Enriched Cr1-xAlxN Multilayer-Like Coatings Manufactured by Dynamic Glancing Angle Direct Current Magnetron Sputtering.

Multilayer-like CrN and Cr1-xAlxN coatings with different Al contents were deposited onto a stainless steel substrate using dynamic glancing angle deposition direct current magnetron sputtering (DGLAD dcMS) in a N rich atmosphere to understand the role of Al on the growth of the films and mechanical properties of the nitrides with a multilayer architecture. Chemical analysis by means of energy dispersive analysis (EDS) and glow discharge optical emission spectroscopy (GDOES) depth profiling revealed that while CrN samples were close to stoichiometric, the Cr1-xAlxN coatings presented excess N between 70 and 80% at. An expressive change in texture was observed as the CrN coating changed its preferred orientation from (111) to (200) with the addition of Al, followed by a modification in morphology from grains with faceted pyramidal tops in CrN to dome-shaped grains in Cr1-xAlxN coatings. Multilayer-like nanostructures of corrugated grains were produced with a periodicity of approximately 30 nm using dynamic glancing angle deposition. The deposition rate was drastically reduced with an increase of Al, meanwhile, the best mechanical performance was achieved for the coating with a higher content of Al, with hardness up to 27 GPa and a higher value of maximum resistance to plastic deformation.

Avaliação da reatividade ao ataque químico de resíduo oriundo da mineração da scheelita utilizado como agregado em argamassas cimentícias / Evaluation of reactivity to the chemical attack of waste from the mining of scheelite used as aggregate in cementitious mortars

RESUMO A mineração de scheelita, localizada em Currais Novos, Rio Grande do Norte, tem gerado grandes volumes de resíduos sólidos que são destinados inadequadamente aos sistemas ambientais, causando impactos ambientais negativos ao município. Uma das alternativas encontradas para destinar adequadamente esses resíduos é o uso em argamassas de matriz cimentícia. No entanto, não há estudos consistentes sobre a viabilidade técnica quanto aos ataques químicos e à influência na sua durabilidade. Nesse contexto, este trabalho teve como objetivo verificar se as argamassas confeccionadas com resíduos da mineração de scheelita em substituição total ao agregado convencional são suscetíveis ao ataque por sulfato de sódio. A caracterização física, química e mineralógica do resíduo foi realizada fazendo uso das seguintes técnicas: análise granulométrica por peneiramento; determinação da massa unitária; obtenção do teor de material pulverulento; espectrometria de fluorescência de raios X, e difração de raios X. A investigação da ocorrência do ataque por sulfato de sódio foi avaliada pela variação dimensional dos corpos de prova quando imersos em solução de sulfato de sódio, de acordo com a metodologia da Associação Brasileira de Normas Técnicas NBR 13583. Os resultados do traço 1:3 indicaram que os agregados oriundos dos resíduos da mineração de scheelita apresentaram comportamento reativo ao ataque por sulfato de sódio (expansão maior que 0,06%), bem como houve aumento da resistência à compressão simples em 4,74%. Portanto, embora tenha sido constatado que os corpos de prova incorporados com resíduos de scheelita tenham sido reativos ao sulfato, observou-se que não foram capazes de deteriorar mecanicamente os corpos de prova.

ABSTRACT The scheelite mining, located in Currais Novos, Rio Grande do Norte, has generated large volumes of solid waste that are inadequately destined for environmental systems, causing negative environmental impacts to the municipality. One of the alternatives to destination of these residues is the use in cementitious matrix mortars. However, there are no consistent studies on the technical feasibility of chemical attacks and influence on their durability. In this context, this work aimed to verify whether mortars made with scheelite mining residues in total substitution to conventional aggregate are susceptible to attack by sodium sulfate. The physical, chemical, and mineralogical characterization of the residue was carried out using the following techniques: sieve particle size analysis; determination of unit mass; obtaining the content of powdery material; X-ray fluorescence spectrometry, and X-ray diffraction. In the investigation of the occurrence of sodium sulfate attack was evaluated by the dimensional variation of the specimens when immersed in sodium sulfate solution, according to the methodology of Associação Brasileira de Normas Técnicas NBR 13583. The results of mixture 1:3 indicated that the aggregates from scheelite mining residues showed a reactive behavior to attack by sodium sulfate (expansion greater than 0.06%), as well as an increase in resistance to simple compression by 4.74%. Therefore, although it was found that specimens incorporated with scheelite residues were reactive to sulfate, it was observed that they were not able to mechanically deteriorate the specimens.

Imobilização de metais pesados presentes nos resíduos de quartzito por meio da incorporação em argamassas com substituição total do agregado natural / Immobilization of heavy metals present in quartzite residues through incorporation in mortars with total substitution of the natural aggregate

RESUMO Este trabalho objetivou imobilizar metais pesados presentes nos resíduos de quartzito por meio da incorporação em argamassas em substituição total ao agregado natural. Dois tipos de resíduos foram utilizados: os resíduos de fragmentação das aparas (QS) e os do pó de serragem (QP). Os resíduos foram caracterizados por fluorescência de raios X, difração de raios X e ensaios de toxidade conforme metodologia da Norma Brasileira (NBR) 10005, da NBR 10006 e do Toxicity Characteristic Leaching Procedure (TCLP) 1311. Então, foram analisadas composições de argamassas contendo cimento, cal e os resíduos (QS, QP) utilizando-se a técnica de delineamento de mistura, determinando os melhores traços, o melhor tipo de cura (imersa ou úmida) e, posteriormente, avaliando a resistência dos corpos de prova após cura. A caracterização do resíduo de quartzito revelou a presença de vários metais pesados e extratos lixiviados em contato com a água, classificando-o como resíduo de Classe I — Perigoso. Os resultados indicam que as composições determinadas foram capazes de imobilizar os metais pesados presentes nos resíduos de quartzitos, bem como resultou em argamassas com resistências mecânicas superiores a 2 MPa. Por fim, mostrou-se que essa técnica de solubilização e estabilização dos contaminantes presentes nos resíduos de quartzito é uma alternativa tecnologicamente viável e ambientalmente adequada para a destinação final desses resíduos.

ABSTRACT This work aims to immobilize heavy metals present in the quartzite residues by means of the incorporation in mortars in total substitution to the natural aggregate. Two types of residues were used: quartzite sand (QS) and powder (QP). The residues were characterized by x-ray fluorescence, x-ray diffraction, and toxicity tests according to the methodology of the NBR 10005, 10006 and Toxicity Characteristic Leaching Procedure (TCLP) 1311. Then, compositions of mortar containing cement, lime and residues (QS, QP) were analyzed using technique of designing the mixture, determining the best mixture, the best type of cure (immersed or wet), and subsequently evaluated at resistance of the body of evidences after curing. The characterization of quartzite residue revealed the presence of multiple heavy metals and leached extracts in contact with the water, classifying it a Class I-Hazardous waste. Regarding the production of mortars, the results indicated that the compositions determined were able to immobilize the heavy metals present in the quartzite residues, as well as resulted in mortars with mechanical resistances higher than 2 MPa. Finally, it was shown that this technique of solubilization and stabilization of contaminants present in quartzite residues is a technologically viable and environmentally adequate alternative for the final destination of these residues.