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.

Tailoring the Hybrid Magnetron Sputtering Process (HiPIMS and dcMS) to Manufacture Ceramic Multilayers: Powering Conditions, Target Materials, and Base Layers.

The mechanical and wear behavior of CrN/CrAlN multilayers were improved by tailoring the experimental conditions of a hybrid magnetron sputtering process based on a high-power impulse (HiPIMS) and two direct current magnetron sputtering (dcMS) power supplies. To this end, the influence of the base layer and of the combination of Cr and CrAl targets, which were switched to the dcMS and HiPIMS power supplies in different configurations, were investigated with respect to the growth of ceramic CrN/CrAlN multilayers onto commercial gas-nitrided diesel piston rings. The microstructure, grain morphology, and mechanical properties were evaluated by field emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM), X-ray diffraction (XRD), and instrumented nanoindentation. Bench wear tests simulating the operation of a combustion engine were conducted against a gray cast iron cylinder liner under reciprocating conditions using 0W20 oil as a lubricating agent enriched with Al2O3 particles. The results revealed a significant increase in hardness, resistance to plastic strain, and wear resistance when two CrAl targets were switched to a HiPIMS and a dcMS power supply, and a Cr target was powered by another dcMS power supply. The compressive coating stresses were slightly reduced due to the soft Cr base layer that enabled stress relief within the multilayer. The proposed concept of hybrid magnetron sputtering outperformed the commercial PVD coatings of CrN for diesel piston rings manufactured by cathodic arc evaporation.

Innovative adsorbents based on bentonite mining waste for removal of cationic dyes from wastewater.

Waste rock from bentonite mining (WRBM) was evaluated as potential adsorbents for removing crystal violet (CV) and methylene blue (MB) cationic dyes from contaminated water. The waste samples (AM01, AM02, and AM03) were collected from different locations of the bentonite mine and characterized through X-ray diffraction, X-ray fluorescence, Fourier-transform infrared spectroscopy, N2 adsorption/desorption, and cation exchange capacity. The adsorption efficiency of CV and MB dyes was investigated through the effect of initial concentration, contact time, pH, the dosage of adsorbent, and temperature. Sample AM02 showed the largest surface area (69.13 m2/g) and the best adsorptive performance for both dyes, with removal more significant than 90%. The adsorption of CV and MB in the waste followed the Langmuir isothermal model. Samples AM01 and AM02 followed the pseudo-second-order (PSO) kinetic model, while AM03 better fitted the Elovich kinetic model. The enthalpy (ΔH), entropy (ΔS), and Gibbs energy (ΔG) were evaluated as adsorption parameters. The process of adsorption of CV and MB dyes in the waste was predominantly endothermic and occurred spontaneously. WRBM samples proved to be a promising candidate for removing cationic dyes present in water.

Adsorption of Sodium Diclofenac in Functionalized Palygoskite Clays.

The effects of acid and organo-functionalizations on the surface of Brazilian palygorskite clay was investigated, evaluating its potential in the adsorptive capacity of the drug sodium diclofenac present in wastewaters. The modifications on the clay structure were investigated by X-ray diffraction, X-ray fluorescence, thermogravimetric, differential thermal analysis, Fourier transform infrared spectroscopy, surface area by N2 adsorption (77.5 K) and Zeta potential. The experimental design was carried out to find the best conditions for the adsorption tests, in which concentration, mass and pH were significant. In the kinetic study, the pseudo-second-order model better described the adsorption process for acid and organo-functionalized samples. Such results indicate that the adsorption behavior probably occurs due to the phenomenon of chemisorption. Regarding the adsorption isotherms, the Langmuir model was the one that best adjusted both the experimental data of acid and the organo-functionalized samples, whose maximum adsorption capacity were 179.88 and 253.34 mg/g, respectively. This model also indicates that the sodium diclofenac is adsorbed to monolayers homogeneously through chemisorption. In general, the studied clays proved to be suitable adsorbents for the removal of sodium diclofenac.

Hybrid magnetron sputtering of ceramic superlattices for application in a next generation of combustion engines.

A hybrid magnetron sputtering process (dcMS/HiPIMS) was developed to manufacture nanostructured CrN/Cr1-xAlxN multilayers, motivated by improving the low-emission efficiency when applied on gas-nitrided diesel piston rings of a next-generation of combustion engines. In order to improve the mechanical, tribological, and corrosion behavior of the multilayers, the hybrid dcMS/HiPIMS process was designed by selecting the optimal sputtering procedure applied to AISI 440 base steel. The effect of substrate bias and carousel rotational speed on the phase composition, crystallographic texture, residual stresses, surface roughness, coating periodicity and densification, instrumented hardness, elastic modulus, as well as wear and corrosion resistance was determined. The results have demonstrated that hybrid magnetron sputtering produces multilayers with a superlattice structure, which outperforms commercial PVD coatings of CrN for diesel piston rings manufactured by cathodic arc evaporation. Also, multilayer periodicities in the range of 5 to 10 nm yield the best tribological performance under bench tests for the piston ring/cylinder liner system.

New Clayey Deposit and Their Potential as Raw Material for Red or Structured Ceramics: Technological Characterization.

Mineralogical and technological characterization of ceramic raw materials from a new deposit located at Caxias city, Maranhão State-Brazil, was accomplished to determine their potential as raw materials for the ceramics industry in northeastern Brazil. The ceramic raw materials were collected from three different locations on the site and characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD), differential thermal analysis (DTA), and thermogravimetry (TG). The XRF analysis of the fraction < 2 µm revealed that most samples had SiO2 (35-51 wt%), Al2O3 (19-29 wt%), Fe2O3 (2-21 wt%), MgO (0.7 to 4.5 wt%) and K2O (0.9 to 5 wt%) as components. Quartz, kaolinite, illite, hematite and montmorillonite were the main mineral phases identified. DTA and TG analysis confirmed the mineral identification. The technological potential of the ceramic raw materials was investigated by: cation exchange capacity (CEC), plastic behavior (Atterberg Limits), linear shrinkage at 950 °C (LSF), flexural strength (FS), apparent porosity (AP), water absorption (WA) and bulk density (BD). The main experimental results-WA (9-17%), AP (19-31%), FS (2.0-23 MPa), and the Atterberg limits-indicated that the ceramic raw materials investigated have high potential to be used to develop mass for red or structured ceramics, such as bricks and roof tiles.

Adsorption Behavior of Crystal Violet and Congo Red Dyes on Heat-Treated Brazilian Palygorskite: Kinetic, Isothermal and Thermodynamic Studies.

The effect of heat treatment on the adsorptive capacity of a Brazilian palygorskite to remove the dyes crystal violet (CV) and congo red (CR) was investigated. The natural palygorskite was calcined at different temperatures (300, 500 and 700 °C) for 4 h. Changes in the palygorskite structure were evaluated using X-ray diffraction, X-ray fluorescence, thermogravimetric and differential thermal analysis, N2 adsorption/desorption and Fourier transform infrared spectroscopy. The adsorption efficiency of CV and CR was investigated through the effect of initial concentration, contact time, temperature, pH and dosage of adsorbent. The calcination increased the adsorption capacity of palygorskite, and the greatest adsorption capacity of CV and CR dyes occurred in the sample calcined at 700 °C (Pal-700T). The natural and calcined samples at 300 and 500 °C followed the Freundlich isothermal model, while the Pal-700T followed the Langmuir isothermal model. Adsorption kinetics results were well described by the Elovich model. Pal-700T showed better adsorption performance at basic pH, with removal greater than 98%, for both dyes. Pal-700T proved to be a great candidate for removing cationic and anionic dyes present in water.

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.

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.

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.

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.

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.

On manufacturing multilayer-like nanostructures using misorientation gradients in PVD films.

Due to their applicability for manufacturing dense, hard and stable coatings, Physical Vapor Deposition (PVD) techniques, such as High Power Impulse Magnetron Sputtering (HiPIMS), are currently used to deposit transition metal nitrides for tribological applications. Cr-Al-N is one of the most promising ceramic coating systems owing to its remarkable mechanical and tribological properties along with excellent corrosion resistance and high-temperature stability. This work explores the possibility of further improving Cr-Al-N coatings by modulation of its microstructure. Multilayer-like Cr1-xAlxN single films were manufactured using the angular oscillation of the substrate surface during HiPIMS. The sputtering process was accomplished using pulse frequencies ranging from 200 to 500 Hz and the resulting films were evaluated with respect to their hardness, Young's modulus, residual stresses, deposition rate, crystallite size, crystallographic texture, coating morphology, chemical composition, and surface roughness. The multilayer-like structure, with periodicities ranging from 250 to 550 nm, were found associated with misorientation gradients and small-angle grain boundaries along the columnar grains, rather than mesoscopic chemical modulation of the microstructure. This minute modification of microstructure along with associated compressive residual stresses are concluded to explain the increased hardness ranging from 25 to 30 GPa, which is at least 20% over that expected for a film of the same chemical composition grown by a conventional PVD processing route.