High-temperature Na2SO4 interaction with air plasma sprayed Yb2Si2O7 + Si EBC system: Topcoat behavior

The high-temperature interaction between ~2.5 mg/cm² of Na₂SO₄ and an atmospheric plasma sprayed (APS) Yb₂Si₂O₇ topcoat–Si bond coat system on SiC CMC substrates was studied for times up to 240 h at 1000°C–1316°C in a 0.1% SO₂–O₂ gaseous environment. Yb₂Si₂O₇ reacted with Na₂SO₄ to form Yb₂SiO₅ and an intergranular amorphous Na-silicate phase. Below 1200°C, the reaction was sluggish, needing days to cause morphological changes to the “splat microstructure” associated with APS coatings. The reaction was rapid at 1200°C and above, needing only a few hours for the entire topcoat to transform into a granulated microstructure consisting of Yb₂SiO₅ and Yb₂Si₂O₇ phases. Na₂SO₄ deposits infiltrated the Yb₂Si₂O₇ topcoat and transformed into an amorphous Na-silicate in less than 1 h at all exposure temperatures. Quantitative assessment of the Yb₂SiO₅ area fraction in the topcoat showed a linear decrease over time at 1316°C, attributed to reaction with the SiO₂ thermally grown oxide (TGO) formed on the Si bond coat and rapid transport through the interpenetrating amorphous Na-silicate grain boundary phase. It was predicted that nearly 2 weeks is needed for complete removal of Yb₂SiO₅ from the topcoat at 1316°C for a single applied loading of Na₂SO₄.     

Na2SO4 deposit-induced hot corrosion of SiC fibers relevant for SiC CMCs

Hi Nicalon, Hi Nicalon S, Sylramic, and Sylramic iBN SiC fibers were exposed to ~60 μg/cm² of Na₂SO₄ in a 0.1% SO₂/O₂ gaseous environment for times between 0.75 and 24 h at 1000°C. After exposure, the corrosion products were characterized using SEM, EDS, ICP-OES, TEM, and EFTEM to determine their high-temperature resistance to Na₂SO₄ and key reaction mechanisms. All SiC fiber types tested in this work exhibited little resistance to Na₂SO₄ deposit-induced attack relative to their behavior in dry O₂ environments. It was found that Hi-Nicalon displayed the least resistance to Na₂SO₄ deposit-induced attack due to excess carbon content resulting in the formation of a highly porous crystalline oxide and promotion of basic corrosion conditions. All fiber types formed a crystalline SiO₂ reaction product, either cristobalite or tridymite. Sylramic and Sylramic iBN formed a crystalline SiO₂ reaction layer containing TiO₂ needles due oxidation of TiB₂ particles. Additionally, Na₂SO₄ deposits resulted in pitting of all fiber surfaces.     

Mid‐infrared spectroscopy as a tool for real‐time monitoring of ethanol absorption in glycols

Fast, simple, accurate, and inexpensive methods for obtaining analyte concentration data are desirable in the industrial sector. In the present study, the use of Fourier transform mid‐infrared (FT‐MIR) spectroscopy, combined with partial least squares (PLS) regression, was investigated as a tool for real‐time monitoring of processes of ethanol absorption in glycols. Calibration was performed using simple synthetic samples containing ethanol, water, and monoethylene glycol (MEG) or diethylene glycol (DEG). The PLS models presented excellent performance, with correlation coefficients (R²) close to unity and root‐mean‐square errors of cross‐validation (RMSECV) and prediction (RMSEP) lower than 2% of the calibration data ranges for both analytes (ethanol and water) in both absorbents (MEG and DEG). The monitoring technique developed has potential to be applied in absorption processes and could also be used in other large‐scale unit operations, providing information in real time and enhancing process control.     

An investigation of the synergistic effect between magnetite nanoparticles and polypyrrole in nanostructured layer-by-layer films

In this paper, we report the controlled fabrication of layer-by-layer (LbL) films deposited on gold substrates with three different supramolecular architectures using polypyrrole (Ppy) and magnetite nanoparticles (Fe₃O₄-np), besides conventional poly(allylamine hydrochloride) (PAH) e poly(vinyl sulfonic acid) (PVS) polyelectrolytes, demonstrating the synergistic effect between Ppy and Fe₃O₄-np such as a result of their interaction. Modified gold electrodes were analyzed by contact angle (wettability), surface plasmon resonance (SPR), raman spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. The (Fe₃O₄-np/Ppy)₃ architecture was also evaluated by scanning electron microscopy. The modified gold electrodes present more homogeneous covering, higher electron transfer and a decrease of resistance with the incorporation of the nanostructured materials such as Ppy and Fe₃O₄-np forming (Fe₃O₄-np/Ppy)₃ LbL film. The results carried out in this study suggest that the (Fe₃O₄-np/Ppy)₃ LbL film can be applied as a possible electrochemical or optical non-enzymatic sensor for analytical detection.     

Evaluation of the removal of n-butanol vapor by the poly(lactic acid)-zeolite-TiO2 composite and formation of by-products

The use of polymeric films incorporated with zeolite-TiO₂ composites associated with UV radiation can be an alternative in the removal of volatile organic compounds (VOCs) through the adsorption and photodegradation processes. This study produced poly(lactic acid) (PLA) films incorporated with 13× zeolite, TiO₂, and 13×-TiO₂ zeolite composite to remove n-butanol and evaluate the by-products generated in the process. The results showed that 13× zeolite and TiO₂ added individually or as a composite to PLA, gave the polymer matrix a significant increase in the removal capacity of n-butanol. The best performance was presented by the zeolite-TiO₂, composite, confirming a synergistic effect. However, the formation of CO and CO₂ exceeded the expected values, with the verification that the polymeric matrix underwent photodegradation action by TiO₂. The polymeric film only containing zeolite is the most suitable for the removal of VOCs, as it did not present degradation of the PLA, generating a lower concentration of by-products.     

Poly(vinylidene fluoride) with zinc oxide and carbon nanotubes applied to pressure sheath layers in oil and gas pipelines

In this work, PVDF composites containing 0.2% (m/m) of carbon nanotubes (MWCNTs), PVDF with 5.0% (m/m) of zinc oxide (ZnO), and composites containing both particles in the same contents in the matrix were melt processed in a mini-extruder machine with double screws, using the counter-rotation mode. Composites were characterized by scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray diffraction (XRD), dynamic-mechanical analysis (DMA), and contact angle tests (CA). The samples presented the predominance of the α phase, with an increased degree of crystallinity as well as an increase in dimensional stability by incorporating both fillers, showing a synergistic effect between these particles, as shown on FTIR, DSC, and XRD results. SEM images showed a good dispersion of high aspect ratio particles. In general, DMA and TGA analysis showed that composites had not decreased their thermal and mechanical performance when compared to neat PVDF. Results of CA analysis showed an increase in the hydrophobicity of the sample containing MWCNTs. Permeability tests were also performed using a differential pressure system, combining high temperature and pressure, obtaining permeability measures and time lag. This work presents an alternative of composite materials, suggesting its application in the internal pressure sheath layers of oil and gas flexible pipes.     

Melt processing of nanocomposites of cellulose nanocrystals with biobased thermoplastic polyurethane

Nanocomposites of thermoplastic polyurethane (TPU) with cellulose nanocrystals (CNC) without and with surface treatment are obtained by melt processing. Nanocomposites are obtained with nanofiller weight content near of the theoretical percolation threshold (3.9 wt%). Visual observation of CNC agglomerates is sufficient to prove the inefficiency of the mixing in systems with untreated CNC. The crystallization kinetics of the TPU changes with the addition of CNC and this is confirmed by differential scanning calorimetry analysis. Thermogravimetric analysis prove that the addition of CNC increases the thermal stability of the TPU. From the rheological analysis it is possible to verify the absence of percolation and an intermediate state of sol–gel transition in the nanocomposites. CNC/TPU nanocomposites with 5 wt% of treated CNC present better mechanical performance than de neat TPU and the other processed nanocomposites and display around 130% increase in Young's modulus while retaining significant values of toughness, tensile strength and elongation at break.     

High-velocity oxyfuel thermal spray coatings for biomedical applications

Plasma spraying is used to produce most commercially available bioceramic coatings for dental implants; however, these coatings still contain some inadequacies. Two types of coatings produced by the high- velocity oxyfuel (HVOF) combustion spray process using commercially available hydroxyapatite (HA) and fluorapatite (FA) powders sprayed onto titanium were characterized to determine whether this relatively new coating process can be applied to bioceramic coatings. Diffuse reflectance Fourier transform infrared (FTIR) spectroscopy, x- ray diffraction (XRD), and scanning electron microscopy (SEM) were used to characterize the composition, microstructure, and morphology of the coatings. The XRD and FTIR techniques revealed an apatitic structure for both HA and FA coatings. However, XRD patterns indicated some loss in crystallinity of the coatings due to the spraying process. Results from FTIR showed a loss in the intensity of the OH^∼ and F^∼ groups due to HVOF spraying; the phosphate groups, however, were still present. Analysis by SEM showed a coating morphology similar to that obtained with plasma spraying, with complete coverage of the titanium substrate. Interfacial SEM studies revealed an excellent coating-to-substrate apposition. These results indicate that with further optimization the HVOF thermal spray process may offer another method for producing bioceramic coatings.     

XPS spectra of the AFe4Al8 compounds with A=Y, Sc, U and Th

The XPS electronic structures of the AFe₄Al₈ (A=Sc, Y, U, Th) single crystals were measured. The valence band of UFe₄Al₈ exhibits domination of the U 5f states at the Fermi level, while for the other AFe₄Al₈ compounds the valence states are shifted by 0.5 eV toward higher binding energy. The multiplet structure of the U 4f and Th 4f states was analyzed in comparison with the U 4f states of U₃Ge₅ and UNiSb₂.     

Impact of virtual atmospherics and functional qualities on the online gambler's experience

This study empirically tests a stimulus–organism–response (S–O–R) structural model that proposes that an online casino's atmospheric cues and functional qualities influence individuals' affective and cognitive responses, which in turn impact consumer behavioural intentions. Using self-reported data from a primarily US-based sample, analysed elements of the online gambling site stimulus included high and low task-relevant cues, financial trust, and gambling value. Demographic characteristics were found to moderate the relationship between the stimulus and internal satisfaction, with demographic group differences found among all stimulus constructs. Results emphasise the significant role that atmospherics and functional qualities play in generating positive behaviours from online gamblers, with additional implications in marketplace competitiveness and in responsible gambling practices.