Unipolar plasma electrolytic oxidation: Waveform optimisation for corrosion resistance of commercially pure titanium

This study deals with the anodisation of titanium grade 2 in 0.5-M sulphuric acid using a pulsed signal in a unipolar regime. The electrical parameters investigated are voltage, frequency and duty cycle. The use of duty cycles with a high percentage of anodic polarisation (90%), combined with high frequencies (1000 Hz) and the higher voltage tested (220 V), favoured the establishment of a plasma regime involving strong dielectric discharges, allowing the growth of thicker oxides but with rough architecture. The corrosion resistance of the formed film has been characterised by potentiodynamic tests in 0.5-M NaBr for localised corrosion resistance and by immersion tests in 10% v/v sulphuric acid solution for a uniform corrosion assessment. Current–time curves, visual observations and electron microscope analysis (scanning electron microscopy, energy-dispersive X-ray spectroscopy) were the tools selected to provide a correlation between technological parameters and oxide growth mechanism. For localised and uniform corrosion, anodisation at 220 V with a high level of anodic polarisation (90%) and frequency (1000 Hz) was verified to be particularly advantageous.     

Structure,mechanical and thermal properties of Y-doped CrAlN coatings

CrAlYN coatings with different Y contents (0, 5 and 12 at.%) were deposited by cathodic arc evaporation to investigate the influence of Y-addition on the structure, mechanical and thermal properties of CrAlN coatings by using X-ray diffraction, scanning electron microscopy, differential scanning calorimetry, thermal gravimetric analysis and nanoindentation. The structural transformation of single phase cubic Cr_0.42Al_0.58N and Cr_0.39Al_0.56Y_0.05N coatings to cubic–wurtzite mixed Cr_0.32Al_0.56Y_0.12N coating leads to a drop in hardness from (30.2±0.7) GPa of Cr_0.42Al_0.58N and (32.0±1.0) GPa of Cr_0.39Al_0.56Y_0.05N to (25.2±0.7) GPa of Cr_0.32Al_0.56Y_0.12N. The incorporation of 5 at.% Y retards the thermal decomposition of CrAlN, verified by the postponed precipitation of w-AlN and N-loss upon annealing. Correspondingly, Cr_0.39Al_0.56Y_0.05N coating consistently exhibits the highest hardness value during thermal annealing. Nevertheless, alloying with Y exerts an adverse effect on the oxidation resistance of CrAlN.     

Mesoporous SmMnO3/CuMnOx catalyst for photothermal synergistic degradation of gaseous toluene

Mesoporous SmMnO₃/CuMnO_x catalyst was prepared by a two-step method using flaky CuMnO_x with high specific surface and excellent catalytic ability as the carrier, which was further applied to photothermal synergistic degradation of gaseous toluene. Quantitative analysis of O₂-TPD and H₂-TPR showed that SmMnO₃/CuMnO_x exhibited abundant of the surface oxygen species and oxygen vacancies content, which enabled it to convert free oxygen to lattice oxygen more quickly during the reaction, and thus improving the reaction process. I-t and photoluminescence experiments demonstrated the improvement of photogenerated electron and hole separation ability of SmMnO₃/CuMnO_x catalyst. UV–Vis analysis manifested the full spectral range of absorption. XPS analysis verified the unequal positions of valence band of the two materials, which can facilitate the separation of photogenerated electrons from holes and improve the ability of better electron transfer. SmMnO₃/CuMnO_x catalyst has higher adsorbed oxygen content and light absorption capacity, which is beneficial to the catalytic oxidation. In situ DRIFTs proved that the oxidation reaction on the catalyst followed the Mars-van Krevelen redox cycle. The VOCs test found that SmMnO₃/CuMnOx composite catalyst is with lower onset reaction temperature (T₉₀ = 190 °C, T₉₀, corresponding to 90% conversion) and good mineralization (100% at 275 °C).     

Excision of Oxidatively Generated Guanine Lesions by Competitive DNA Repair Pathways

The base and nucleotide excision repair pathways (BER and NER, respectively) are two major mechanisms that remove DNA lesions formed by the reactions of genotoxic intermediates with cellular DNA. It is generally believed that small non-bulky oxidatively generated DNA base modifications are removed by BER pathways, whereas DNA helix-distorting bulky lesions derived from the attack of chemical carcinogens or UV irradiation are repaired by the NER machinery. However, existing and growing experimental evidence indicates that oxidatively generated DNA lesions can be repaired by competitive BER and NER pathways in human cell extracts and intact human cells. Here, we focus on the interplay and competition of BER and NER pathways in excising oxidatively generated guanine lesions site-specifically positioned in plasmid DNA templates constructed by a gapped-vector technology. These experiments demonstrate a significant enhancement of the NER yields in covalently closed circular DNA plasmids (relative to the same, but linearized form of the same plasmid) harboring certain oxidatively generated guanine lesions. The interplay between the BER and NER pathways that remove oxidatively generated guanine lesions are reviewed and discussed in terms of competitive binding of the BER proteins and the DNA damage-sensing NER factor XPC-RAD23B to these lesions.     

Improved formic acid oxidation using electrodeposited Pd–Cd electrocatalysts in sulfuric acid solution

In the present research, nanostructured Pd–Cd alloy electrocatalysts with different compositions were produced using the electrodeposition process. The morphology of the samples was studied by scanning electron microscopy analysis. Also, the elemental composition of the samples was determined by energy-dispersive X-ray spectroscopy and elemental mapping tests. Tafel polarization and electrochemical impedance spectroscopy methods were employed to determine the electrochemical corrosion properties of the synthesized samples in a solution containing 0.5 M sulfuric acid and 0.1 M formic acid. The linear sweep voltammetry, cyclic voltammetry, and chronoamperometry techniques were also employed to evaluate the electrocatalytic activity of prepared samples toward the oxidation of formic acid. In this respect, the influence of some factors such as formic acid and sulfuric acid concentrations and also potential scan rate was investigated. Compared to the pure Pd sample, the Pd–Cd samples were more reactive for the oxidation of formic acid. Besides, the sample with a lower amount of Pd (Pd_1·3Cd) demonstrated much higher electrocatalytic activity than the Pd_7·1Cd and Pd_2·1Cd samples. The observed high mass activity of 15.06 A mg^?1_Pd for the Pd_1·3Cd sample which is 21.1 times higher than Pd/C is an interesting result of this study.     

Catalytic Activity of Ceramic Honeycombs in the Exhaust Gas Oxidation of a Waste Treatment Plant

The activity of ceramic honeycombs with varying material composition and degree of utilization is compared on a suitable model gas in a test plant. The tested honeycombs are standard products that have not been surface‐treated in any way. A propane‐air mixture was fed to the test plant and then oxidized in a high‐temperature furnace. The analysis of the conversion rate over the reaction temperature showed remarkable differences in activity. The honeycomb with the most promising results was further investigated with the exhaust gas from the drying process of a waste treatment plant. Finally, the activity of this honeycomb was assessed in a large‐scale trial in an existing running regenerative thermal oxidizer.     

Effects of hydroxyl radical induced oxidation on water holding capacity and protein structure of jumbo squid (Dosidicus gigas) mantle

Protein oxidation is considered as an important issue in food preservation process. In the present study, the potential influence of protein oxidation on water holding capacity and protein structure of jumbo squid (Dosidicus gigas) mantle was investigated. After the hydroxyl radical oxidation, it was found that the carbonyl, surface hydrophobicity and dityrosine content of myofibrillar protein significantly increased (P < 0.05), while the content of total sulphydryl decreased significantly (P < 0.01). Meanwhile, the fluorescence intensity of squid was weakened, and the maximum absorption peak of fluorescence red shift as the H₂O₂ concentration increased. The sodium dodecyl sulphate polyacrylamide gel electrophoresis (SDS-PAGE) showed that not only the protein cross-linking but also degradation could have occurred. The content of α-helix decreased, the content of β-sheet, β-turn and the unordered structures increased after oxidation. In addition, oxidation resulted in a decrease in water holding capacity. Taken together, oxidation resulted in the damage of the myofibrillar structure, the increase in muscle loss rate and the decrease in water holding capacity.     

Boosting the activity of FeOOH via integration of ZIF-12 and graphene to efficiently catalyze the oxygen evolution reaction

Transition metal oxyhydroxides have been used as promising electrocatalysts for water splitting however, their catalytic activity is restricted due to low surface area and poor conductivity. Herein, we report novel composite FeOOH@ZIF-12/graphene composite as electrocatalyst for water oxidation, whereby ZIF-12 provide extra surface for the FeOOH dispersion whilst graphene act as excellent electron mediator. The composite shows a low overpotential value of 291 mV to attain a current density of 10 mA cm^?2 and a low Tafel slope value of 78 mV dec^?1. The catalyst offers a maximum current density of 101 mA cm^?2, while it gives a turnover frequency (TOF) value of 0.031 s^?1 at an overpotential of 291 mV only. The excellent activity and remarkable stability of composite is attributed to highly conductive and porous support.     

Simulation studies on a rotating ring disk electrode: Effects of ionic migration with kinetic complication-disk results

In continuation to my previous work (Guha S. AIChE J. 2013;59(4):1390-1399), in this work, effects of ionic migration are evaluated for disk region of a rotating ring disk electrode system by numerically solving complex differential equations, developed for mass transfer along with kinetic complication in presence of ionic migration under limiting current condition. The system for simulation is 0.01 M Fe₂(SO₄)₃ solution with H₂SO₄ as supporting electrolyte. Simulation cases are presence and absence of ionic migration with kinetic complication (oxidation of Fe²⁺ to Fe³⁺ under O₂ pressure). Results show that concentration boundary layer thickness of reactant Fe³⁺ reduces appreciably and steady-state disk current reduces substantially in presence of migration. Simulated steady-state disk current in absence of migration case agrees well with published data. Results indicate higher Fe²⁺ concentration in presence of migration and thereby higher rate of oxidation of Fe²⁺ to Fe³⁺ at all rate constant values.