Search results for: oxidation stability

Authors: Yuri A. Kalvachev, Totka D. Todorova

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Zeolite mordenite has been investigated as a transition metal support for the preparation of efficient catalysts in the oxidation of volatile organic compounds (VOCs). The highly crystalline mordenite samples were treated with hydrofluoric acid and ammonium fluoride to get hierarchical material with secondary porosity. The obtained supports by this method have a high active surface area, good diffusion properties and prevent the extraction of metal components during catalytic reactions. The active metal phases platinum and copper were loaded by impregnation on both mordenite materials (parent and acid treated counterparts). Monometalic Pt and Cu, and bimetallic Pt/Cu catalysts were obtained. The metal phases were fine dispersed as nanoparticles on the functional porous materials. The catalysts synthesized in this way were investigated in the reaction of complete oxidation of propane and benzene. Platinum, copper and platinum/copper were loaded and there catalytic activity was investigated and compared. All samples are characterized by X-ray diffraction analysis, nitrogen adsorption, scanning electron microscopy (SEM), X-ray photoelectron measurements (XPS) and temperature programed reduction (TPR). The catalytic activity of the samples obtained is investigated in the reaction of complete oxidation of propane and benzene by using of Gas Chromatography (GC). The oxidation of three organic molecules was investigated—methane, propane and benzene. The activity of metal loaded mordenite catalysts for methane oxidation is almost the same for parent and treated mordenite as a support. For bigger molecules as propane and benzene, the activity of catalysts based on treated mordenite is higher than those based on parent zeolite.

Keywords: metal loaded catalysts, mordenite, VOCs oxidation, zeolites

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Authors: Z. Khalifa, K. M. Hassan, M. Abdel Azzem

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Potential strategies for deriving useful forms of renewable high density energy from abundant energy stored in carbohydrates is direct conversion of glucose (GLU) to electrical power. A three novel versatile modified electrodes, synthesized by electrochemical polymerization of organic monomers on glassy carbon electrodes (GC), have been developed for biofuel cells results in stable and long-term power production. Electrocatalytic oxidation of glucose in alkaline solution on conducting polymers electrodes modified by incorporation of Ni nanoparticles (NiNPs) onto poly(1,5-aminonaphthalene) (1,5-PDAN), poly(1,8-diaminonaphthalene) (1,8-PDAN) and poly(1-amino-2-methyl-9,10-anthraquinone) (PAMAQ) was investigated. The electrocatalytic oxidation of glucose at NiNPs-modified 1,5-PDAN/GC, 1,8-PDAN/GC and PAMAQ/GC electrodes has been studied using voltammetry technique. The PDAN electrodes show a slight activity in the potential of interest. The prepared NiNPs/PAMAQ/GC catalyst showed a very interesting catalytic activity that was nicely comparable to the NiNPs/1,5-PDAN/GC, NiNPs/1,8-PDAN/GC modified electrodes. In advance, both shows a significant more catalytic activity compared to the reported data for electrodes for glucose electrocatalytic oxidation.

Keywords: biofuel cells, glucose oxidation, electrocatalysis, nanoparticles and modified electrodes

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Authors: M. J. Kim, D. B. Lee

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Centrifugal casting is a metal casting method that uses forces make by centripetal acceleration to distribute molten material in mold. Centrifugal cast parts manufactured in industry contain gas pipes and water supply lines, moreover rings, turbocharger, bushings, brake drums. Turbochargers were exposed to exhaust temperatures of 900-1050°C require a material for the corrosion resistance that will withstand such high component temperatures during the entire service life of the vehicle. Hence, the study of corrosion resistance for turbocharger is important for practical application. DIN1.4091 steels were used widely. The DIN1.4091 steels whose compositions were Fe-34.4Cr-14.5Ni-2.5Mo-0.4W-0.4Mn-0.5Si-(0.009 or 0.35)S (wt.%) were centrifugally cast, and oxidized at 900°C for 50-200 h in order to find the effect of sulfur on the high-temperature oxidation of Fe-34.4Cr-14.5Ni-2.5Mo-0.4W-0.4Mn-0.5Si-(0.009 or 0.35)S (wt.%) alloys. These alloys formed oxide scales that consisted primarily of Cr₂O₃ as the major oxide and Cr₂MnO₄ as the minor one through preferential oxidation of Cr and Mn. Cr formed a thin CrOx oxide film on the surface to prevent further oxidation, and when it is added more than 20%, the sulphide decreased corrosion rate. The high affinity of Mn with S, led to the formation of scattered MnS inclusions, particularly in the 0.35S-containing cast alloy. Sulfur was harmful to the oxidation resistance because it deteriorated the scale/alloy adherence so as to accelerate the adherence and compactness of the formed scales. Acknowledgement: This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (2016R1A2B1013169).

Keywords: centrifugal casting, turbocharger, sulfur, oxidation, Fe-34.4Cr-14.5Ni alloy

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Authors: Ádám Vass, István Bakos, Irina Borbáth, Zoltán Pászti, István Sajó, András Tompos

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Important requirements for the anode side electrocatalysts of polymer electrolyte membrane (PEM) fuel cells are CO-tolerance, stability and corrosion resistance. Carbon is still the most common material for electrocatalyst supports due to its low cost, high electrical conductivity and high surface area, which can ensure good dispersion of the Pt. However, carbon becomes degraded at higher potentials and it causes problem during application. Therefore it is important to explore alternative materials with improved stability. Molybdenum-oxide can improve the CO-tolerance of the Pt/C catalysts, but it is prone to leach in acidic electrolyte. The Mo was stabilized by isovalent substitution of molybdenum into the rutile phase titanium-dioxide lattice, achieved by a modified multistep sol-gel synthesis method optimized for preparation of Ti0.7Mo.3O2-C composite. High degree of Mo incorporation into the rutile lattice was developed. The conductivity and corrosion resistance across the anticipated potential/pH window was ensured by mixed oxide – activated carbon composite. Platinum loading was carried out using NaBH4 and ethylene glycol; platinum content was 40 wt%. The electrocatalyst was characterized by both material investigating methods (i.e. XRD, TEM, EDS, XPS techniques) and electrochemical methods (cyclic-voltammetry, COads stripping voltammetry, hydrogen oxidation reaction on rotating disc electrode). The electrochemical activity of the sample was compared to commercial 40 wt% Pt/C (Quintech) and PtRu/C (Quintech, Pt= 20 wt%, Ru= 10 wt%) references. Enhanced CO tolerance of the electrocatalyst prepared using the Ti0.7Mo.3O2-C composite material was evidenced by the appearance of a CO-oxidation related 'pre-peak' and by the pronounced shift of the maximum of the main CO oxidation peak towards less positive potential compared to Pt/C. Fuel cell polarization measurements were also carried out using Bio-Logic and Paxitech FCT-150S test device. All details on the design, preparation, characterization and testing by both electrochemical measurements and fuel cell test device of electrocatalyst supported on Ti0.7Mo.3O2-C composite material will be presented and discussed.

Keywords: anode electrocatalyst, composite material, CO-tolerance, TiMoOx

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Authors: Nur Sulihatimarsyila Abd Wafti, Harrison Lik Nang Lau, Nabilah Kamaliah Mustaffa, Nur Azreena Idris

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The use of biolubricant has gained its popularity over the last decade. Base stock produced using methyl ester and trimethylolethane (TME) can be potentially used for biolubricant production due to its biodegradability, non-toxicity and good thermal stability. The synthesis of biolubricant base stock e.g. triester (TE) via transesterification of palm methyl ester and TME in the presence of sodium methoxide as the catalyst was conducted. Factors influencing the reaction conditions were investigated including reaction time, temperature and pressure. The palm-based biolubricant base stock produced was analysed for its monoester (ME), diester (DE) and TE contents using gas chromatography as well as its lubricating properties such as viscosity, viscosity index, oxidation stability, and density. The resulting base stock containing 90 wt% TE was successfully synthesized.

Keywords: biolubricant, methyl ester, triester transesterification, lubricating properties

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Authors: Smita Krishnan, Krittika Chandran, Chandra Mohan Sinnathambi

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Produced water and its treatment and management are growing challenges in all producing regions. This water is generally considered as a nonrevenue product, but it can have significant value in enhanced oil recovery techniques if it meets the required quality standards. There is also an interest in the beneficial uses of produced water for agricultural and industrial applications. Advanced Oxidation Process is a chemical technology that has been growing recently in the wastewater treatment industry, and it is highly recommended for non-easily removal of organic compounds. The efficiency of AOPs is compound specific, therefore, the optimization of each process should be done based on different aspects.

Keywords: advanced oxidation process, photochemical processes, degradation, organic contaminants

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Authors: Jin Lin, Shouxiang Lu, Kim Meow Liew

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In a fire accident, fire smoke often poses a serious threat to human safety especially in the enclosed space such as submarine and space-crafts environment. Efficient removal of the hazardous gas products particularly a large amount of CO and CO₂ gases from these confined space is critical for the security of the staff and necessary for the post-fire environment recovery. In this work, Cu-Mn-Ce composite oxide catalysts coupled with CO₂ sorbents were prepared using wet impregnation method, solid-state impregnation method and wet/solid-state impregnation method. The as-prepared samples were tested dynamically and isothermally for CO oxidation and CO₂ sorption and further characterized by the X-ray diffraction (XRD), nitrogen adsorption and desorption, and field emission scanning electron microscopy (FE-SEM). The results showed that all the samples were able to catalyze CO into CO₂ and capture CO₂ in situ by chemisorption. Among all the samples, the sample synthesized by the wet/solid-state impregnation method showed the highest catalytic activity toward CO oxidation and the fine ability of CO₂ sorption. The sample prepared by the solid-state impregnation method showed the second CO oxidation performance, while the coupled sample using the wet impregnation method exhibited much poor CO oxidation activity. The various CO oxidation and CO₂ sorption properties of the samples might arise from the different dispersed states of the CO₂ sorbent in the CO catalyst, owing to the different preparation methods. XRD results confirmed the high-dispersed sorbent phase in the samples prepared by the wet and solid impregnation method, while that of the sample prepared by wet/solid-state impregnation method showed the larger bulk phase as indicated by the high-intensity diffraction peaks. Nitrogen adsorption and desorption results further revealed that the latter sample had a higher surface area and pore volume, which were beneficial for the CO oxidation over the catalyst. Hence, the Cu-Mn-Ce oxide catalyst coupled with CO₂ sorbent using wet/solid-state impregnation method could be a good choice for fire smoke removal in the enclosed space.

Keywords: CO oxidation, CO₂ sorption, preparation methods, smoke removal

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Authors: Yalçın Kılıç, İbrahim Kani

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In recent years, interest in the synthesis of coordination compounds has greatly increased due to various application areas (such as catalysis, gas storage, luminescence). Dicarboxylic acids are often used in the synthesis of metal complexes. Bis-thiosalicylate derivative ligands contribute to the synthesis of structures of crystal engineering interest, as they can have both rigid and flexible properties. In addition, these ligands have great potential in terms of catalytic applications with the sulfur and oxygen donor atoms in their structures. In this study, we synthesized a Cu(II) complex [Cu(tsaxyl)(phen)2]•CH3OH (where tsaxyl = 2,2'-(1,2-phylenebis(methylene))bis(sulfanedyl)dibenzoate, phen = 1,10-phenantroline) and characterized through X-ray crystallography. The catalytic activities of Cu(II) complex on oxidation of ethylbenzene, cyclohexane, diphenylmethane, p-xylene were performed in acetonitrile with t-BuOOH as the source of oxygen.

Keywords: complex, crystallography, catalysis, oxidation

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Authors: Mannar R. Maurya, Bithika Sarkar, Fernando Avecilla

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Peroxidase activity is possibly successfully used for different industrial processes in medicine, chemical industry, food processing and agriculture. However, they bear some intrinsic drawback associated with denaturation by proteases, their special storage requisite and cost factor also. Now a day’s artificial enzyme mimics are becoming a research interest because of their significant applications over conventional organic enzymes for ease of their preparation, low price and good stability in activity and overcome the drawbacks of natural enzymes e.g serine proteases. At present, a large number of artificial enzymes have been synthesized by assimilating a catalytic center into a variety of schiff base complexes, ligand-anchoring, supramolecular complexes, hematin, porphyrin, nanoparticles to mimic natural enzymes. Although in recent years a several number of vanadium complexes have been reported by a continuing increase in interest in bioinorganic chemistry. To our best of knowledge, the investigation of artificial enzyme mimics of vanadium complexes is very less explored. Recently, our group has reported synthetic vanadium schiff base complexes capable of mimicking peroxidases. Herein, we have synthesized monoidovanadium(IV) and dioxidovanadium(V) complexes of pyrazoleone derivateis ( extensively studied on account of their broad range of pharmacological appication). All these complexes are characterized by various spectroscopic techniques like FT-IR, UV-Visible, NMR (1H, 13C and 51V), Elemental analysis, thermal studies and single crystal analysis. The peroxidase mimic activity has been studied towards oxidation of pyrogallol to purpurogallin with hydrogen peroxide at pH 7 followed by measuring kinetic parameters. The Michaelis-Menten behavior shows an excellent catalytic activity over its natural counterparts, e.g. V-HPO and HRP. The obtained kinetic parameters (Vmax, Kcat) were also compared with peroxidase and haloperoxidase enzymes making it a promising mimic of peroxidase catalyst. Also, the catalytic activity has been studied towards the oxidation of 1-phenylethanol in presence of H2O2 as an oxidant. Various parameters such as amount of catalyst and oxidant, reaction time, reaction temperature and solvent have been taken into consideration to get maximum oxidative products of 1-phenylethanol.

Keywords: oxovanadium(IV)/dioxidovanadium(V) complexes, NMR spectroscopy, Crystal structure, peroxidase mimic activity towards oxidation of pyrogallol, Oxidation of 1-phenylethanol

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Authors: Karla Lienau, Rafael Müller, René Moré, Debora Ressnig, Dan Cook, Richard Walton, Greta R. Patzke

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The increasing demand for renewable energy sources and storable fuels underscores the high potential of artificial photosynthesis. The four electron transfer process of water oxidation remains the bottleneck of water splitting, so that special emphasis is placed on the development of economic, stable and efficient water oxidation catalysts (WOCs). Our investigations introduced cobalt carbodiimide CoNCN and its transition metal analogues as WOC types, and further studies are focused on the interaction of different transition metals in the convenient all-nitrogen/carbon matrix. This provides further insights into the nature of the ‘true catalyst’ for cobalt centers in this non-oxide environment. Water oxidation activity is evaluated with complementary methods, namely photocatalytically using a Ru-dye sensitized standard setup as well as electrocatalytically, via immobilization of the WOCs on glassy carbon electrodes. To further explore the tuning potential of transition metal combinations, complementary investigations were carried out in oxidic spinel WOC matrices with more versatile host options than the carbodiimide framework. The influence of the preparative history on the WOC performance was evaluated with different synthetic methods (e.g. hydrothermally or microwave assisted). Moreover, the growth mechanism of nanoscale Co3O4-spinel as a benchmark WOC was investigated with in-situ PXRD techniques.

Keywords: carbodiimide, photocatalysis, spinels, water oxidation

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Authors: Jiazhen Liao, Xiaolan Zeng

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A series of BiOCl nanoplates with different oxygen vacancies (OVs) concentrations were successfully synthesized via a facile solvothermal method. The concentration of OVs of BiOCl can be tuned by the ratios of water/ethylene glycol. Such nanoplates containing oxygen vacancies served as an efficient visible-light-driven photocatalyst for NO oxidation. Compared with pure BiOCl, the enhanced photocatalytic performance was mainly attributed to the introduction of OVs, which greatly enhanced light absorption, promoted electron transfer, activated oxygen molecules. The present work could provide insights into the understanding of the role of OVs in photocatalysts for reference. Combined with characterization analysis, such as XRD（X-ray diffraction）, XPS（X-ray photoelectron spectroscopy), TEM（Transmission Electron Microscopy）, PL（Fluorescence Spectroscopy）, and DFT (Density Functional Theory) calculations, the effect of vacancies on photoelectrochemical properties of BiOCl photocatalysts are shown. Furthermore, the possible reaction mechanisms of photocatalytic NO oxidation were also revealed. According to the results of in situ DRIFTS （ Diffused Reflectance Infrared Fourier Transform Spectroscopy）, various intermediates were produced during different time intervals of NO photodegradation. The possible pathways are summarized below. First, visible light irradiation induces electron-hole pairs on the surface of OV-BOC (BiOCl with oxygen vacancies). Second, photogenerated electrons form superoxide radical with the contacted oxygen. Then, the NO molecules adsorbed on the surface of OV-BOC are attacked by superoxide radical and form nitrate instead of NO₂ (by-products). Oxygen vacancies greatly improve the photocatalytic oxidation activity of NO and effectively inhibit the production of harmful by-products during the oxidation of NO.

Keywords: OVs-BiOCl nanoplate, oxygen vacancies, NO oxidation, photocatalysis

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Authors: Elitsa Kolentsova, Dimitar Dimitrov, Krasimir Ivanov

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The catalytic oxidation of methanol to formaldehyde is an important industrial process in which the waste gas in addition to CO contains methanol and dimethyl ether (DME). Evaluation of the possibility of removing the harmful components from the exhaust gasses needs a more complex investigation. Our previous work indicates that supported Cu-Mn oxide catalysts are promising for effective deep oxidation of these compounds. This work relates to the catalyst, comprising copper-manganese spinel, coated on carrier γ-Al₂O₃. The effect of preparation conditions on the active component composition and activity behavior of the catalysts is discussed. Different organometallic compounds on the base of four natural amino acids (Glycine, Alanine, Valine, Leucine) as precursors were used for the preparation of catalysts with Cu/Mn molar ratio 1:5. X-Ray and TEM analysis were performed on the catalyst’s bulk, and surface composition and the specific surface area was determined by BET method. The results obtained show that the activity of the catalysts increase up to 40% although there are some specific features, depending on the nature of the amino acid and the oxidized compound.

Keywords: Cu-Mn/γ-Al₂O₃, CO and VOCs oxidation, heterogeneous catalysis, amino acids

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Authors: Jae-Ho Kim, Ryosuke Yokochi, Miho Fuzihashi, Susumu Yonezawa

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The use of silver nanoparticles in conductive inks and their printing by injecting technology has been known for years. However, the very high cost of silver limits wide industrial applications. Since copper is much cheaper but possesses a very high conductivity (only 6% less than that of Ag), Cu nanoparticles can be considered as a replacement for silver nanoparticles. However, a major problem in utilizing their copper nanoparticles is their inherent tendency to oxidize in ambient conditions. In conductive printing applications, the presence of copper oxide on the surface of nanoparticles has two negative consequences: it increases the required sintering temperature and reduces the electrical conductivity. Only a limited number of reports have attempted to address the oxidation problem, which in general is based on minimizing the exposure of the copper nanoparticles to oxygen by a protective layer composed of a second material at the surface of the particles. To form the protective layer on the surface, carbon-based materials, surfactants, metals, and so on. In this study, we tried to modify the oxide on Cu particles using fluorine gas. And the creation effects of oxyfluorides or fluorides on the oxidation resistance of Cu particles were investigated. Compared with untreated sample (a), the fluorinated samples can restrain the weight increase even at 200℃ from the TG-DTA results. It might be considered that the substantial oxyfluorides on the surface play a role in protecting metal oxidation.

Keywords: copper metal, electrical conductivity, oxidation resistance, surface fluorination

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Authors: Erica T. R. Mendonça, Caroline M. B. de Araujo, Filho, Osvaldo Chiavone, Sobrinho, Maurício A. da Motta

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Oil and gas exploration is an essential activity for modern society, although the supply of its global demand has caused enough damage to the environment, mainly due to produced water generation, which is an effluent associated with the oil and gas produced during oil extraction. It is the aim of this study to evaluate the treatment of produced water, in order to reduce its oils and greases content (OG), by using flotation as a pre-treatment, combined with oxidation for the remaining organic load degradation. Thus, there has been tested Advanced Oxidation Process (AOP) using both Fenton and photo-Fenton reactions, as well as a chemical oxidation treatment using sodium ferrate(VI), Na₂[FeO₄], as a strong oxidant. All the studies were carried out using real samples of produced water from petroleum industry. The oxidation process using ferrate(VI) ion was studied based on factorial experimental designs. The factorial design was used in order to study how the variables pH, temperature and concentration of Na₂[FeO₄] influences the O&G levels. For the treatment using ferrate(VI) ion, the results showed that the best operating point is obtained when the temperature is 28 °C, pH 3, and a 2000 mg.L^-1 solution of Na₂[FeO₄] is used. This experiment has achieved a final O&G level of 4.7 mg.L^-1, which means 94% percentage removal efficiency of oils and greases. Comparing Fenton and photo-Fenton processes, it was observed that the Fenton reaction did not provide good reduction of O&G (around 20% only). On the other hand, a degradation of approximately 80.5% of oil and grease was obtained after a period of seven hours of treatment using photo-Fenton process, which indicates that the best process combination has occurred between the flotation and the photo-Fenton reaction using solar radiation, with an overall removal efficiency of O&G of approximately 89%.

Keywords: advanced oxidation process, ferrate (VI) ion, oils and greases removal, produced water treatment

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Authors: Abolfazl Kamkar

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Vegetable oils and fats are recognized as important components of our diet. They provide essential fatty acids, which are precursors of important hormones and control many physiological factors such as blood pressure, cholesterol level, and the reproductive system.Vegetable oils with higher contents of unsaturated fatty acids, especially polyunsaturated fatty acids (PUFAs) are more susceptible to oxidation.Protective effects of Sature jahortensis(SE) extracts in stabilizing soybean oil at different concentrations (200 and 400 ppm) were tested. Results showed that plant extracts could significantly (P< 0.05) lower the peroxide value and thiobarbituric acid value of oil during storage at 60 oC. The IC50 values for methanol and ethanol extracts were 31.5 ± 0.7 and 37.00 ± 0 µg/ml, respectively. In the β- carotene/linoleic acid system, methanol and ethanol extracts exhibited 87.5 ± 1.41% and 74.0 ±2.25 % inhibition against linoleic acid oxidation. The total phenolic and flavonoid contents of methanol and ethanol extracts were (101.58 ± 0. 26m g/ g) and (96.00 ± 0.027 mg/ g), (44.91 ± 0.14 m g/ g) and (14.30 ± 0.12 mg/ g) expressed in Gallic acid and Quercetin equivalents, respectively.These findings suggest that Satureja extracts may have potential application as natural antioxidants in the edible oil and food industry.

Keywords: satureja hortensis, antioxidant activity, oxidative stability, vegetable oil, extract

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Authors: Elitsa N. Kolentsova, Dimitar Y. Dimitrov, Petya Cv. Petrova, Georgi V. Avdeev, Diana D. Nihtianova, Krasimir I. Ivanov, Tatyana T. Tabakova

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Recently, copper and manganese-containing systems are recognized as active and selective catalysts in many oxidation reactions. The main idea of this study is to obtain more information about γ-Al₂O₃ supported Cu-La catalysts and to evaluate their activity to simultaneous oxidation of CO, CH₃OH and dimethyl ether (DME). The catalysts were synthesized by impregnation of support with a mixed aqueous solution of nitrates of copper, manganese and lanthanum under different conditions. XRD, HRTEM/EDS, TPR and thermal analysis were performed to investigate catalysts’ bulk and surface properties. The texture characteristics were determined by Quantachrome Instruments NOVA 1200e specific surface area and pore analyzer. The catalytic measurements of single compounds oxidation were carried out on continuous flow equipment with a four-channel isothermal stainless steel reactor in a wide temperature range. On the basis of XRD analysis and HRTEM/EDS, it was concluded that the active component of the mixed Cu-Mn-La/γ–alumina catalysts strongly depends on the Cu/Mn molar ratio and consisted of at least four compounds – CuO, La₂O₃, MnO₂ and Cu_1.5Mn_1.5O₄. A homogeneous distribution of the active component on the carrier surface was found. The chemical composition strongly influenced catalytic properties. This influence was quite variable with regards to the different processes.

Keywords: Cu-Mn-La oxide catalysts, carbon oxide, VOCs, deep oxidation

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Authors: Amin Mojiri, Akiyoshi Ohashi, Tomonori Kindaichi

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Synthetic domestic wastewater was treated via combining treatment methods, including electrochemical oxidation, adsorption, and sequencing batch reactor (SBR). In the upper part of the reactor, an anode and a cathode (Ti/RuO₂-IrO₂) were organized in parallel for the electrochemical oxidation procedure. Sodium sulfate (Na₂SO₄) with a concentration of 2.5 g/L was applied as the electrolyte. The voltage and current were fixed on 7.50 V and 0.40 A, respectively. Then, 15% working value of the reactor was filled by activated sludge, and 85% working value of the reactor was added with synthetic wastewater. Powdered cockleshell, 1.5 g/L, was added in the reactor to do ion-exchange. Response surface methodology was employed for statistical analysis. Reaction time (h) and pH were considered as independent factors. A total of 97.0% biochemical oxygen demand, 99.9% phosphorous and 88.6% cadmium were eliminated at the optimum reaction time (80.0 min) and pH (6.4).

Keywords: adsorption, electrochemical oxidation, metals, SBR

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Authors: Valentina Paolucci, Jessica De Santis, Vittorio Ricci, Giacomo Giorgi, Carlo Cantalini

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Despite their potential in gas sensing applications, the major drawback of 2D exfoliated metal dichalcogenides (MDs) is that they suffer from spontaneous oxidation in air, showing poor chemical stability under dry/wet conditions even at room temperature, limiting their practical exploitation. The aim of this work is to validate a synthesis strategy allowing microstructural and electrical stabilization of the oxides that inevitably form on the surface of 2D dichalcogenides. Taking advantage of spontaneous oxidation of MDs in air, we report on liquid phase exfoliated 2D-SnSe2 flakes annealed in static air at a temperature below the crystallization temperature of the native a-SnO2 oxide. This process yields a new class of 2D Layered Amorphous Metal Oxides Sensors (LAMOS), specifically few-layered amorphous a-SnO2, showing excellent gas sensing properties. Sensing tests were carried out at low operating temperature (i.e. 100°C) by exposing a-SnO2 to both oxidizing and reducing gases (i.e. NO2, H2S and H2) and different relative humidities ranging from 40% to 80% RH. The formation of stable nanosheets of amorphous a-SnO2 guarantees excellent reproducibility and stability of the response over one year. These results pave the way to new interesting research perspectives out considering the opportunity to synthesize homogeneous amorphous textures with no grain boundaries, no grains, no crystalline planes with different orientations, etc., following gas sensing mechanisms that likely differ from that of traditional crystalline metal oxide sensors. Moreover, the controlled annealing process could likely be extended to a large variety of Transition Metal Dichalcogenides (TMDs) and Metal Chalcogenides (MCs), where sulfur, selenium, or tellurium atoms can be easily displaced by O2 atoms (ΔG < 0), enabling the synthesis of a new family of amorphous interfaces.

Keywords: layered 2D materials, exfoliation, lamos, amorphous metal oxide sensors

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Authors: Vishnu V. Pillai, Sunil P. Lonkar, Akhil M. Abraham, Saeed M. Alhassan

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An effectual technology for wastewater treatment is a great demand now in order to encounter the water pollution caused by organic pollutants. Photocatalytic oxidation technology is widely used in removal of such unsafe contaminants. Among the semi-conducting metal oxides, robust and thermally stable TiO2 has emerged as a fascinating material for photocatalysis. Enhanced catalytic activity was observed for nanostructured TiO2 due to its higher surface, chemical stability and higher oxidation ability. However, higher charge carrier recombination and wide band gap of TiO2 limits its use as a photocatalyst in the UV region. It is desirable to develop a photocatalyst that can efficiently absorb the visible light, which occupies the main part of the solar spectrum. Hence, in order to extend its photocatalytic efficiency under visible light, TiO2 nanoparticles are often doped with metallic or non-metallic elements. Non-metallic doping of TiO2 has attracted much attention due to the low thermal stability and enhanced recombination of charge carriers endowed by metallic doping of TiO2. Amongst, sulfur doped TiO2 is most widely used photocatalyst in environmental purification. However, the most of S-TiO2 synthesis technique uses toxic chemicals and complex procedures. Hence, a facile, scalable and environmentally benign preparation process for S-TiO2 is highly desirable. In present work, we have demonstrated new and facile solid-state reaction method for S-TiO2 synthesis that uses abundant elemental sulfur as S source and moderate temperatures. The resulting nano-sized S-TiO2 has been successfully employed as visible light photocatalyst in methylene blue dye removal from aqueous media.

Keywords: ecofriendly, nanomaterials, methylene blue, photocatalysts

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Authors: Yaling Gou, Sucai Yang, Pengwei Qiao

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Integrated chemical-biological treatment is an attractive alternative to remove polycyclic aromatic hydrocarbons (PAHs) from contaminated soil; wherein indigenous bacteria is the key factor for the biodegradation of residual PAHs concentrations after the application of chemical oxidation. However, the systematical study on the impact of persulfate (PS) oxidation on indigenous bacteria as well as PAHs removal is still scarce. In this study, the influences of different PS dosages (1%, 3%, 6%, and 10% [w/w]), as well as various activation methods (native iron, H2O2, alkaline, ferrous iron, and heat) on PAHs removal and indigenous bacteria in highly contaminated aged soil were investigated. Apparent degradation of PAHs in the soil treated with PS oxidation was observed, and the removal efficiency of total PAHs in the soil ranged from 38.28% to 79.97%. The removal efficiency of total PAHs in the soil increased with increasing consumption of PS. However, the bacterial abundance in soil was negatively affected following oxidation for all of the treatments added with PS, with bacterial abundance in the soil decreased by 0.89~2.88 orders of magnitude compared to the untreated soil. Moreover, the number of total bacteria in the soil decreased as PS consumption increased. Different PS activation methods and PS dosages exhibited different influences on the bacterial community composition. Bacteria capable of degrading PAHs under anoxic conditions were composed predominantly by Proteobacteria and Firmicutes. The total amount of Proteobacteria and Firmicutes also decreased with increasing consumption of PS. The results of this study provide important insight into the design of PAHs contaminated soil remediation projects.

Keywords: activation method, chemical oxidation, indigenous bacteria, polycyclic aromatic hydrocarbon

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Authors: Saba Didarataee, Abbas Ali Khodadadi, Yadollah Mortazavi, Fatemeh Mousavi

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Photocatalytic water splitting is one of the most attractive alternative methods for hydrogen evolution. A variety of nanoparticle engineering techniques were introduced to improve the activity of semiconductor photocatalysts. Among these methods, heterojunction formation is an appealing method due to its ability to effectively preventing electron-hole recombination and improving photocatalytic activity. Reaching an optimal ratio of the two target semiconductors for the formation of heterojunctions is still an open question. Considering environmental issues as well as the cost and availability, ZnS and ZnO are frequently studied as potential choices. In this study, first, the ZnS nanoparticle was synthesized in a hydrothermal process; the formation of ZnS nanorods with a diameter of 14-30 nm was confirmed by field emission scanning electron microscope (FESEM). Then two different methods, partial oxidation and chemical precipitation were employed to construct ZnS/ZnO core-shell heterojunction. X-ray diffraction (XRD), BET, and diffuse reflectance spectroscopy (DRS) analysis were carried out to determine crystallite phase, surface area, and bandgap of photocatalysts. Furthermore, the temperature of oxidation was specified by a temperature programmed oxidation (TPO) and was fixed at 510℃, at which mild oxidation occurred. The bandgap was calculated by the Kubelka-Munk method and decreased by increasing oxide content from 3.53 (pure ZnS) to 3.18 (pure ZnO). The optimal samples were determined by testing the photocatalytic activity of hydrogen evolution in a quartz photoreactor with side irradiation of UVC lamps with a wavelength of 254 nm. In both procedures, it was observed that the photocatalytic activity of the ZnS/ZnO composite was sensibly higher than the pure ZnS and ZnO, which is attributed to forming a type-II heterostructure. The best ratio of oxide to sulfide was 0.24 and 0.37 in partial oxidation and chemical precipitation, respectively. The highest hydrogen evolution was 1081 µmol/gr.h, gained from partial oxidizing of ZnS nanoparticles at 510℃ for 30 minutes.

Keywords: heterostructure, hydrogen, partial oxidation, photocatalyst, water splitting, ZnS

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Authors: Tatyana T. Tabakova, Elitsa N. Kolentsova, Dimitar Y. Dimitrov, Krasimir I. Ivanov, Yordanka G. Karakirova, Petya Cv. Petrova, Georgi V. Avdeev

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The catalytic oxidation of CO and volatile organic compounds (VOCs) is considered as one of the most efficient ways to reduce harmful emissions from various chemical industries. The effectiveness of gold-based catalysts for many reactions of environmental significance was proven during the past three decades. The aim of this work was to combine the favorable features of Au and Cu-Ce mixed oxides in the design of new catalytic materials of improved efficiency and economic viability for removal of air pollutants in waste gases from formaldehyde production. Supported oxides of copper and cerium with Cu: Ce molar ratio 2:1 and 1:5 were prepared by wet impregnation of g-alumina. Gold (2 wt.%) catalysts were synthesized by a deposition-precipitation method. Catalysts characterization was carried out by texture measurements, powder X-ray diffraction, temperature programmed reduction and electron paramagnetic resonance spectroscopy. The catalytic activity in the oxidation of CO, CH₃OH and (CH₃)₂O was measured using continuous flow equipment with fixed bed reactor. Both Cu-Ce/alumina samples demonstrated similar catalytic behavior. The addition of gold caused significant enhancement of CO and methanol oxidation activity (100 % degree of CO and CH₃OH conversion at about 60 and 140 ^oC, respectively). The composition of Cu-Ce mixed oxides affected the performance of gold-based samples considerably. Gold catalyst on Cu-Ce/γ-Al₂O₃ 1:5 exhibited higher activity for CO and CH₃OH oxidation in comparison with Au on Cu-Ce/γ-Al₂O₃ 2:1. The better performance of Au/Cu-Ce 1:5 was related to the availability of highly dispersed gold particles and copper oxide clusters in close contact with ceria.

Keywords: CO and VOCs oxidation, copper oxide, Ceria, gold catalysts

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Authors: Tareg Omar Mansour, Khaled Omar Elhaji

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Model solutions of pentanol in the salt water of various concentrations were subjected to electrochemical oxidation using a dimensionally stable anode (DSA) and a platinised titanium cathode. The removal of pentanol was analysed over time using gas chromatography (GC) and by monitoring the total organic carbon (TOC) concentration of the reaction mixture. It was found that the removal of pentanol occurred more efficiently at higher salinities and higher applied electrical current values. When using a salt concentration of 20,000 ppm and an applied current of 100 mA there was a decrease in concentration of pentanol of 15 %. When the salt concentration and applied current were increased to 58,000 ppm and 500 mA respectively, the decrease in concentration was improved to 64 %.

Keywords: dimensionally stable anode (DSA), total organic hydrocarbon (TOC), gas chromatography mass spectrometry (GCMS), electrochemical oxidation

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Authors: Cahit Demetgul, Sahin Bayraktar, Neslihan Beyazit

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Metalloenzymes are enzyme proteins containing metal ions, which are directly bound to the protein or to enzyme-bound nonprotein components. One of the major metalloenzymes that play a key role in oxidation reactions is catechol oxidase, which shows catecholase activity i.e. oxidation of a broad range of catechols to quinones through the four-electron reduction of molecular oxygen to water. Studies on the model compounds mimicking the catecholase activity are very useful and promising for the development of new, more efficient bioinspired catalysts, for in vitro oxidation reactions. In this study, a new tetradentate asymmetrical Schiff-base and its Cu(II) complex were synthesized by condensation of 4-nitro-1,2-phenylenediamine with 6-formyl-7-hydroxy-5-methoxy-2-methylbenzopyran-4-one and by using an appropriate Cu(II) salt, respectively. The prepared compounds were characterized by elemental analysis, FT-IR, NMR, UV-Vis and magnetic susceptibility. The catecholase-mimicking activity of the new Schiff Base Cu(II) complex was performed for the oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) in methanol at 25 °C, where the electronic spectra were recorded at different time intervals. The yield of the quinone (3,5-DTBQ) was determined from the measured absorbance at 400 nm of the resulting solution. The compatibility of catalytic reaction with Michaelis-Menten kinetics was also investigated. In conclusion, we have found that our new Schiff Base Cu(II) complex presents a significant capacity to catalyze the oxidation reaction of the catechol to o-quinone.

Keywords: catecholase activity, Michaelis-Menten kinetics, Schiff base, transition metals

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Authors: L. Le Priol, A. Nesterenko, K. El Kirat, K. Saleh

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Introduction and objectives: Polyunsaturated fatty acids (PUFAs) omega-3 and omega-6 are widely recognized as being beneficial to the health and normal growth. Unfortunately, due to their highly unsaturated nature, these molecules are sensitive to oxidation and thermic degradation leading to the production of toxic compounds and unpleasant flavors and smells. Hence, it is necessary to find out a suitable way to protect them. Microencapsulation by spray-drying is a low-cost encapsulation technology and most commonly used in the food industry. Many compounds can be used as wall materials, but there is a growing interest in the use of biopolymers, such as proteins and polysaccharides, over the last years. The objective of this study is to increase the oxidative stability of sunflower oil by microencapsulation in plant protein matrices using spray-drying technique. Material and methods: Sunflower oil was used as a model substance for oxidable food oils. Proteins from brown rice, hemp, pea, soy and sunflower seeds were used as emulsifiers and microencapsulation wall materials. First, the proteins were solubilized in distilled water. Then, the emulsions were pre-homogenized using a high-speed homogenizer (Ultra-Turrax) and stabilized by using a high-pressure homogenizer (HHP). Drying of the emulsion was performed in a Mini Spray Dryer. The oxidative stability of the encapsulated oil was determined by performing accelerated oxidation tests with a Rancimat. The size of the microparticles was measured using a laser diffraction analyzer. The morphology of the spray-dried microparticles was acquired using environmental scanning microscopy. Results: Pure sunflower oil was used as a reference material. Its induction time was 9.5 ± 0.1 h. The microencapsulation of sunflower oil in pea and soy protein matrices significantly improved its oxidative stability with induction times of 21.3 ± 0.4 h and 12.5 ± 0.4 h respectively. The encapsulation with hemp proteins did not significantly change the oxidative stability of the encapsulated oil. Sunflower and brown rice proteins were ineffective materials for this application, with induction times of 7.2 ± 0.2 h and 7.0 ± 0.1 h respectively. The volume mean diameter of the microparticles formulated with soy and pea proteins were 8.9 ± 0.1 µm and 16.3 ± 1.2 µm respectively. The values for hemp, sunflower and brown rice proteins could not be obtained due to the agglomeration of the microparticles. ESEM images showed smooth and round microparticles with soy and pea proteins. The surfaces of the microparticles obtained with sunflower and hemp proteins were porous. The surface was rough when brown rice proteins were used as the encapsulating agent. Conclusion: Soy and pea proteins appeared to be efficient wall materials for the microencapsulation of sunflower oil by spray drying. These results were partly explained by the higher solubility of soy and pea proteins in water compared to hemp, sunflower, and brown rice proteins. Acknowledgment: This work has been performed, in partnership with the SAS PIVERT, within the frame of the French Institute for the Energy Transition (Institut pour la Transition Energétique (ITE)) P.I.V.E.R.T. (www.institut-pivert.com) selected as an Investments for the Future (Investissements d’Avenir). This work was supported, as part of the Investments for the Future, by the French Government under the reference ANR-001-01.

Keywords: biopolymer, edible oil, microencapsulation, oxidative stability, release, spray-drying

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Authors: Mairaj Ahmad, L. Paglia, F. Marra, V. Genova, G. Pulci

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This study employed Rene N4 and FSX 414 superalloys, which are used in numerous turbine engine components due of their high strength, outstanding fatigue, creep, thermal, and corrosion-resistant properties. An in-depth examination of corrosion mechanisms with vapor present at high temperature is necessary given the industrial trend toward introducing increasing amounts of hydrogen into combustion chambers in order to boost power generation and minimize pollution in contrast to conventional fuels. These superalloys were oxidized in recent tests for 500, 1000, 2000, 3000 and 4000 hours at 982±5°C temperatures with a steady airflow at a flow rate of 10L/min and 1.5 bar pressure. These superalloys were also examined for wet corrosion for 500, 1000, 2000, 3000, and 4000 hours in a combination of air and water vapor flowing at a 10L/min rate. Weight gain, X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive x-ray spectroscopy (EDS) were used to assess the oxidation and heat corrosion resistance capabilities of these alloys before and after 500, 1000, and 2000 hours. The oxidation/corrosion processes that accompany the formation of these oxide scales are shown in the graph of mass gain vs time. In both dry and wet oxidation, oxides like Al2O3, TiO2, NiCo2O4, Ni3Al, Ni3Ti, Cr2O3, MnCr2O4, CoCr2O4, and certain volatile compounds notably CrO2(OH)2, Cr(OH)3, Fe(OH)2, and Si(OH)4 are formed.

Keywords: hot corrosion, oxidation, turbine materials, high temperature corrosion, super alloys

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Authors: Wei-Chou Hsu, Ching-Sung Lee, Han-Yin Liu

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This work uses H2O2 oxidation technique to improve the pH sensitivity of the AlGaN/GaN-based ion-sensitive field-effect transistors (ISFETs). 10-nm-thick Al2O3 was grown on the surface of the AlGaN. It was found that the pH sensitivity was improved from 41.6 mV/pH to 55.2 mV/pH. Since the H2O2-grown Al2O3 was served as a passivation layer and the problem of Fermi-level pinning was suppressed for the ISFET with the H2O2 oxidation process. Hysteresis effect in the ISFET with the H2O2 treatment also became insignificant. The hysteresis effect was observed by dipping the ISFETs into different pH value solutions and comparing the voltage difference between the initial and final conditions. The hysteresis voltage (Vhys) of the ISFET with the H2O2 oxidation process was improved from 8.7 mV to 4.8 mV. The hysteresis effect is related to the buried binding sites which are related to the material defects like threading dislocations in the AlGaN/GaN heterostructure which was grown by the hetero-epitaxy technique. The H2O2-grown Al2O3 passivate these material defects and the Al2O3 has less material defects. The long-term stability of the ISFET is estimated by the drift effect measurement. The drift measurement was conducted by dipping the ISFETs into a specific pH value solution for 12 hours and the ISFETs were operating at a specific quiescent point. The drift rate is estimated by the drift voltage divided by the total measuring time. It was found that the drift rate of the ISFET was improved from 10.1 mV/hour to 1.91 mV/hour in the pH 7 solution, from 14.06 mV/hour to 6.38 mV/pH in the pH 2 solution, and from 12.8 mV/hour to 5.48 mV/hour in the pH 12 solution. The drift effect results from the capacitance variation in the electric double layer. The H2O2-grown Al2O3 provides an additional capacitance connection in series with the electric double layer. Therefore, the capacitance variation of the electric double layer became insignificant. Generally, the H2O2 oxidation process is a simple, fast, and cost-effective method for the AlGaN/GaN-based ISFET. Furthermore, the performance of the AlGaN/GaN ISFET was improved effectively and the non-ideal effects were suppressed.

Keywords: AlGaN/GaN, Al2O3, hysteresis effect, drift effect, reliability, passivation, pH sensors

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Authors: Loai Ben Naji, Osama M. Ibrahim, Khaled J. Al-Fadhalah

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The objective of this paper is to investigate the formation and adhesion of a protective aluminum-oxide (Al₂O₃, alumina) layer on the surface of Iron-Chromium-Aluminum Alloy (Fe-Cr-Al) sintered-metal-fibers. The oxide-scale layer was developed via multi-stage thermal oxidation at 930 ^oC for 1 hour, followed by 1 hour at 960 ^oC, and finally at 990 ^oC for 2 hours. Scanning Electron Microscope (SEM) images show that the multi-stage thermal oxidation resulted in the formation of predominantly Al₂O₃ platelets-like and whiskers. SEM images also reveal non-uniform oxide-scale growth on the surface of the fibers. Furthermore, peeling/spalling of the alumina protective layer occurred after minimum handling, which indicates weak adhesion forces between the protective layer and the base metal alloy.  Energy Dispersive Spectroscopy (EDS) analysis of the heat-treated Fe-Cr-Al sintered-metal-fibers confirmed the high aluminum content on the surface of the protective layer, and the low aluminum content on the exposed base metal alloy surface. In conclusion, the failure of the oxide-scale protective layer exposes the base metal alloy to further oxidation, and the fragile non-uniform oxide-scale is not suitable as a support for catalysts.

Keywords: high-temperature oxidation, iron-chromium-aluminum alloy, alumina protective layer, sintered-metal-fibers

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Authors: A. Kabir, D. Boulainine, I. Bouanane, N. Benslim, B. Boudjema, C. Sedrati

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SnO₂ is an n-type semiconductor with a direct gap of about 3.6 eV. It is largely used in several domains such as nanocrystalline photovoltaic cells. Due to its interesting physic-chemical properties, this material was elaborated in thin film forms using different deposition techniques. It was found that SnO₂ properties were directly affected by the deposition method parameters. In this work, the RGTO method (Rheotaxial Growth and Thermal Oxidation) was used to deposit elaborate SnO₂ thin films. This technique consists on thermal oxidation of the Sn films deposited onto a substrate heated to a temperature close to Sn melting point (232°C). Such process allows the preparation of high porosity tin oxide films which are very suitable for the gas sensing. The films structural, morphological and optical properties pre and post thermal oxidation were studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), UV-Visible spectroscopy and Fourier transform infrared spectroscopy (FTIR) respectively. XRD patterns showed a polycrystalline structure of the cassiterite phase of SnO₂. The grain growth was found affected by the oxidation temperature. This grain size evolution was confronted to existing grain growth models in order to understand the growth mechanism. From SEM images, the as deposited Sn film was formed of difference diameter spherical agglomerations. As a function of the oxidation temperature, these spherical agglomerations shape changed due to the introduction of oxygen ions. The deformed spheres started to interconnect by forming bridges between them. The volume porosity, determined from the UV-Visible reflexion spectra, Changes as a function of the oxidation temperature. The variation of the crystalline fraction, determined from FTIR spectra, correlated with the variation of both the grain size and the volume porosity.

Keywords: tin oxide, RGTO, grain growth, volume porosity, crystalline fraction

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Authors: Arcady Ponosov., Ramazan Kadiev

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The work studies the global moment stability of solutions of systems of nonlinear differential Itô equations with delays. A modified regularization method (W-method) for the analysis of various types of stability of such systems, based on the choice of the auxiliaryequations and applications of the theory of positive invertible matrices, is proposed and justified. Development of this method for deterministic functional differential equations is due to N.V. Azbelev and his students. Sufficient conditions for the moment stability of solutions in terms of the coefficients for sufficiently general as well as specific classes of Itô equations are given.

Keywords: asymptotic stability, delay equations, operator methods, stochastic noise

Procedia PDF Downloads 225