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  • oxidation
  • Springer  (604)
  • National Academy of Sciences
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of applied electrochemistry 30 (2000), S. 727-731 
    ISSN: 1572-8838
    Keywords: electrosynthesis ; oxidation ; lignin ; vanillin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Electrochemical oxidative degradation of Kraft lignin was investigated in batch and flow cells on Pt, Au, Ni, Cu, DSA–O2 and PbO2 anodes. Production of vanillin was evaluated by means of formal kinetic analyses. Conversion and chemical yields were found to be dependent mainly on the applied current density, that is on the partial pressure of oxygen at the interface, while the nature of the electrode influenced the reaction rates.
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  • 2
    ISSN: 1572-879X
    Keywords: oxidation ; reduction of palladium catalysts ; chlorine effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Pd–chloride precursor salt was used to prepare Pd/Al2O3 catalysts. TPSR measurements showed three distinct reactions for the oxidation of propane on palladium surface under excess of hydrocarbon: complete oxidation, steam reforming and propane hydrogenolysis. Propane oxidation on palladium catalysts was related to the Pd2+ sites observed on Pd/Al2O3 through infrared of adsorbed carbon monoxide. In fresh catalysts reduced by H2, the IR spectra showed the linear and bridge adsorbed CO species on the Pd0 surface. After propane reaction, a new band at 2130 cm-1 related to CO adsorption on Pd2+ species was noted. Carbon monoxide species adsorbed on Pd0 were also observed in all samples after reaction. Our results suggest surface ratios of Pd0/PdO during the propane oxidation. On the other hand, time on stream conversions of the complete oxidation of propane were affected by either the water generated during the reaction or added as a reactant at 10 vol%. The water generated by the reaction helped to eliminate chlorine residues in the form of oxychloride species leading to an increasing of the activity. However, the presence of water into the reaction mixture caused a strong decreasing of the activity. The inhibition mechanism of propane oxidation in the presence of water consisted in the dissociative adsorption of water on palladium sites with the possible formation of palladium hydroxide (Pd–OH) at the surface, diminishing the number of active surface sites. Dynamic fluctuations into the reaction conditions supported the idea that a pseudo‐equilibrium adsorption–desorption of water was reached. After water removal or increasing in the reaction temperature the equilibrium was shifted to the direction of OH–Pd decomposition. This behavior suggests that the inhibitory effect of water is a reversible phenomenon, being a function of the amount of water and the reaction temperature.
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  • 3
    ISSN: 1572-879X
    Keywords: methane ; oxidation ; aliphatic hydrocarbons ; zeolite ; recycle reactor
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Conversion of methane in high yields to C4+ nonaromatic hydrocarbons was demonstrated in a recycle system. The principal components of the recycle system included an oxidative coupling reactor with a Mn/Na2WO4/SiO2 catalyst at 800°C for conversion of methane to ethylene, and a reactor with an H-ZSM-5 zeolite at 275°C for subsequent conversion of ethylene to higher hydrocarbons. Total yields of C4+ products were in the range of 60–80%, and yields of C4+ nonaromatic hydrocarbons were in the range of 50–60%.
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  • 4
    ISSN: 1572-9028
    Keywords: oxidation ; oxyacetoxylation ; alloy ; palladium ; bismuth ; benzylacetate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Benzylacetate synthesis from toluene, acetic acid and oxygen on Pd–Bi binary catalyst was studied in the liquid phase. By incorporation of Bi with Pd, both the activity and selectivity were improved. Especially better stability was obtained with the catalyst having Pd/Bi = 3. Deactivation of the catalyst was investigated in detail by XRD, XPS, TEM, elemental analysis, EPMA and so on. Comparing the used catalyst with the fresh one, it was indicated that the main cause of deactivation was the dissolution of Pd into the reaction mixture from the most outer surface of the catalyst. By adopting proper reaction conditions to prevent the Pd dissolution, the catalyst having Pd/Bi = 3 was suggested to be used as an industrial catalyst.
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  • 5
    ISSN: 1572-9028
    Keywords: nitric oxide ; ammonia ; oxidation ; X-ray photoelectron spectroscopy ; scanning tunnelling microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The dissociative chemisorption of nitric oxide at Cu(110) has been shown to result in rapid ordering of oxygen adatoms as (2×1)O chains oriented along the 〈100〉 direction while the associated nitrogen adatoms are mainly disordered at 295 K. Surface diffusion of the N adatoms, following bond cleavage, is activated and ordering of the (2×3)N strings occurs on heating to 430 K. A number of distinct reaction pathways have been isolated during the oxidation of ammonia resulting in the formation of either chemisorbed imide or nitrogen adatoms. The latter depending on temperature, may exhibit a (2×3)N, a (3×3)N or both structures may exist simultaneously. The concentration of nitrogen in the complete (2×3)N structure has been determined to be 6.6×1014 cm-2, with only a 25% decrease in nitrogen concentration leading to the transformation to the (3×3)N structure. The oxygen atoms at a Cu(110)–O overlayer, and present at the ends of the (2×1) strings terminating in steps, show specific reactivity when exposed to ammonia at 375 K resulting in the “decoration” of the steps with imide species while the oxygens within the (2×1) strings remain unreactive.
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  • 6
    ISSN: 1572-879X
    Keywords: alkylbenzene ; toluene ; ethylbenzene ; xylene ; mesitylene ; p‐ethyltoluene ; cumene ; p‐cymene ; oxidation ; palladium ; 1,10‐phenanthroline
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Only the side‐chain oxidation of alkylbenzenes (R–C6H3–R′–R″ R=H, Me, Et, Pri R′=H, Me; and R″=H, Me) by oxygen (35–50 atm, 200)C° is promoted in the presence of [Pd(phen)(OAc)2].
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  • 7
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    Topics in catalysis 11-12 (2000), S. 359-367 
    ISSN: 1572-9028
    Keywords: zeozyme ; encapsulated complexes ; copper acetate ; copper dimers ; enzyme mimic ; EPR of copper ; tyrosinase ; oxidation ; oxygenase ; tyrosine oxidation ; phenol oxidation ; hydroxylation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxygenase mimicking activity of copper acetate dimers in the regioselective ortho-hydroxylation of L-tyrosine to L-dopa is enhanced on encapsulation in zeolite Y. The structure and magnetic properties of the catalytic active site were characterized by EPR spectroscopy. The spectra of this “zeozyme” reveal the presence of (1) copper acetate dimers in the supercages and (2) isolated Cu(II) ions in the sodalite cages of the zeolite. There are significant differences in the EPR spectra of the “neat” and encapsulated complexes: on encapsulation in zeolite, the Cu–Cu exchange coupling constant, −, increases to 310 from 259 cm−1 for the “neat” complex (i.e., by about 19.7%). Simultaneously the Cu–Cu separation in the dimer, estimated indirectly from the exchange coupling constant, shortens to 2.40 Å in the encapsulated state from 2.64 Å in the “neat” complex. There is, hence, a relatively greater overlap of the metal orbitals of the dimer copper atoms inside the restricted confines of the zeolite cages. The consequent, enhanced, trans axial lability of the phenolate and dioxygen ligands promotes the catalytic oxygenase activity of copper acetate dimers on encapsulation in zeolites. A causal relationship between changes in the structural features of an active site on encapsulation in the zeolite and the corresponding catalytic activity has, thus, been established.
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  • 8
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    Catalysis letters 64 (2000), S. 113-118 
    ISSN: 1572-879X
    Keywords: X‐ray photoelectron spectroscopy (XPS) ; scanning electron microscopy (SEM) ; silver ; oxidation ; surface chemical reaction ; NO ; NO x
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The behavior of a AgNO3/Ag2O/Ag “sandwich” upon heating in vacuum was studied by in situ X‐ray photoelectron spectroscopy (XPS) and ex situ scanning electron microscopy (SEM). The AgNO3/Ag2O/Ag “sandwich” was prepared by exposure of a silver foil to a NO : O2 mixture. The upper layer of the “sandwich” consists of AgNO3 crystals of a mean size between 0.1 and 0.4 μm. Heating at 550 K in vacuum results in melting of the AgNO3 crystals. A liquid film of AgNO3, readily wetting the silver, covers the surface. Cooling below the melting point of AgNO3 leads to the agglomeration of silver nitrate to long islands with a size reaching a few tens of micrometers (μm). The possible effects of AgNO3 liquid‐phase formation on surface processes are discussed.
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  • 9
    ISSN: 1572-879X
    Keywords: chlorinated hydrocarbons ; chromia ; titania ; alumina ; CVOCs ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of perchloroethylene (PCE) was investigated over chromium oxide catalysts supported on TiO2, Al2O3, SiO2, SiO2–Al2O3 and activated carbon. The phase of chromium oxide on the catalyst surface is critical for the oxidation of PCE. The catalytic activity of PCE removal enhances as the formation of Cr(VI) species on the catalyst surface increases. The surface area and the type of the catalyst supports were also essential for high performance in the PCE oxidation. In addition, the structure of Cr(VI) on the catalyst surface also plays an important role for the decomposition of PCE. The polymerized Cr(VI) mainly formed by the interaction of metals with the support is the active reaction site for the present reaction system. CrOx/TiO2 reveals the strongest PCE removal activity among the catalysts examined in the present study.
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  • 10
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    Journal of thermal analysis and calorimetry 61 (2000), S. 181-189 
    ISSN: 1572-8943
    Keywords: characteristic temperatures ; concentrates ; DTA ; DTG ; oxidation ; sulphides ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of metal sulphides and sulphide concentrates was studied by means of DTA, TG and DTG curves. The behaviour of ZnS, CdS, GaS, Tl2S, Sb2S3 and Sb2S5 during thermal treatment in an oxidizing medium was investigated. The properties of these sulphides were compared and conclusions were drawn about their probable oxidation reactions and the kind of end-products obtained. The characteristic temperatures of the studied sulphides were determined on the basis of curves (DTA). The values obtained were used to compare the behaviour of the sulphides during the oxidation process in a fluid bed. The results can be used to improve the technological and economic indices in the industrial production of zinc.
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  • 11
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    Journal of nanoparticle research 2 (2000), S. 315-319 
    ISSN: 1572-896X
    Keywords: nanostructure ; silicon ; oxidation ; CNT tip ; ion trap ; research management
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics , Technology
    Notes: Abstract Joint Research Center for Atom Technology (JRCAT) and its Atom Technology Project are described. The project covers a wide range of research subjects; manipulation of atoms and molecules, formation of nanostructures of semiconductors, spin electronics and first-principles calculation of dynamic processes of atoms and molecules on solid-state surfaces. Several recent achievements on nanotechnology and nanoscience are roughly sketched.
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  • 12
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    Journal of thermal analysis and calorimetry 62 (2000), S. 575-578 
    ISSN: 1572-8943
    Keywords: active metal ; high-dispersed iron powder ; oxidation ; thermogravimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Two oxidation stages of electrolytic ultradispersed iron powder at the temperature range of 90–450°C have been stated. The contribution of increasing mass and evolving heat at the first oxidation stage due to changing Fe0 into Fe2O3 in the total oxidation effect is predominant. The thermal method of active metal determination in electrolytic iron powders has been developed. The coarse-grained reduced iron powder was not oxidized completely just to 900°C because of local sintering of big iron particles as a result of evolving heat at oxidation of high-dispersed iron particles.
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  • 13
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    Journal of thermal analysis and calorimetry 63 (2000), S. 507-515 
    ISSN: 1572-8943
    Keywords: boron carbide ; kinetic modelling ; oxidation ; water vapour
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation behaviour of a B4C based material was investigated in a dry atmosphere O2(20 vol.%)-CO2(5 vol.%)-He and also in the presence of moisture H2O (2.3 vol%) as boron oxide is very sensitive to water vapour. The mass changes of samples consisting of a chemical vapour deposit of B4C on silicon nitride substrates were continuously monitored in the range 500–1000°C during isothermal experiments of 20 h. The stability of boron oxide formed by oxidation of B4C was also studied in dry and wet atmospheres to explain the kinetic curves. In both atmospheres, oxidation is diffusion controlled at 700 and 800°C and enhanced by water vapour. At 900°C and higher temperatures, boron oxide volatilisation and consumption by reaction with water vapour modifies the properties of the oxide film and the material is no more protected. At 600°C, B4C oxidation is weak but the process remains diffusion controlled in dry conditions as boron oxide volatilisation is negligible. However, in the presence of water vapour, B2O3 consumption rate is significant and mass losses corresponding to this consumption and to the combustion of the excess carbon are observed.
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  • 14
    ISSN: 1573-4889
    Keywords: ion implantation ; oxidation ; thermal ; stainless steel ; ion-beam analysis ; aluminum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract AISI-321 steel samples were implanted with Al ions (implantation-energy:40 keV; dose: 2×1017 ions/cm2). Thermal oxidationof the samples was performed at 450, 550, 600, and 650°C for periodsvarying from 1 to 6 days in air and in a corrosive CO2-containingenvironment. Nuclear Reaction Analysis (NRA) and Rutherford BackscatteringSpectrometry (RBS) were used to investigate the oxidized samples. Asignificant improvement of the oxidation resistance of the implantedmaterial in comparison to the nonimplanted material was observed. Thisespecially applies for samples oxidized at high temperatures. The aluminumdepth distribution determined by NRA [using the resonance at 992 keV of the27Al(p, γ )28Si nuclear reaction] and RBS,indicated no variation of the Al profile in the temperature region450–600°C, whereas at 650°C a slight Al diffusion wasobserved. Scanning electron microscopy (SEM–EDS) was applied to studythe surface morphology and the constitution of the oxide scale formed, aswell as to explain the influence of Al implantation on the oxidation behaviorof AISI-321 austenitic stainless steel.
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  • 15
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    Oxidation of metals 53 (2000), S. 467-479 
    ISSN: 1573-4889
    Keywords: Ni–5Cr–5Al ; oxidation ; magnetron sputtering ; nanocrystalline coating
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A NiO-forming Ni–5Cr–5Al (at.%) alloy has been developed anddeposited as a sputtered nanocrystalline coating. The oxide formation andoxidation behavior of this coating have been studied at 1000°C inair. The oxidation rate markedly decreased with time and the oxidationkinetics obeyed the fourth power law. Complex oxide scales, consisting ofNiO, NiAl2O4 and α-Al2O3,were formed during 200 hr oxidation. The outer oxide layer consisted of NiOand NiAl2O4 and an inner oxide layer ofα-Al2O3. The sputtered Ni–5Cr–5Alnanocrystalline coating showed good oxidation resistance due to theformation of an α-Al2O3 inner layer andexcellent adhesion of the complex oxide scales.
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  • 16
    ISSN: 1573-4889
    Keywords: ion plating ; steel ; TiAlN coating ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract To improve the high-temperature oxidation resistance of STD61 steels used ashot dies or cutting tools, Ti0.3Al0.2N0.5films were deposited on STD61 steel substrates by arc-ion plating. Thedeposited film consisted of Ti3Al2N2 andTi2N phases. The oxidation characteristics were studied attemperatures ranging from 700 to 900°C in air. The deposited STD61steels displayed excellent oxidation resistance up to 800°C, butexhibited large weight gains and breakaway oxidation at 900°C. Theoxidation products were primarily Fe2O3, TiO, TiO2,and α-Al2O3, the relative amount of each oxidebeing dependent on the oxidation condition. Among various oxides, TiO2and α-Al2O3 were the major oxides at 800°Cfor at least up to 16 hr. However, at a higher temperature or a longeroxidation period, the significant outward diffusion of iron from thesubstrate resulted in the formation of iron oxides, together with otheroxides of Ti and Al.
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  • 17
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    Oxidation of metals 54 (2000), S. 155-162 
    ISSN: 1573-4889
    Keywords: Ni–8Cr–3.5Al ; nanocrystallization ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Magnetron-sputter deposition was used to produce a Ni–8Cr–3.5Al(wt.%) nanocrystalline coating on substrates of the same alloy. Theoxidation behavior of the cast Ni–8Cr–3.5Al alloy and itssputtered coating were investigated at 1000°C in air. Complex,layered-oxide scales composed of Cr2O3 outer layer,mixed spinel NiAl2O4 and NiCr2O4middle layer, and α-Al2O3 inner layer were formedon the Ni–8Cr–3.5Al nanocrystalline coating during 200-hroxidation, whereas Cr2O3, with some NiCr2O4external layer with internal Al2O3, formed on the castalloy. Because of the formation of this α-Al2O3inner layer on the coating, the sputtered Ni–8Cr–3.5Al coatingshowed better oxidation resistance than the cast alloy. The effect ofnanocrystallization on oxide formation is discussed. It was indicated thatthe formation of this α-Al2O3 inner layer was closely related to therapid diffusion of Al through grain boundaries in the nanocrystallinecoating and the relatively high Cr content in Ni–8Cr–3.5Al.
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  • 18
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    Oxidation of metals 54 (2000), S. 189-209 
    ISSN: 1573-4889
    Keywords: oxidation ; β-FeAlCr ; coatings ; magnetron sputter-deposition ; ridge-type oxide ; Al2O3 phase transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract β-FeAl coatings containing various Cr contents of 6.5–45 wt.%were produced with a closed-field, unbalanced magnetron sputter (CFUMS)deposition technique. Cyclic oxidation tests at 1100°C in air for100 1-hr cycles and isothermal exposures at 1000°C in pure O2 for100 hr were carried out with the coatings and an as-cast FeAlspecimen. All of the coatings showed good scale-spallation resistanceduring cyclic oxidation and the coating with 6.5 wt.% Cr exhibited thelowest oxidation rates in both cyclic and isothermal oxidationexposures. After oxidation, fine-grain ridge-type oxide scales formed onthe coatings, while the oxide scale formed on the cast FeAl showed alarge quantity of θ-Al2O3 blades and large interfacial voids on thebase–alloy surface. The transformation from θ to α-Al2O3was accelerated due to the presence of Cr in the coatings. The fasttransformation considerably reduced oxidation rates, suppressed fastoutward Al diffusion for the growth of a θ-Al2O3 scale, and preventedthe formation of interfacial voids that played a major role in causing thescale spallation.
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  • 19
    ISSN: 1573-4889
    Keywords: plasma spraying ; chromium steel ; oxidation ; Fe–Cr spinel oxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract During plasma spraying of metals in air, rapid-oxidation reactions occur, inmost cases. In oxidation products of Cr-rich steels, Fe–Cr spineloxide is often found as a dominant oxide phase. A thermodynamic analysisof a system composed of Fe–13%Cr alloy and water vapor or air showedthat the oxidation product in a wide range of high temperatures isFe3-wCrwO4 (w〉2). This tetragonallydistorted spinel oxide is not stable at room temperature. Water vapor andair were considered as limits of the gaseous-phase composition inatmospheric spraying by a water-stabilized plasma gun, where the compositionof the plasma plume is modified by air entrainment. The equilibriumcalculations enabled determination of the effects of temperature andgas-to-solid ratio on w. To show the existence of chromium-rich,tetragonally distorted spinel oxide experimentally, a typical productresulting from oxidation of 13%Cr–steel particles during their flightin the plasma plume was studied after rapid solidific ation. This was madepossible by trapping and quenching the flying particles in liquid nitrogenat a distance from the plasma-gun nozzle corresponding to thenozzle–substrate distance in conventional plasma spraying. The resultsobtained by X-ray diffraction, Mössbauer spectroscopy, and X-rayfluorescence analysis showed that this oxide, in which w≈2.4, constitutedthe dominant phase in the oxidation product.
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  • 20
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    Molecular and cellular biochemistry 206 (2000), S. 151-157 
    ISSN: 1573-4919
    Keywords: cardiac function ; diabetes ; ischemia ; oxidation ; propionyl-L-carnitine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Previous studies have shown that propionyl-L-carnitine (PLC) can exert cardiac antiischemic effects in models of diabetes. In the nonischemic diabetic rat heart, PLC improves ventricular function secondary to stimulation in the oxidation of glucose and palmitate. Whether this increase in the oxidation of these substrates can explain the beneficial effects of PLC in the ischemic reperfused diabetic rat heart has yet to be determined. Diabetes was induced in male Sprague-Dawley rats by an intravenous injection of streptozotocin (60 mg/kg). Treatment was initiated by supplementing the drinking water with propionyl-L-carnitine at the concentration of 1 g/L. After a 6-week treatment period, exogenous substrate oxidation and recovery of mechanical function following ischemia were determined in isolated working hearts. In aerobically perfused diabetic hearts, compared with those of controls, rates of glucose oxidation were lower, but those of palmitate oxidation were similar. Diabetes was also characterized by a pronounced decrease in heart function. Following treatment with by propionyl-L-carnitine, however, there was a marked increase in rates at which glucose and palmitate were oxidized by diabetic hearts and a significant improvement in heart performance. Postischemic recovery of function in diabetic hearts was also improved with PLC. This improvement in contractile function was accompanied by an increase in both glucose and palmitate oxidation. Our findings show that postischemic diabetic rat heart can be improved following chronic PLC treatment. This beneficial effect of propionyl-L-carnitine can be explained, in part, by an improvement in the oxidation of glucose and palmitate.
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  • 21
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    Journal of materials synthesis and processing 8 (2000), S. 359-363 
    ISSN: 1573-4870
    Keywords: Mechanical activation ; brown coal ; electrophoretic mobility ; oxidation ; humic acids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract This paper presents a study of the influence of mechanochemical activation of coal on the process of formation and degradation of humic acids. The increasing period of mechanical activation of coal causes an increase in hydrophility, electrophoretic mobility, and of electrokinetic potential of surface layers as a result of acidic carboxyl and phenolic OH groups. The effective activation requires a short period of grinding. The increased time of activation causes the secondary processes of grain agglomeration and degradation of humic acids.
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  • 22
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    Oxidation of metals 53 (2000), S. 427-449 
    ISSN: 1573-4889
    Keywords: sulfidation ; carburization ; oxidation ; high-temperature corrosion ; commerical alloys
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A sulfidation/carburization study of seven commercial heat-resistant alloyswas carried out at 900°C in a H2–25 vol.%CH4–14.8N2–4CO–0.6CO2–0.6H2Satmosphere. The equilibrium partial pressures for oxygen (O2) andsulfur (S2) were 1.1×10−22 and 4.1×10−8 atm,respectively, and the carbon activity for this system was unity. The time ofexposure was 500 hr. Relatively thick, mixed sulfide scales were formed onall of the alloys tested. In addition, internal carburization occurred inall of the alloys. Using metal loss (i.e., the reduction in samplethickness) plus internal attack (internal sulfidation plus internalcarburization) as a performance criterion, an alloy with a nominalcomposition of Ni–29 wt.% Co–28Cr–2.75Si performed thebest, showing 0.71 mm of attack. An alloy with a nominal composition ofFe–20 wt.% Ni–25Cr performed the worst, being totally consumedby the test (〉3.18 mm of attack). Alloys containing relatively highamounts of silicon (〉2.5%) showed a dramatic increase in theirsulfidation resistance compared to the other alloys containing lowersilicon contents. The amount of iron present within a given material playeda dominant role in the carburization attack that occurred, with as expected,high-iron alloys showing significant internal carburization because of ahigh solubility and diffusivity of carbon in the matrix. The importance ofthe various alloying elements with respect to sulfidation and carburizationresistance is discussed.
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  • 23
    ISSN: 1573-4889
    Keywords: oxidation ; chromia ; alumina ; thin oxide films ; reactive element
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In order to study the effects on oxidation behavior of changing thecomposition of oxide scales without changing the composition of theunderlying alloys, thin films, which contained various amounts of Y2O3,Cr2O3, or Al2O3 have been deposited on Fe–25%Cr andFe–25%Cr–5%Al prior to oxidation. There were major differencesbetween the (Fe–25%Cr)–(Cr2O3–Y2O3) and(Fe–25%Cr–5%Al)–(Al2O3–Y2O3) systems. A film ofCr2O3 on Fe–25%Cr reduced the oxidation rate and Cr2O3–Y2O3films reduced it still further. A film of Al2O3 onFe–25%Cr–5%Al reduced the rate considerably, butAl2O3–Y2O3 films exhibited rates that were greater than those forAl2O3 alone. A film, which consisted entirely of Y2O3, greatly decreasedthe oxidation rate of Fe–25%Cr, but increased that ofFe–25%Cr–5%Al. The changes in oxidation rate produced byY2O3 in the (Fe–25%Cr)–(Cr2O3–Y2O3) system weremuch greater than those produced in the(Fe–25%Cr–5%Al)–(Al2O3–Y2O3) system. As far asoxidation rate is concerned, the optimum amount of Y2O3 in the(Fe–25%Cr)–(Cr2O3–Y2O3) system was found to begreater than or equal to 40% and less than 100%; in theFe–25%Cr–5%Al)–(Al2O3–Y2O3) systemit was approximately 10%. In thermal-cycling tests, the resultsfor the (Fe–25%Cr)–(Cr2O3–Y2O3) system followedthe same pattern as that for the isothermal tests; a film of Y2O3reduced the oxidation rate and a film of Cr2O3–33%Y2O3reduced it still further.
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  • 24
    ISSN: 1573-4889
    Keywords: Fe–Cr–Al alloy ; oxidation ; molybdenum ; breakaway oxidation ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Thin foils of Fe–20Cr–5Al alloys are susceptible to breakawayoxidation once the aluminum content of the substrate has fallen below somecritical value. The combined addition of 0.1 wt.% lanthanum and 0, 1, or 2wt% molybdenum has a beneficial effect on the high-temperature oxidation ofsuch foils. Lanthanum has the well-known reactive-element effect on adhesionof the protective alumina scale, thereby increasing the time to onset ofbreakaway oxidation, while, for alloys containing molybdenum, breakawayoxide spreads relatively slowly over the specimen in comparison to alloysthat contain no molybdenum. In particular, molybdenum-containing alloys areable to develop a protective Cr2O3 layer at the breakawayoxide–substrate interface. Conversely, molybdenum-free alloys form aninternal-oxide zone in the substrate adjacent to this interface, rather thana Cr2O3 layer, so breakaway oxide spreads rapidly. A martensitic phase isobserved in the substrate adjacent to the breakaway oxide formed on Fe–20Cr–5Al–La specimens, which means that theα-phase has transferred to the γ -phase at the temperature ofthe oxidation test (1150°C). Conversely, α-phase is retained inthe molybdenum-containing alloy, even after breakaway takes place, sincemolybdenum, which is a strong ferrite former, is enriched in the alloyadjacent to areas of breakaway oxide. The diffusion rate of chromium isslower in the γ than in the α-phase so a continuouschromium-rich oxide layer, which is effective in inhibiting breakawayoxide from spreading, cannot be established at the breakawayoxide–substrate interface for the molybdenum-free alloys.
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    Oxidation of metals 54 (2000), S. 63-71 
    ISSN: 1573-4889
    Keywords: microstructure ; Inconel 625 ; oxidation ; deformation substructure ; deformation twins ; energy-dispersive spectroscopy (EDS) ; internal oxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The high-temperature, isothermal-oxidation behavior of a superalloy was studied in the as-rolled and deformed conditions. The microstructural changes occurring during the oxidation of samples were examined using optical, scanning electron microscopy (SEM), fine-probe EDS microanalysis, and X-ray diffraction techniques. The topography of the oxide layers formed in the as-rolled and cold-deformed specimens exposed at various temperatures and time intervals is also examined. The kinetics and microstructural results are presented for the comparative study of the structural changes occurring during high-temperature oxidation. It was found that a Cr2O3 external layer was adherent and uniform on the rolled specimens in comparison to the scattered and preferential oxide developed on the deformed specimens. The latter can be attributed to the concurrent dynamic changes occurring in the deformed substructure that subsequently lead to breaking and spallation of the oxide.
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  • 26
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    Oxidation of metals 54 (2000), S. 121-138 
    ISSN: 1573-4889
    Keywords: titanium aluminides ; oxidation ; oxygen-affected zone ; alpha case ; TEM
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The isothermal oxidation behavior of binary Ti–25 at.% Al was studiedat 1073, 1173, and 1273 K in air and oxygen with emphasis on themicrostructure of the subsurface zone underneath the external oxidescale. Thermogravimetric analysis, acoustic-emission (AE) analysis, lightmicroscopy, scanning electron microscopy (SEM), atomic force microscopy(AFM), and cross-sectional transmission electron microscopy (TEM) werecarried out. Three layers could be identified in the subsurface regionconsisting of an internal oxidation zone of α-Al2O3,and α-Ti, a ternary phase with the empirical formulaTi–21Al–15O (at.%), and an oxygen penetration zone consisting ofα2-Ti3Al(O).
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  • 27
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    Oxidation of metals 54 (2000), S. 445-456 
    ISSN: 1573-4889
    Keywords: quasicrystals ; aluminides ; oxidation ; nodules
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of a quasicrystal with the nominal compositionAl63Cu25Fe12 was studied around 800°Cin environmental and synthetic air by means of thermogravimetric analysis,electron microscopy, and analytical electron spectroscopy. In an earlyoxidation stage, γ-Al2O3 formed with an orientational relationship tothe quasicrystal. At the oxide–metal interface, γ-Al2O3transformed into large hexagonal shaped α-Al2O3grains. The change in surface morphology indicated that at theoxide–gas interface γ-Al2O3 continued togrow as Θ-Al2O3. Locally the metastable aluminalayer was transformed thoroughly into α-Al2O3,which then continued to grow with a nodular morphology. On top of the oxidenodules, several at.% of Cu2+ were detected.
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  • 28
    ISSN: 1573-4889
    Keywords: oxidation ; marginal chromia formers ; water vapor effect ; chromia evaporation ; breakaway corrosion ; flow-rate dependence ; 304L
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The effect of roman PH 2 O and flow rate on the oxidation of 304Lat 873 K in oxygen is reported. High concentrations of water vapor and highflow rates result in breakaway corrosion. The mass gain after 168 hrincreased by four to five times, compared to oxidation in dry O2. Inthe presence of H2O, the corrosion products consisted of arelatively thin (Cr,Fe)2O3 oxide plus large oxide islandsconsisting mainly of Fe2O3. A mechanism explaining theeffect of water vapor on marginal chromia formers is proposed.
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  • 29
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    Oxidation of metals 54 (2000), S. 47-62 
    ISSN: 1573-4889
    Keywords: oxygen sensor ; oxygen pump ; solid-state electrolyte ; ZrO2 ; oxygen partial pressure ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract An ultralow oxygen partial pressure-controlling system, based on solid-stateelectrochemical principles, has been developed. This system consists of anoxygen sensor and an oxygen pump and is controlled by a PC computer. Theoxygen sensor is used to measure the oxygen partial pressure in an enclosedsystem, while the oxygen pump is used to transport oxygen from the ambientair into the enclosed system or from the enclosed system to the ambientair. The operating conditions of this system have been studied. The resultsshowed that it can be used to establish a stable oxygen partial pressure inthe range of 10−18∼5×105 Pa (1×10−23∼5 atm)in the enclosed system. This system has been used to investigate theselective oxidation of the Cr and the oxide formation on the surface of aNi–Cr alloy under three different low oxygen partial pressures. Theoxide morphology was studied using atomic force microscopy (AFM). The resultsagreed well with those in the literature and also confirm the reliability of this system.
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  • 30
    ISSN: 1573-4889
    Keywords: TiAl ; oxidation ; phosphorus ; microdiffraction ; doping ; rutile
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Recently it has been found that very small amounts (a few 100 ppm) of Padded to γ -titanium aluminide can significantly alter the oxidationbehavior between 973 and 1273 K. The mechanism responsible for this changeis, however, still not clear. In the present study, phosphorus wasincorporated into the surface of TiAl (containing 50 at.% Al) by ionimplantation and oxidation tests were carried out at 1173 K inair. Improvement of oxidation resistance is only temporary up to 100 hr forphosphorus-implanted TiAl. After 100 hr, the oxidation rate increases andbreakaway oxidation follows. XRD and EPMA showed that the breakawayoxidation is connected with massive nitride formation. Two different modelsare proposed which can explain the effect of phosphorus additions on theoxidation kinetics of TiAl during the protective stage within the first100 hr. The breakaway effect can be explained by penetration of air to themetal–oxide interface zone because of microcrack formation in theoxide scale, which was experimentally proved by acoustic-emission analysis.
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  • 31
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    Oxidation of metals 54 (2000), S. 339-371 
    ISSN: 1573-4889
    Keywords: Fe–Al alloys ; oxidation ; sulfidation ; nodular growth ; corrosion mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The mechanisms for nodular corrosion-product development were investigatedin various high-temperature gaseous environments. Fe–Al alloys, with5–20 wt.% Al, were exposed in both oxidizing and sulfidizing[p(S2)=10−4 atm, p(O2)=10−25 atm] atmospheres at 700°Cfor times up to 100 hr. The corrosion kinetics were monitored by theuse of a thermogravimetric balance and the morphological developmentthrough light-optical and scanning-electron microscopies,energy-dispersive spectroscopy, electron-probe microanalysis,and quantitative-image analysis. Under both conditions, theelimination of nodule formation was observed by increasing thealuminum content of the alloy, above 5 and 7.5 wt.% Al for oxidizingand sulfidizing environments, respectively, which promoted the growthand maintenance of a continuous surface scale of alumina. For thosealloys that were observed to develop nodular corrosion products, theirmorphological appearance was similar in nature regardless of thecorroding species. The nodules typically consisted of an outeriron-rich product, either sulfide or oxide, that was randomly dispersedacross an alumina scale. Samples from the oxidizing atmosphere displayeda single growth-rate time constant from the kinetics data, suggesting thatthe nodule growth mechanism was by the simultaneous or codevelopment oftwo different (Fe and Al) oxides from the onset of exposure. Measurementof nodule planar diameter and depth of penetration into the alloyindicated that growth occurred through diffusional processes. Kineticsdata from the development of sulfide nodules in the reducingenvironment revealed a different type of mechanism. Multiplegrowth-rate time constants were found due to the localized mechanicalfailure of an initially formed surface scale. At early times in thesulfidizing atmosphere, a low corrosion rate was recorded as acontinuous-alumina scale afforded protection from excessive productdevelopment. However, with the mechanical failure of the scale, sulfurwas able to attack the underlying substrate through a short-circuitdiffusion mechanism that resulted in rapid weight gains from nonprotective,iron sulfide growth. The sulfide morphologies observed were very complex ascontinued growth of the nodule did not solely depend upon the diffusingspecies through the previously formed corrosion products, but also,continued mechanical failure of the oxide scale. It is suggested that thedifference in development mechanisms between the two environments may liein the relative growth rates of the nonprotective, Fe-base corrosionproducts formed.
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    Oxidation of metals 54 (2000), S. 559-574 
    ISSN: 1573-4889
    Keywords: silver–nickel ; mechanical alloying ; oxidation ; two-phase alloys
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Two nanophase Ni-base alloys containing 50 and 25 at.% Ag prepared by mechanical alloying, denoted Ni–50Ag and Ni–25Ag were oxidized in air at 600 and 700°C for 24 hr. Ni–50Ag underwent internal oxidation of nickel, associated with the formation of a continuous outermost layer of silver metal with scaling rates larger than those for pure nickel. On the contrary, Ni–25Ag formed a continuous NiO layer surmounted by a discontinuous silver layer and internal oxidation was suppressed. The oxidation rate of Ni–25Ag decreased with time much more rapidly than predicted by the parabolic rate law during the initial stage and eventually became parabolic, with rate constants much lower than those for the oxidation of pure nickel. These results are attributed to the two-phase nature and, particularly, to the very small grain size of the two alloys.
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  • 33
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    Oxidation of metals 53 (2000), S. 1-23 
    ISSN: 1573-4889
    Keywords: Aluminum ; SEM ; oxidation
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Fine powders of aluminum were produced in a pilot-plant, inert-gas atomizerwith a “confined-design” nozzle, which operated vertically upward. Argonand helium at 1.85 MPa and nitrogen at 1.56 MPa were used as the atomizingagent. The morphology of the powder particles was examined by SEM. Powderswere sieved dry and wet. The Sauter mean diameter of the powders varied from20.70 to 10.25 μm depending on the atomizing gas. The distribution ofsizes was bimodal. The mean thickness of oxide on the surface of the powderwas calculated from the total oxygen contents of powder samples (determinedby a Leco analyzer). In addition, ESCA measurements and BET tests werecarried out for surface-oxide thickness and area measurements,respectively. The finest powder produced under helium incorporated thinnersurface-oxide layers than the coarser ones produced under argon andnitrogen. This was due to differences in physical properties (such asdensity, thermal conductivity) and flow properties (such as gasvelocity and relative velocity) of the atomizing gases used, i.e., helium,argon, and nitrogen. The oxide was very irregular in thickness in thecoarse-size range of the Al powders produced under argon and nitrogen. Thiswas presumably because of the high- and low-temperature oxidation ofaluminum droplets during the atomization and subsequent solidification andcooling periods leading to the rough surfaces observed with SEMinvestigation in the present work.
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  • 34
    ISSN: 1573-4889
    Keywords: γ-TiAl-based intermetallic alloy ; oxidation ; microstructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The influence of microstructure of the two-phase alloyTi–46Al–1Cr–0.2Si on the oxidation behavior in air between600 and 900°C was studied. The oxidation rate, type of scale, and scalespallation resistance were strongly affected by the type of microstructure,i.e., lamellar in as-cast material and duplex after extrusion at1300°C. The oxidation rate was affected by the size and distribution ofthe α2-Ti3Al phase, being faster for the extrudedmaterial with coarse α2-Ti3Al. The type of oxide scaledetermines the spalling resistance. Cast material developed a uniform scalethat spalled off after short exposure times at 800 and 900°C when a criticalthickness was reached. The extruded material presented a heterogeneous scalewith predominant thick regions formed on γ-TiAl-α2-Ti3Algrains and thin scale regions formed on γ-TiAl grains. Thistype of scale could permit an easier relaxation in the matrix of stressesgenerated by both thermal-expansion mismatch between scale and alloy andoxide growth, resulting in a higher spallation resistance.
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  • 35
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    Oxidation of metals 54 (2000), S. 575-589 
    ISSN: 1573-4889
    Keywords: TiAl ; oxidation ; Si3N4 ; dispersed particles
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation kinetics of TiAl alloys with and without 3 and 5 wt.%additions of Si3N4 particles were studied at 1173 and1273 K in 1 atm of air. The Si3N4 dispersions wereunstable in the matrix phase, so that some of them reacted with titaniumduring sintering to form Ti5Si3 and dissolvednitrogen. The oxide scale formed on TiAl–Si3N4alloys consisted of an outer TiO2, an intermediate(Al2O3+TiO2), and an inner(TiO2+Al2O3) mixed layers. The enhancedalumina-forming tendency, the presence of discrete SiO2 particlesbelow the outer TiO2 layer, and the improved scale adhesion bySi3N4 dispersions were attributable mainly to theincreased oxidation resistance compared to the Si3N4-freeTiAl alloys. Marker experiments showed that, for TiAl–Si3N4 alloys, the primary mode of scale growth was the outward diffusion oftitanium ions for the outer scale and the inward transport of oxygen ionsfor the inner scale.
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  • 36
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    Journal of sol gel science and technology 19 (2000), S. 17-22 
    ISSN: 1573-4846
    Keywords: Reactive materials ; heterogenized reagents ; oxidation ; dehydration ; esterification ; doped sol-gel
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract We advance the use of reactive doped sol-gel materials as heterogeneous reagents for organic-chemistry synthesis. Three approaches were demonstrated with SiO2-based materials: Direct physical entrapment of the organic reagent; in-situ generation of an inorganic reagent within the matrix; and covalent attachment of the reagent to the matrix. With the first, entrapped p-toluenesulfonic acid facilitated the 100% yield esterification of benzoic acid with 1-pentanol, and the 100% dehydration of 1-tetralol to 1,2-dihydronaphthalene; with the second approach, a sol-gel oxidant, SiO2/MnO2 was used to convert benzyl alcohol to benzaldehyde and 1-tetralol to 1-tetralone; and with the third, anchored propylamine facilitated dehydrobromination reactions resulting in double-bond formation. Several other reactions with these reagents are described, and their reactivities analyzed.
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  • 37
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    Journal of porous materials 7 (2000), S. 373-376 
    ISSN: 1573-4854
    Keywords: porous silicon ; superlattices ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Initial stage of porous silicon (PS) formation has been studied in an original way. Multilayer structures constituting of very thin layers of low porosity and thick layers of high porosity have been fabricated and characterised by optical tools and electron microscopy. The non linear behaviour resulting in a change in the dissolution velocity has been quantified by using a stack layer structure. Finally using thermal oxidation it has been shown that, due to the selective oxidation as a function of the porosity, porous silicon can be used to produce a Si/SiO2 like structure.
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  • 38
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    Journal of porous materials 7 (2000), S. 335-338 
    ISSN: 1573-4854
    Keywords: porous silicon ; oxidation ; calorimeter ; desorption ; activation energy
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of porous silicon has been studied using differential scanning calorimeter. The oxidation was found to consist of two parts with different activation energies. This indicates the existence of two different reaction mechanism. The results from the hydrogen desorption measurements have been used to study the different oxidation behaviour of the n- and p+-type porous silicon. The results show that the dihydride structure dominates on the surface of the n-type porous silicon, contrary to p+-type porous silicon, where the monohydride is the major structure. Explanations of these features are discussed. Using the activation energy, the surface termination effects are investigated. The best improvement in the activation energy was observed in the sample, whose surface was partially stabilized by ammonium groups.
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  • 39
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    Journal of porous materials 7 (2000), S. 339-343 
    ISSN: 1573-4854
    Keywords: porous silicon ; infrared spectroscopy ; oxidation
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The Si–Si vibrational states near the surface region of porous silicon has been characterized using Fourier Transform Infrared Spectroscopy (FTIR) due to its enlarged surface area. By means of anodic etch and oxidization experiments, two Si–Si vibration modes of porous silicon have been identified as near the surface regions and in the bulk, respectively. The intensity of absorption peak at 620 cm−1, which originates from the Si–Si bonds vibrations on the surface and near surface regions of porous silicon, is found to vary depending on the length of etch and degree of oxidation of porous silicon, which exists before etching and is recovered again after fully oxidation. The peak of 610 cm−1 doesn't change throughout the oxidation experiment, and to be assigned for Si–Si bond vibrations in the bulk. With an extra irradiation of Nd:Yag laser on the PS sample the Raman and FTIR spectra reveal a red shift. These results can give an interpretation to explain the different phenomenon of Si–Si vibrations of Raman and FTIR spectroscopy.
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  • 40
    ISSN: 1573-4854
    Keywords: porous silicon ; oxidation ; liquid crystal
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In this paper we demonstrate the filling of porous silicon (PS) layers with liquid crystals (LC's) in order to control the reflectance electrically. The preparation of PS and the choice of the right group of LC's will be presented. Especially an oxidation of PS is necessary so that the methods and parameters of oxidation will also be discussed. As a first result the increasing and decreasing of the thickness oscillations in the reflectance as a function of the applied voltage can be observed.
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  • 41
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    Journal of porous materials 7 (2000), S. 243-246 
    ISSN: 1573-4854
    Keywords: porous silicon ; oxidation ; refractive index ; optical waveguide ; optical losses
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Further results on the optical properties of oxidised porous silicon as a function of porosity and oxidation conditions are presented in this paper. The refractive index varies logarithmically with the oxidation time irrespective of the porosity of the sample and the oxidation temperature. Burried waveguides have been realised from as-prepared and oxidised porous silicon. Optical losses of 18 dB cm−1 at λ = 1.3 μm have been obtained after oxidation at 800°C for 35 min.
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  • 42
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    Journal of porous materials 7 (2000), S. 139-142 
    ISSN: 1573-4854
    Keywords: porous silicon carbide ; oxidation ; effective medium theory ; infrared reflectance (or IR) ; reststrahlen
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract We present a study of the infrared reflectance of porous silicon carbide (PSC) formed by the electrochemical dissolution of silicon carbide substrates of both 6H and 4H polytypes. The reflectance from n-PSC, both as-anodized and passivated, is reported for the first time. The passivation of PSC has been accomplished using a short thermal oxidation. Fourier transform infrared (FTIR) reflectance spectroscopy is employed ex situ after different stages of the thermal oxidation process. The characteristics of the reststrahlen band normally observed in bulk SiC are altered by anodization; further changes in the reflectance spectra occur following oxidation for different periods of time. An effective medium theory model that includes air, SiC and SiO2 as component materials is shown to characterize the observed changes in the reflectance spectra after different stages of PSC oxidation.
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  • 43
    ISSN: 1573-5176
    Keywords: active oxygen ; blue-green alga ; cyanobacteria ; liposome ; oxidation ; phycobilin ; phycobiliprotein ; phycocyanin ; radical
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The antioxidative activity of phycocyanobilin fromSpirulina platensis was evaluated againstoxidation of methyl linoleate in a hydrophobic systemor with phosphatidylcholine liposomes. Phycocyanobilin as well as phytochemicals includingα-tocopherol, caffeic acid and zeaxanthin,effectively inhibited the peroxidation of methyllinoleate and produced a prolonged induction period.Oxidation of phosphatidylcholine liposomes was alsocontrolled markedly by adding phycocyanobilin orα-tocopherol. Phycocyanobilin was distributedoutside in the liposomes to scavenge radicals fromAAPH and to prevent initiation of radical chainreactions. When the concentrations of phycocyanin andphycocyanobilin in the reaction mixture were adjustedequally on a phycocyanobilin basis, the activity ofphycocyanobilin was almost the same as that ofphycocyanin in the AAPH-containing reaction mixture.The antioxidizing action of phycocyanin prepared fromspray-dried Spirulina almost agreed with thatfrom fresh Spirulina in the AAPH-containingreaction mixture. These results suggest thatphycocyanobilin is responsible for the majority of theantioxidative activity of phycocyanin and may act asan effective antioxidant in a living human body.
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    Chemistry of natural compounds 36 (2000), S. 416-417 
    ISSN: 1573-8388
    Keywords: cotton lignin ; oxidation ; redox catalysts
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The effects of anthraquinone and demethylated lignin on the oxidation of cotton lignin are compared. Results of the estrogen activity of certain aromatic acids are presented.
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    Chemistry of heterocyclic compounds 36 (2000), S. 1359-1360 
    ISSN: 1573-8353
    Keywords: 1,2,5-thiadiazoles ; 1,2,5-selenadiazoles ; oxidation
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    Topics: Chemistry and Pharmacology
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    Chemistry of heterocyclic compounds 36 (2000), S. 870-871 
    ISSN: 1573-8353
    Keywords: sesquiterpene lactones ; britanin ; bigelovin ; oxidation
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    Topics: Chemistry and Pharmacology
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  • 47
    ISSN: 1573-4935
    Keywords: erythrocyte ; macrophage ; oxidation ; mouse
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Membrane protein modification can change cell surface properties which canbe correlated with altered macrophage-erythrocyte interactions. Mouseerythrocytes were incubated in phosphate buffer for different times toinduce protein modification. Mouse erythrocyte membrane changes wereanalyzed by infrared analyses and gel electrophoresis. Proteolyticdigestion of membrane proteins was observed. After 22 hours preliminaryincubation, the number of erythrocytes adhering to a monolayer ofmacrophages reached a maximum, the majority of which had not beenphagocytosed. Most of the erythrocytes incubated for 40 hours underwentphagocytosis after adhesion to the macrophages.
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  • 48
    ISSN: 1573-904X
    Keywords: methionine-enkephalin ; oxidation ; solid state ; secondary ion mass spectrometry ; peptide stability ; methionine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. A surface sensitive mass spectrometric technique: Time ofFlight Secondary Ion Mass Spectrometry (ToF-SIMS) was introducedto study the solid state instability of a methionine containing peptidecaused by the oxidation of the methionine residue. Methods. The oxidation of a neuropeptide Methinonine-Enkephalin(ME) in air and under UV acceleration was studied by ToF-SIMS. Results. The apparent oxidation rate is defined by the peak ratio ofoxidized molecular ion over unoxidized molecular ion. ME is oxidizedat a faster rate to its sulfoxide derivative in the UV accelerated oxidationenvironment than in lab air. The calibration curve for evaluating theionization probability ratio of the oxidized deprotonated molecular iondivided by the unoxidized deprotonated molecular ion was obtained.This could be used to extract the real oxidation rate of ME in thesolid state. Conclusions. The preliminary results showed that ToF-SIMS with simplesample handling, fast data acquisition, together with excellentsurface sensitivity and detection limit could be an applicable and convenienttool to study peptide reactions in the solid state such as oxidationand deamidation process.
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  • 49
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    Powder metallurgy and metal ceramics 39 (2000), S. 560-562 
    ISSN: 1573-9066
    Keywords: niobium ; coating ; silicon ; corrosion ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Coatings based on TiSi2 have been used to protect niobium alloys from corrosion at temperatures up to 1300°C. Kinetic oxidation curves are given for these coatings on niobium. The phase compositions of the coatings have been determined and also of the layers formed during oxidation. EPMA has been applied to the element distributions in the coating, from which it is concluded that the silicon is mobile. The high resistance to oxygen of coatings based on TiSi2 is due to the formation of films of TiO2 and SiO2 on them.
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    Topics in catalysis 11-12 (2000), S. 195-204 
    ISSN: 1572-9028
    Keywords: 3-fluorotoluene ; 3-fluorobenzaldehyde ; iron molybdate ; Fe–Mo/boralite ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The gas-phase selective synthesis of 3-fluorobenzaldehyde from 3-fluorotoluene over bulk iron molybdate and Fe–Mo oxide in a host boralite sample is described. The latter samples, prepared by adding Fe and Mo by chemical vapor deposition to the boralite, show high selectivity in oxidation, making yields of 3-fluorobenzaldehyde of over 40% possible. The pretreatment of the zeolite to eliminate extra-framework boron improves behavior, and secondary post-addition of molybdenum by CVD to increase the Mo/Fe ratio in the catalyst has a similar enhancing effect. The behavior of Fe–Mo/boralite samples proves significantly better, in terms of both specific activity (per mass of active phase) and selectivity, than bulk Fe2(MoO4)3, but at high conversion lower selectivities are found probably due to the presence of limitations in the backdiffusion of 3-fluorobenzaldehyde.
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    Topics in catalysis 11-12 (2000), S. 213-222 
    ISSN: 1572-9028
    Keywords: CaO ; MgO ; carbon monoxide complexes ; oxidation ; adsorption calorimetry
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The heat evolved during the adsorption and oligomerization of CO on outgassed CaO and MgO has been determined with a heat-flow calorimeter. The chemisorbed complexes formed include highly-conjugated (CO) n 2 anions which impart colour to the oxides. The reaction of these complexes with oxygen has been quantified calorimetrically and correlated with changes observed spectroscopically.
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    International journal of infrared and millimeter waves 21 (2000), S. 31-37 
    ISSN: 1572-9559
    Keywords: HgCdTe ; oxidation ; surface treatment ; passivation ; XPS
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract This report presents a surface pre-treatment method of LPE HgCdTe epilayer to reduce and remove the oxides and contaminants. The surface oxidative characterization of LPE HgCdTe epilayer has been studied by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). HgCdTe surface exposed by various processing steps has been measured and analyzed, the results show the native oxide film can be removed by the solution of lactic acid in ethylene glycol after etching by bromine in absolute ethyl alcohol. It indicates that the mainly optical and electrical parameters of LPE HgCdTe epilayer have not been changed. It is evident that the pre-treatment before HgCdTe surface passivation affects the passivant/HgCdTe interface properties.
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  • 53
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    Water, air & soil pollution 118 (2000), S. 13-26 
    ISSN: 1573-2932
    Keywords: aeration ; decomposition ; nitrite ; nitrogen oxides ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract Studies on the decomposition/oxidation of nitrite at differentpH values and aeration flow rates were investigated using abench-scale batch reactor. The conditions were pH 2.85, 3.50,5.80, 7.0, and 11.6, and with or without aeration at airflowrates of 1.50, 2.25, and 3.25 L min-1.Decomposition/oxidation of nitrite may be described by apseudo-first order expression, and the rate constants fornitrite decomposition/oxidation ranged from 1.2 ×10-6 s-1 to 1.12 × 10-4 s-1 depending on the experimental conditions. The rate ofdecomposition/oxidation of nitrite was found to increase for lowpH conditions and for high airflow rates. The experimentalresults showed that the dominant reaction in thedecomposition/oxidation of nitrite in low pH solutions and inthe presence of some aeration was most probably thedecomposition of nitrous acid to NO and NO2. Oxidation ofnitrite to nitrate appeared to proceed in a smaller proportionin comparison to the breakdown of nitrous acid to nitrogen oxidecompounds. Results from this study showed that emissions ofnitrogen oxides from nitrite-containing solutions are possible ifthe solutions were agitated and the pHs of the solutions wereless than 6.
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  • 54
    ISSN: 1573-4854
    Keywords: oxidized porous silicon ; anodization ; oxidation ; dielectric isolation ; optical waveguide
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A brief review of 20-years research of formation, processing and utilizing of oxidized porous silicon (OPS) is presented. Electrolytes to form porous silicon (PS) layers, special features of PS chemical cleaning and thermal oxidation are discussed. OPS application for dielectric isolation of components of bipolar ICs and for the formation of silicon-on-insulator structures has been demonstrated. Although these OPS-based techniques have found limited current commercial use, experience gained is applicable to the fabrication of optoelectronic devices. Specifically, integrated optical waveguides based on OPS have been developed.
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    Journal of porous materials 7 (2000), S. 63-66 
    ISSN: 1573-4854
    Keywords: porous silicon ; oxidation ; IR spectroscopy ; vibrational analysis
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Oxidation behavior of porous silicon under various environments of dry and wet air, and solution with and without appropriate oxidant at mild temperatures has been investigated. The progress of oxidation was followed by infrared spectroscopy. The presence of water vapor greatly accelerates the oxidation rate in comparison with the rate in dry air. The oxidized states are clarified with the help of oxidation experiments of partially hydrogen-desorbed porous silicon, which does not contain SiH2 and SiH3 as the hydride species. An oxidation mechanism is proposed to explain that oxidation is accelerated in the presence of water vapor and at the partially hydrogen-desorbed porous silicon. Further, oxidation behavior of porous silicon in solution containing appropriate oxidant is also investigated. The rate is very rapid and the oxidation does not produce the back-bond oxidized state of OySiHx in contrast to the oxidation in air.
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    Reaction kinetics and catalysis letters 69 (2000), S. 31-38 
    ISSN: 1588-2837
    Keywords: MMH ; oxidation ; gas-phase ; oxygen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The objective of this study is to characterize the lifetime of monomethylhydrazine mixed with O2, both in the gas phase, at 298 K. A detailed kinetic model has been built to allow a numerical study of the homogeneous MMH/O2 reactivity.
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    Reaction kinetics and catalysis letters 71 (2000), S. 115-120 
    ISSN: 1588-2837
    Keywords: Mechanism ; oxidation ; alkylperoxo complexes ; vanadium ; NMR spectroscopy
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Using 51V, 17O, 13C and 1H NMR spectroscopy, vanadium(V) alkylperoxo complexes VO(OOtBu)k(OnBu)3-k, where k = 1, 2 and 3, were characterized in the reaction of VO(OnBu)3 with tBuOOH in CH2Cl2.
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  • 58
    ISSN: 1588-2837
    Keywords: Hydrogen sulfide ; oxidation ; iron compounds
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The correlation of the state of iron in supported Fe/Al2O3 catalysts with catalytic properties in H2S oxidation, studied by Mössbauer spectroscopy, indicates that the Fe oxide particles promote the formation of sulfur, whereas FeS2 catalyzes the H2S oxidation to SO2.
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    Reaction kinetics and catalysis letters 71 (2000), S. 319-323 
    ISSN: 1588-2837
    Keywords: Benzene ; oxidation ; aqueous phase
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Aqueous phase heterogeneous catalytic oxidation of benzene by dissolved oxygen is reported. Using a bimetallic platinum-ruthenium catalyst supported on a high surface area activated carbon, good conversions were obtained at temperatures above 100°C and space-times greater than 40 seconds. Complete conversion of benzene to carbon dioxide and water was achieved at 100°C with a reactor space-time of 300 s.
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    Reaction kinetics and catalysis letters 69 (2000), S. 247-252 
    ISSN: 1588-2837
    Keywords: Phosphorous acid ; oxidation ; kinetics ; mechanism
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of lower phosphorus oxyacids by benzyltrimethylammonium chlorobromate (BTMACB) proceeds by a mechanism involving a hydride-ion transfer from oxyacids to the oxidant in the rate-determining step.
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    Reaction kinetics and catalysis letters 69 (2000), S. 369-374 
    ISSN: 1588-2837
    Keywords: Thioacids ; oxidation ; mechanism ; hexamethylenetetramine-bromine
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Oxidation of thioacids by hexamethylenetetramine-bromine proceeds through an intermediate complex in the pre-equilibrium and its subsequent decomposition in the slow step.
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    International journal of peptide research and therapeutics 7 (2000), S. 347-351 
    ISSN: 1573-3904
    Keywords: chromogenic substrates ; oxidation ; Oxone® ; para-nitroanilides ; solid-phase synthesis
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A new strategy has been developed for the rapid synthesis ofpeptide para-nitroanilides (pNA). The method involves derivatization of commercially available tritylchloride resin(TCP-resin) with 1,4-phenylenediamine, subsequent coupling withdesired amino acids by the standard Fmoc protocol, and oxidationof the intermediate para-aminoanilides (pAA) with Oxone®. This procedure allows easy assembly of the desired para-aminoanilides (pAA) on standard resin and efficient oxidation and purification of the corresponding para-nitroanilides (pNA). The method allows easy access to any desired peptide para-nitroanilides, which are useful substrates for the characterization and study of proteolytic enzymes.
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    International journal of peptide research and therapeutics 7 (2000), S. 347-351 
    ISSN: 1573-3904
    Keywords: chromogenic substrates ; oxidation ; Oxone® ; para-nitroanilides ; solid-phase synthesis
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    Topics: Chemistry and Pharmacology
    Notes: Summary A new strategy has been developed for the rapid synthesis of peptide para-nitroanilides (pNA). The method involves derivatization of commercially available tritylchloride resin (TCP-resin) with 1,4-phenylenediamine, subsequent coupling with desired amino acids by the standard Fmoc protocol, and oxidation of the intermediate para-aminoanilides (pAA) with Oxone®. This procedure allows easy assembly of the desired para-aminoanilides (pAA) on standard resin and efficient oxidation and purification of the corresponding para-nitroanilides (pNA). The method allows easy access to any desired peptide para-nitroanilides, which are useful substrates for the characterization and study of proteolytic enzymes.
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    Chemistry of heterocyclic compounds 36 (2000), S. 885-898 
    ISSN: 1573-8353
    Keywords: 2,3-dihydroimidazo[1,2-a]pyridines ; reduction ; nucleophilic reactions ; oxidation ; electrophilic reactions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Published data on the physical and chemical characteristics of 2,3-dihydroimidazo[1,2-a]pyridines to 1998 are reviewed.
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  • 65
    ISSN: 1572-8773
    Keywords: acidophilic ; strain ; oxidation ; kinetics
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    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Recovery of metal values from sulfide ores by use of acidophilic microorganisms is gaining importance. A number of commercial/pilot plants are setup to find out the techno-economic feasibility of the overall process. The main drawback in the process is the slow kinetics of dissolution of metal values from the sulfide ores. To make the technology e attractive the kinetics should be improved considerably. There are various factors which determine the overall kinetics such as bacterial activity and concentration, iron and sulfur oxidation, oxygen consumption, reactor design and nature of ore. A brief review has been made dealing with the above parameters
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  • 66
    ISSN: 1572-879X
    Keywords: propane ; oxidation ; calcium-based catalysts ; tetrachloromethane
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of propane has been investigated in the presence and absence of tetrachloromethane (TCM) on calcium hydroxyapatite (CaHAp), Ca3(PO4)2, CaSO4 and CaO at 723 K. In the absence of TCM, the conversion of C3H8 on CaHAp was 7.7–9.2% during 6 h on-stream while that on Ca3(PO4)2, CaSO4 and CaO was 0.6, 0 and 0.2–0.4%, respectively. The principal products on all catalysts in the absence of TCM were CO and CO2 with small selectivities to C3H6 and C2H4 (both 5–6%) observed on CaHAp. Upon addition of TCM, the selectivity to C3H6 on all catalysts and the conversion of C3H8 on CaSO4 increased while, with increasing time-on-stream, the changes in the conversion and selectivity were dependent upon the nature of the catalysts. XPS and XRD analyses provide evidence for the presence of chlorine in the surface and/or bulk of three of the catalysts, suggesting that chlorinated species on the solids play a role in the selectivity enhancement, but the absence of chlorine from the sulphate demonstrates the dissimilarities of the catalysts in their abilities to sorb and decompose TCM.
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  • 67
    ISSN: 1572-879X
    Keywords: methane ; oxidation ; strontium hydroxyapatite ; lead hydroxyapatite ; tetrachloromethane
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of methane has been investigated on lead hydroxyapatite (PbHAp), strontium hydroxyapatite (SrHAp) and their binary mixtures at 873 K. PbHAp showed no activity for the oxidation of methane, while SrHAp produced carbon monoxide selectively at 2–4% conversion. On binary mixtures of the hydroxyapatites the conversion of methane and the selectivity to C2 compounds reached values higher than those of the separate constituents of the mixture. With tetrachloromethane in the feed stream a similar synergistic effect was observed with conversions of methane and selectivities to CH3Cl higher on the binary mixtures than those on either SrHAp or PbHAp. The strontium-containing hydroxyapatite appears to play a crucial role in the activation of methane, while the presence of the lead-containing analogue is apparently required for the minimization of undesirable processes involving methyl radicals.
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    Catalysis surveys from Japan 3 (1999), S. 55-60 
    ISSN: 1572-8803
    Keywords: acetic acid ; oxidation ; Pd ; heteropoly acid ; ethylene
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A new process for acetic acid production by direct oxidation of ethylene which was established and commercialized is described. The catalyst system consisting of Pd and heteropoly acid exhibits excellent activity and selectivity. The addition of Se or Te to the catalyst system is effective to suppress the formation of carbon dioxide. This new process is applicable to a plant of a wide range of size corresponding to the local demand. Because this new process produces little waste water, it is very friendly to the environment.
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    Catalysis letters 57 (1999), S. 109-113 
    ISSN: 1572-879X
    Keywords: superacid ; zirconia ; molybdenum oxide ; methane ; oxidation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A series of zirconia-supported molybdenum oxide catalysts with different molybdenum loadings prepared using conditions reported to generate “superacidity” have been evaluated for their performance as catalysts for methane oxidation. A marked dependence of Mo content on activity has been observed, with the most active material being that with intermediate molybdenum content. 5 wt% MoO3/ZrO2 compares favourably with ZrxCe1-xO2 for methane combustion. The presence of MoO3 is observed to stabilise the tetragonal polymorph of ZrO2 and, as Mo content is increased, dispersed MoO3 crystallites are formed as evidenced by Raman spectroscopy. Temperature-programmed reduction studies evidence differences in the reduction behaviour of the materials as a function of loading. The results indicate that molybdenum oxide supported on monoclinic zirconia gives rise to the most active catalyst. It is tentatively suggested that the formation of a MoO3 monolayer during reaction may be of importance.
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    Catalysis surveys from Japan 3 (1999), S. 27-35 
    ISSN: 1572-8803
    Keywords: oxidation ; oxygen ; alkane ; N‐hydroxyphthalimide ; radical catalyst
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A practical catalytic method to convert alkanes into the corresponding oxygen‐containing compounds with O2 under mild conditions using N‐hydroxyphthalimide (NHPI) in the presence or absence of a transition metal was developed. Thus, cyclohexane was successfully converted into adipic acid in good conversion and selectivity by a combined catalytic system consisting of NHPI and Mn(acac)2. Lower alkane such as isobutane was converted into t‐butyl alcohol (83%) under 10 atm of air by NHPI‐Co(OAc)2 system. Alkylbenzene such as toluene was oxidized to benzoic acid in high yield (81%) under normal temperature and pressure of dioxygen in the presence of a catalytic amount of NHPI and Co(OAc)2. ESR measurements showed that phthalimide‐N‐oxyl generated from NHPI under dioxygen atmosphere is a key species in this oxidation and functions as a radical catalyst.
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    Journal of solid state electrochemistry 3 (1999), S. 179-186 
    ISSN: 1433-0768
    Keywords: Key words Cathodic protection system ; Carbon ; oxidation ; Composite carbon/polymer anode ; Lifetime
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The suitability of a polymeric composite material for use as part of an anode structure in a cathodic protection system has been examined. The composite material was a conductive blend (volume resistivity typically 1.5 Ω cm) of carbon black in a polyethylene binder. A long operational lifetime for the material demands that the rate of carbon loss must be low. In the work reported here, electrochemical and in situ analytical techniques were employed to characterise the performance of the material over a wide range of anodic current densities in a variety of aqueous electrolytes. The predominant anodic electrochemical reaction on the polymeric material is CO2 formation in acid and neutral solutions, which causes loss of carbon from the surface and the development of a non-conducting layer of polyethylene. The characteristics of the reaction suggest that it occurs via the discharge of H2O. In alkaline pH, however, the anodic reactions are more complex. A high OH− concentration (pH 12 or higher) favours the formation of oxygen rather than CO2, particularly at low anodic potentials. The presence of CO3 2− in the electrolyte catalyses the evolution of oxygen at pH values as low as 9. The electrochemical formation of oxygen always occurs in parallel with the generation of some humic acid in the solution.
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  • 72
    ISSN: 1432-072X
    Keywords: Key words Heterologous expression ; Methane ; oxidation ; Methane monooxygenase ; Methanotroph ; Regulation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The methanotrophs Methylococcus capsulatus (Bath) and Methylosinus trichosporium OB3b contain particulate methane monooxygenase (pMMO) and soluble methane monooxygenase (sMMO) genes. Other methanotrophs such as Methylomicrobium album BG8 and Methylocystis parvus OBBP contain only pMMO genes. Although molecular genetic techniques are poorly developed in methanotrophs, sMMO genes were expressed in methanotrophs normally containing only pMMO genes. This was achieved by conjugation using broad-host-range plasmids containing the native promoter and sMMO genes from Mc. capsulatus (Bath) and Ms. trichosporium OB3b. sMMO genes derived from Ms. trichosporium OB3b were expressed in an active form in Mcy. parvus OBBP and in Mm. album BG8. Therefore, all of the genes required for active sMMO synthesis were contained on the broad-host-range plasmids and were expressed in the heterologous hosts. Constitutive synthesis of pMMO was observed in Mm. album BG8 when grown at high and low copper-to-biomass ratios, while transcription of the recombinant sMMO genes was only observed under growth conditions of low copper-to-biomass ratios. Therefore, the regulatory protein(s) for sMMO synthesis was also present on the plasmid used, or the heterologous host contained a regulatory system for sMMO. Expression of sMMO genes in methanotrophs containing only pMMO will assist further investigations on the expression and regulation of MMO genes in methanotrophs.
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    Journal of thermal analysis and calorimetry 57 (1999), S. 875-881 
    ISSN: 1572-8943
    Keywords: charge transfer ; Kelvin probe ; oxidation ; work function ; zirconia
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The extent of the surface charge, that develops during oxidation of zirconia, is determined using work function measurements for both bulk specimen and thin films. The bulk specimen of yttria-doped zirconia (10 mol%) exhibits maxima of the surface electrical effect at 373 and 973 K (130 and 280 mV, respectively) that can be considered in terms of oxygen chemisorption and oxygen non-stoichiometry. Thin film of undoped zirconia exhibits a maximum at 473 K (260 eV). Addition of yttria (10 mol%) to the thin film results in a substantial reduction of the maximum, to about 140 eV, that is shifted up to 600 K.
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    Journal of thermal analysis and calorimetry 57 (1999), S. 473-486 
    ISSN: 1572-8943
    Keywords: cumene ; oxidation ; polymerization ; quinone-amine inhibitors ; solution microcalorimetry ; styrene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The application of solution microcalorimetry was demonstrated on two model examples – inhibited oxidation of cumene and radical polymerization of styrene. From the experimental dependences of the rate of heat release on time, the rate constants k 7 of the interaction of an inhibitor with radicals of substrate (RO 2 . or R.) in oxidation or in polymerization were determined for the set of inhibitors of N-aryl N-(2-quinone) amine series. It was shown that these compounds are weak inhibitors of oxidation of cumene and rather efficient inhibitor of polymerization of styrene.
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    Plasma chemistry and plasma processing 19 (1999), S. 131-151 
    ISSN: 1572-8986
    Keywords: Styrene ; oxidation ; silent discharge ; plasma ; dielectric barrier
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract A silent discharge plasma reactor has been developed to study the oxidation of styrene vapor in argon/oxygen mixtures. A number of analytical techniques were employed to determine the destruction efficiency and to characterize the intermediate products. The destruction efficiency was measured as a function of initial styrene concentration, temperature, and energy density of the plasma. The formation of solid products was observed in most experiments. At low temperature (100°C), the solid deposit was polymeric in nature, while at high temperature (300°C) the solid appeared to be amorphous carbon. A combination of high temperature and high energy density resulted in high destruction efficiency and minimal production of solid films. The destruction efficiency vs. energy density is shown to be more complex than a simple model predicting exponential behavior. Several reasons for the discrepancy are suggested. The “e-folding” energy density for the destruction of styrene is compared to literature values for other organic compounds, measured using similar types of plasma reactors.
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    Plasma chemistry and plasma processing 19 (1999), S. 383-394 
    ISSN: 1572-8986
    Keywords: Nonthermal plasma ; benzene ; Al2O3 ; BaTiO3 ; oxidation ; absorption ; atmospheric pressure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract The combination of plasma discharge and adsorption was examined for oxidation of dilute benzene in air in a plasma reactor packed with a mixture of BaTiO 3 pellets and porous Al 2 O 3 pellets (i.e., an alumina hybrid reactor). The oxidative decomposition of benzene was enhanced by the benzene concentrating on the Al 2 O 3 pellets. Furthermore, there was a higher selectivity to CO 2 in the products from the hybrid than from a plasma reactor packed with BaTiO 3 pellets alone. The presence of the Al 2 O 3 pellets suppressed the formation of N 2 O.
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    Plasma chemistry and plasma processing 19 (1999), S. 421-443 
    ISSN: 1572-8986
    Keywords: Streamer corona ; NO x removal ; nonthermal plasma ; oxidation ; reduction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract In this paper, the NO-to-NO 2 conversion in various gaseous mixtures is experimentally investigated. Streamer coronas are produced with a dc-superimposed high-frequency ac power supply (10–60 kHz). According to NO x removal experiments in N 2 +NO x and N 2 +O 2 +NO x gaseous mixtures, it is supposed that the reverse reaction NO 2 +O→NO+O 2 may not only limit NO 2 production in N 2 +NO x mixtures, but also increase the energy cost for NO removal. Oxygen could significantly suppress reduction reactions and enhance oxidation processes. The reduction reactions, such as N+NO→N 2 +O, induce negligible NO removal provided the O 2 concentration is larger than 3.6%. With adding H 2 O into the reactor, the produced NO 2 per unit removed NO can be significantly reduced due to NO 2 oxidation. NH 3 injection could also significantly decrease the produced NO 2 via NH and NH 2 - related reduction reactions. Almost 100% of NO 2 can be removed in gaseous mixtures of N 2 +O 2 +H 2 O+NO 2 with negligible NO production.
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    Molecular and cellular biochemistry 194 (1999), S. 257-263 
    ISSN: 1573-4919
    Keywords: glycation ; oxidation ; collagen ; diabetes ; free radicals
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract The present investigation was carried out to understand the effect of metal catalyzed oxidation on glycation and crosslinking of collagen. Tail tendons obtained from rats weighing 200-225 g were incubated with glucose (250 mM) and increasing concentrations of copper ions (5, 25, 50 and 100 μM) under physiological conditions of temperature and pH. Early glycation, crosslinking and late glycation (fluorescence) of collagen samples were analyzed periodically. Early glycation was estimated by phenol sulfuric acid method, and the crosslinking was assessed by pepsin and cyanogen bromide digestion. A concentrationdependent effect of metal ions on the rate of glycation and crosslinking of collagen was observed. Tendon collagen incubated with glucose and 100 μM copper ions showed 80% reduction in pepsin digestion within seven days, indicating extensive crosslinking, whereas collagen incubated with glucose alone for the same period showed only 7% reduction. The presence of metal ions in the incubation medium accelerated the development of Maillard reaction fluorescence on collagen, and the increase was dependent on the concentration of metal ions used. The metal chelator Diethylene triamine penta-acetate significantly prevented the increase in collagen crosslinking by glucose and copper ions. Free radical scavengers benzoate and mannitol effectively prevented the increased crosslinking and browning of collagen by glucose. The results indicate that the metal catalyzed oxidation reactions play a major role in the crosslinking of collagen by glucose. It is also suggested that the prevention of increased oxidative stress in diabetes may prevent the accelerated advanced glycation and crosslinking of collagen.
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  • 79
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    Molecular and cellular biochemistry 200 (1999), S. 103-109 
    ISSN: 1573-4919
    Keywords: sugar cataract ; dulcitol ; glycation ; oxidation ; pyruvate ; ethyl pyruvate ; attenuation effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Studies describe an attenuation of sugar cataract formation by topical administration of ethyl pyruvate. Cataract formation was induced by feeding young rats a 30% galactose diet. Mature cataracts appeared in about thirty days. Instillation of the eye drops containing 5% ethyl pyruvate decelerated the process significantly. Biochemically, the effect was reflected by lowering in the contents of dulcitol and glycated proteins. The ATP levels were also higher in comparison to the placebo treated group. The effects are hence attributable to the effect of pyruvate in inhibiting dulcitol synthesis and protein glycation, in addition to its antioxidant properties and metabolic support. The use of esterified pyruvate instead of the unesterified pyruvate was preferred because of its greater penetration through the cornea and consequently a higher concentration attained in the aqueous humor.
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  • 80
    ISSN: 1572-9028
    Keywords: ellipsometry ; carbon monoxide ; methane ; palladium ; palladium oxide ; oxidation ; oscillations ; catalyst
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Spectroscopic ellipsometry is used to monitor the surface of a thick Pd‐film catalyst during the oxidation of either carbon monoxide or methane. Dense PdO layers form under sufficiently lean conditions (excess oxygen) for both reactions. A stable metal surface exists in the case of CO, but a very porous PdO layer develops in the case of methane, under rich conditions. There is a large hysteresis in the conditions for PdO formation in the case of CO oxidation. Spontaneous oscillations in catalytic activity and Pd‐surface composition occur for both reactions, the higher activities corresponding to O‐atom‐rich or PdO‐rich surfaces for CO or methane oxidation, respectively.
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  • 81
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    Topics in catalysis 8 (1999), S. 45-55 
    ISSN: 1572-9028
    Keywords: Raman spectroscopy ; surface‐enhanced Raman spectroscopy ; oxidation ; synergy effects ; oxygen exchange ; oxidative coupling of methane ; nitric oxide decomposition ; methanol oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Advantages and limitations of laser Raman spectroscopy (LRS) as an in situ vibrational spectroscopy for the study of catalytic materials and surfaces under working conditions are discussed. Measurements can be carried out at temperatures as high as 1200 K in controlled atmospheres. Modern instrumentation permits time resolutions in the sub‐second regime for materials with high Raman cross sections. Transient studies are thus possible. Several examples are presented of in situ LRS studies including the phase analysis of bismuth molybdate and VPO oxidation catalysts, synergy effects and oxygen exchange in Sb2O3/MoO3 oxide mixtures, intermediates in oxidative coupling of methane, NO decomposition on Ba/MgO catalysts, and transient SERS studies of partial oxidation of methanol on Ag single crystal surfaces and of the reduction of oxide overlayers on electrodeposited Rh layers.
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  • 82
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    Journal of sol gel science and technology 14 (1999), S. 75-86 
    ISSN: 1573-4846
    Keywords: silicon oxycarbide ; BlackglasTM ; ceramic matrix composites ; 29Si NMR ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract BlackglasTM polysiloxane systems produce silicon oxycarbide glasses by pyrolysis in inert atmosphere. The silicon oxycarbides evidence oxidative degradation that limits their lifetime as composite matrices. The present study characterizes bonding rearrangements in the oxycarbide network accompanying increases in pyrolysis temperature. It also addresses the changes in susceptibility to oxidation due to variations in the distribution of Si bonded species obtained under different processing conditions. The study is carried out using 29Si nuclear magnetic resonance (NMR) spectroscopy and a design of experiments approach to model the oxidation behavior. The NMR results are compared with those obtained by thermogravimetric analysis (TGA). Samples pyrolyzed under inert conditions are compared to those pyrolyzed in reactive ammonia environments.
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  • 83
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    Journal of sol gel science and technology 14 (1999), S. 49-68 
    ISSN: 1573-4846
    Keywords: silicon oxycarbide ; oxidation ; silsesquioxane ; preceramic
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract We have undertaken a systematic study of the oxidation chemistry for a range of SiOC ceramics derived from silsesquioxane polymeric precursors. This study examines the oxidation for 500 hours at 600, 800, 1000 and 1200°C for four SiOC powders. The material changes upon oxidation were characterized qualitatively by color change and optical microscopy and quantitatively by weight and composition change. In this study we employ a very easy method that uses the weight change upon oxidation and a carbon analysis after oxidation to arrive at the composition of the oxidized SiOC. Combined these qualitative and quantitative techniques have shown that on oxidation at 800 and 600°C the SiOC composition is more rapidly changed to that of silica than oxidation over the same time frame at 1000 or 1200°C. The data indicates that this difference is due to the relative rates of oxidation of the excess carbon versus the Si—C bonds in the SiOC. At lower temperatures initially the carbon oxidation predominates which leads to higher porosity throughout the material and an increase in the surface area with eventually ‘complete’ oxidation to silica. At higher temperatures the Si—C bond oxidation rate is comparable to the rate of oxidation of carbon. This allows a silica-like surface to build up on the SiOC, which slows all subsequent reactions due to the necessity to diffuse O2 in and COx out of the bulk. Under these oxidation conditions materials that originally contain high amounts of excess carbon are more quickly oxidized to silica than those that contain minimal amounts of excess carbon, as confirmed by elemental analysis and optical microscopy. Regardless of the time or temperature of the oxidation conditions no materials were found to be completely stable to oxidation. SiOC materials with low levels of excess carbon showed the best resistance to change upon oxidation.
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  • 84
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    Physics and chemistry of minerals 26 (1999), S. 506-512 
    ISSN: 1432-2021
    Keywords: Key words Anapaite ; Mössbauer spectroscopy ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract Mössbauer spectra (MS) of anapaite (Ca2 Fe2+(PO4)2 · 4H2O) and of a sample after being immersed in a 4% H2O2 solution at room temperature (RT) over 12 days (hereafter an4ox) were collected at temperatures in the range 4.2 to 420 K and 11 to 300 K respectively. All MS consist of symmetrical doublets, hence magnetic ordering was not observed. The temperature dependencies of the Fe2+ centre shifts of anapaite and an4ox were analysed with the Debye model for the lattice vibrations. The characteristic Mössbauer temperatures were found as 370 K ± 25 K and 340 K ± 25 K, and the intrinsic isomer shifts as 1.427 ± 0.005 mm/s and 1.418 ± 0.005 mm/s respectively. From the external-field (60 kOe) MS recorded at 4.2 and 189 K for the non-treated sample, the principal component V zz of the electric field gradient (EFG) is determined to be positive and the asymmetry parameter η ≈ 0.2 and 0.4 respectively. The temperature variations of the quadrupole splittings, ΔE Q(T), cannot be interpreted on the basis of the thermal population of the 5 D electronic levels resulting from the tetragonal compression of the O6 co-ordination. The low-temperature linear behaviour of ΔE Q(T) is attributed to a strong orbit-lattice coupling. A field of 60 kOe applied to anapaite at 4.2 K produces magnetic hyperfine splitting with effective hyperfine fields of −136, −254 and −171 kOe along the principal axes Ox, Oy and Oz of the EFG tensor respectively. Additional oxidation treatments in solutions with various H2O2 concentrations up to 20% and subsequent Mössbauer experiments at room temperature, have revealed that the anapaite structure is not sensitive to oxidation since eventually only a small amount of Fe2+ (∼6.5%) is converted into Fe3+.
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  • 85
    ISSN: 1572-8978
    Keywords: Plasma polymers ; oxidation ; XPS ; photoelectron binding energy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract The incorporation of oxygen into nitrogen-containing plasma deposited polymers was studied by X-ray Photoelectron Spectroscopy (XPS). As the oxygen content of the plasma polymer increased, the binding energy of the N 1s photoelectrons increased. Conversely, the binding energy of the O 1s photoelectrons was inversely proportional to the nitrogen content of the plasma polymer. The data from a large number of samples all obeyed the same “universal” correlations of photoelectron binding energy versus chemical composition. The data were described by the same curve regardless of whether the oxygen was incorporated rapidly into the thin film during plasma deposition or whether the oxygen was added slowly during spontaneous oxidation of the film in air. This implies that the same thermodynamic principles of radical reactions governed the addition of oxygen to the plasma polymer. The shift in the O 1s and N 1s photoelectron binding energies as a function of chemical composition was used to monitor the proximity of nitrogen and oxygen. By contrasting the experimental data with a simple binomial model which described the random addition of oxygen to a lattice containing carbon and nitrogen, we were able to show that oxygen was preferentially added near nitrogen-containing groups in plasma polymers.
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  • 86
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    Journal of chemical ecology 25 (1999), S. 611-628 
    ISSN: 1573-1561
    Keywords: Terrestrial isopods ; Oniscidea ; Porcellio scaber ; phenolics ; hydrolysis ; oxidation ; detoxification ; hindgut cuticle ; gut microbiota ; hepatopancreatic bacteria
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract When adults of Porcellio scaber fed on litter prior to an artificial diet containing 5% of commercially available tannic acid, 55% of the ingested galloylglucose esters was excreted unchanged, about 25% was hydrolyzed, and 20% was oxidized during the gut passage. After reducing the counts of microorganisms in the gut of P. scaber, the data obtained indicated an important role of ingested platable microorganisms in hydrolyzing gallotannins. Oxidation of phenolics appeared to be mainly due to the endosymbiotic bacteria of the hepatopancreas. Microbial counts in the hindgut were strongly reduced by ingested galloylglucose esters, while gallic acid in the diet (2%) reduced the number of palatable fungi and bacteria less strikingly, and increased the total number of the gut microbiota. Hepatopancreatic bacteria were only slightly affected by ingested tannic acid, since the hepatopancreas contained only few galloylglucose esters. This may be due to the permeability of the hindgut cuticle: the cuticle of the anterior hindgut was freely permeable to gallic acid, while it was nearly impermeable to larger polyphenols. The cuticle of the posterior hindgut was permeable to only about 4% of the gallic acid present in the hindgut lumen. The results are discussed with respect to potentially harmful effects of ingested hydrolyzable tannins and their digestion in Porcellio scaber.
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  • 87
    ISSN: 1573-0867
    Keywords: elemental sulphur ; oxidation ; organic S ; mineralization ; immobilization ; S fertilizers ; semiarid soils ; subtropical region
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The increasing sulphur (S) deficiency in soils of several parts of world has led to the use of fertilizer S, an important factor in enhancing the production and quality of crops. Very limited information is available on the use of elemental sulphur (S0) as a fertilizer, its oxidation into SO42- and transformation into organic S in semiarid subtropical soils. We studied the impact of three temperature regimes on the mineralization of soil organic S, and the oxidation and immobilization of S0 in acidic (pH 4.9), neutral (pH 7.1) and alkaline (pH 10.2) subtropical soils of north-western India. Repacked soil cores were incubated under aerobic conditions (60% water-filled pore space) for 0, 14, 28 and 42 d with and without incorporated S0 (500 μg g-1 soil). Temperature had profound effects on all three soils processes, the rates of mineralization of native soil organic S, oxidation of applied S0 and transformation of S0 into soil organic S being greatest at 36 °C, irrespective of soil pH. Mineralization of native soil organic S (without added S0) resulted in the accumulation of 39, 66 and 47 μg SO42-–S g-1 soil in acidic, neutral and alkaline soil in 42 d period at 36 °C. Of the total mineralization, the majority (62 – 74%) occurred during the first 14 d period. Oxidation rate of added S0 during initial 14 d period at 36 °C was highest in alkaline soil (292 μg S cm-2 d-1), followed by neutral soil ((180 μg S cm-2 d-1) and lowest in acidic soil (125 μg S cm-2 d-1). Of the applied 500 μg S0 g-1 soil, 3.2 – 10.0%, 6.8 – 15.4% and 10.0 – 23.0% oxidized to SO42-, and 13.4 – 28.6%, 16.0 – 29.0% and 14.6 – 29.0% were transformed into organic S in 42 d period in acidic, neutral and alkaline soil, respectively. The results of our study suggest that in order to synchronize the availability of S with plant need, elemental S may be applied well before the seeding of crops, especially in acidic soil and in regions where temperature remains low. Substantial mineralization of native soil organic S in the absence of applied S0 and immobilization of applied S0 into organic S suggest that the role of soil biomass as source and sink could be exploited in long term S management.
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  • 88
    ISSN: 1572-9729
    Keywords: Diphenyl ether ; ligninolytic enzymes ; metabolites ; oxidation ; Trametes versicolor ; white-rot fungi
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Energy, Environment Protection, Nuclear Power Engineering , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The white-rot fungi Trametes versicolor SBUG 1050, DSM 11269 and DSM 11309 are able to oxidize diphenyl ether and its halogenated derivatives 4-bromo- and 4-chlorodiphenyl ether. The products formed from diphenyl ether were 2- and 4-hydroxydiphenyl ether. Both 4-bromo- and 4-chlorodiphenyl ether were transformed to the corresponding products hydroxylated at the non-halogenated ring. Additionally, ring-cleavage products were detected by high perfomance liquid chromatography and characterized by gas chromatography/mass spectrometry and proton nuclear magnetic resonance spectroscopy. Unhalogenated diphenyl ether was degraded to 2-hydroxy-4-phenoxymuconic acid and 6-carboxy-4-phenoxy-2-pyrone. Brominated derivatives of both these compounds were formed from 4-bromodiphenyl ether, and 4-chlorodiphenyl ether was transformed in the same way to the analogous chlorinated ring cleavage products. Additionally, 4-bromo- and 4-chlorophenol were detected as intermediates from 4-bromo- and 4-chlorodiphenyl ether, respectively. In the presence of the cytochrome-P450 inhibitor 1-aminobenzotriazole, no metabolites were formed by cells of Trametes versicolor from the diphenyl ethers investigated. Cell-free supernatants of whole cultures with high laccase and manganese peroxidase activities were not able to transform the unhydroxylated diphenyl ethers used.
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  • 89
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    Journal of thermal analysis and calorimetry 55 (1999), S. 681-690 
    ISSN: 1572-8943
    Keywords: chromia ; Fe-Cr alloy ; gas-solid reaction kinetics ; H2/H2O gas mixtures ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The high-temperature oxidation behavior of a ferritic alloy (SUS 430) in a SOFC environment, corresponding to the anode (H2/H2O gas mixture) and cathode (air) operating conditions, was determined with regard to application of the alloy as a metallic separator material in SOFC. The oxidation kinetics of Fe-16Cr alloy (SUS 430), was studied by thermogravimetry in H2/H2O gas mixtures with pH/pHO=94/6 and 97/3 and in air, in the temperature range 1023-1223 K, for 3.6 up to 1080 ks. It was found that the protective oxide scale, composed mainly of Cr2O3 with uniform thickness and excellent adhesion to the metal substrate, grows in accordance with the parabolic rate law. The dependence of the parabolic rate constant, kp, of the scale on temperature obeys the Arrhenius equation: kp=6.8×10-4 exp (-202.3 kJ mol-1R-1T-1) for H2/H2O gas mixtures with pH/pHO=94/6. The determined kp was independent of the oxygen partial pressure in the range from 5.2×10-22 to 0.21 atm at 1073 K, which means that the rates of growth of the scale on Fe-16Cr alloy in the above-mentioned atmospheres are comparable. The oxidation test results on Fe-16Cr alloy in H2/H2O gas mixtures and air demonstrate the applicability of SUS 430 alloys as a separator for SOFC.
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  • 90
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    Journal of thermal analysis and calorimetry 55 (1999), S. 981-987 
    ISSN: 1572-8943
    Keywords: nickel phosphates ; nickel phosphides ; Ni-P alloys ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract DTA in conjuction with X-ray diffraction analysis with a high-temperature camera and infrared spectroscopy was employed to determine the mechanism of oxidation of Ni-P alloys. Amorphous Ni-P powders were obtained from a nickel(II) sulphate bath as a nickel source and sodium dihydrophosphate(I) as a reducing agent. The crystallization product is composed of two phases: (f.c.c.) Ni and (b.c.t.) Ni3P. The amorphous to crystalline transformation takes place in the temperature range 280–330°C. Ni3P samples were heated from room temperature to 1050°C in air atmosphere at 5°C min−1. It was found that the first stage of oxidation of Ni3P goes through the intermediate phase of Ni12P5 formation to Ni2P. Some exothermic reactions were observed. Heating runs were interrupted after each reaction for crystal structure determination by IR spectrometry. Infrared spectra are reported and it is shown that the structure units present in the amorphous products at about 700°C were the oxoanions PO3 − and P2O7 −. The final products of the oxidation process are NiO and Ni3(PO4)2.
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  • 91
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    International journal of thermophysics 20 (1999), S. 299-308 
    ISSN: 1572-9567
    Keywords: high temperature ; metal ; spectral emissivity ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract The normal spectral emissivity and its time variation were measured systematically for a total of thirty kinds of pure metals and alloys at temperatures between 780 and 1200°C. The spectral data were obtained at about 100 wavelengths from 0.55 to 5.3 μm under different environmental conditions including oxidation. The spectral data were stored in a database with supplementary information on the specimens. Clear oscillations of the spectral emissivity with time and wavelength were observed for nickel, Inconel, and SUS444 as surface oxidation progressed, while emissivity variations were rather monotonic for other metals such as titanium, cold-rolled steel, and SUS310S. The surface roughness was measured for all specimens by a contact-type instrument before the measurements, and recorded as supplementary information in the database. The database was built on a personal computer operating system (Windows95) to facilitate the dissemination to researchers and engineers interested in the emissivity of metals. Indexes to the emissivity data are metal name, wavelength, temperature, time, and degree of oxidation represented by an effective thickness of oxide film on the specimen surface.
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  • 92
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    International journal of thermophysics 20 (1999), S. 289-298 
    ISSN: 1572-9567
    Keywords: high temperature ; metal ; spectral emissivity ; oxidation ; radiation thermometer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract A system for measuring time variations of the normal spectral emissivity at wavelengths ranging from 0.55 to 5.3 μm was developed and applied to metal specimens in vacuum and oxidizing environments in the temperature range from 780 to 1200° C. The specimen was heated to high temperatures by passing a direct current in a vacuum chamber, and the surface oxidation was controlled by a low-pressure oxidizing gas. The specimen temperature was measured by a single-band (0.9-μm) radiation thermometer viewing at a cavity formed in the specimen from the rear side. The front surface of the specimen was observed by a multiband (112-wavelength) radiation thermometer to measure the normal spectral emissivity. The effective normal spectral emissivity of the specimen cavity was evaluated to be 0.94±0.05 at a wavelength of 0.9 μm in comparison with a metal tube having a small blackbody hole on the rear. The measurement uncertainty of the normal spectral emissivitiy by the system was estimated to be 5 to 10% of the emissivity value in most of the interesting ranges of emissivities, temperatures, and wavelengths.
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  • 93
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    Cellular and molecular neurobiology 19 (1999), S. 533-552 
    ISSN: 1573-6830
    Keywords: benzodiazepines ; cytochromes P450 ; oxidation ; reduction ; conjugation ; drug interactions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract 1. The benzodiazepines are among the most frequently prescribed of all drugs and have been used for their anxiolytic, anticonvulsant, and sedative/hypnotic properties. Since absorption rates, volumes of distribution, and elimination rates differ greatly among the benzodiazepine derivatives, each benzodiazepine has a unique plasma concentration curve. Although the time to peak plasma levels provides a rough guide, it is not equivalent to the time to clinical onset of effect. The importance of α and β half-lives in the actions of benzodiazepines is discussed. 2. The role of cytochrome P450 isozymes in the metabolism of benzodiazepines and in potential pharmacokinetic interactions between the benzodiazepines and other coadministered drugs is discussed. 3. Buspirone, an anxiolytic with minimal sedative effects, undergoes extensive metabolism, with hydroxylation and dealkylation being the major pathways. Pharmacokinetic interactions of buspirone with other coadministered drugs seem to be minimal. 4. Zopiclone and zolpidem are used primarily as hypnotics. Both are extensively metabolized; N-demethylation, N-oxidation, and decarboxylation of zopiclone occur, and zolpidem undergoes oxidation of methyl groups and hydroxylation of a position on the imidazolepyridine ring system. Zopiclone has a chiral centre, and demonstrates stereoselective pharmacokinetics. Metabolic drug–drug interactions have been reported with zopiclone and erythromycin, trimipramine, and carbamazepine. Reports to date indicate minimal interactions of zolpidem with coadministered drugs; however, it has been reported to affect the C max and clearance of chlorpromazepine and to decrease metabolism of the antiviral agent ritonavin. Since CYP3A4 has been reported to play an important role in metabolism of zolpidem, possible interactions with drugs which are substrates and/or inhibitors of that CYP isozyme should be considered.
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  • 94
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    Cellular and molecular neurobiology 19 (1999), S. 133-140 
    ISSN: 1573-6830
    Keywords: Na/K-ATPase ; SH groups ; oxidation ; hydrogen peroxide ; hypochlorite ; antioxidants ; carnosine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract 1. Oxidative modification of Na/K-ATPase from brain and kidney has been studied. Brain enzyme has been found to be more sensitive than kidney enzyme to inhibition by both H2O2 and NaOCl. 2. The inhibition of Na/K-ATPase correlates well with the decrease in a number of SH groups, suggesting that the latter belong mainly to ATPase protein and are essential for the enzyme activity. We suggest that the differences in the number, location, and accessibility of SH groups in Na/K-ATPase isozymes predict their oxidative stability. 3. The hydrophilic natural antioxidant carnosine, the hydrophobic natural antioxidant α-tocopherol, and the synthetic antioxidant ionol as well as the ferrous ion chelating agent deferoxamine were found to protect Na/K-ATPase from oxidation by different concentrations of H2O2. The data suggest that these antioxidants are effective due to their ability to neutralize or to prevent formation of hydroxyl radicals.
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  • 95
    ISSN: 1573-2932
    Keywords: diffusion coefficient ; gaseous oxygen ; mine tailings ; oxidation ; water content
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract To evaluate the effectiveness of soil covers, column experiments were conducted on tailings protected by a three-layer soil cover and tailings directly exposed in the open laboratory for a period of 760 days. Periodic rain application was performed to simulate field conditions, and at four times during the experiments the pore water was completely flushed out of each column for analysis. Profiles of oxygen, temperature, and volumetric water content were measured throughout the experiment, and the post-testing pore water quality was also characterized. A one-dimensional semi-analytic diffusion model was used to simulate oxygen profiles in the uncovered tailings. Modelling performed using the geochemical code MINTEQ showed that in the laboratory, aluminium concentrations in the tailings pore water were controlled by Al(OH)SO4, sulphate by gypsum and Al(OH)SO4and iron by lepidocrocite in the upper half and by ferrihydrite in the lower half. In the field, however, the iron oxyhydroxide minerals formed in the oxidized zone appear to be dissolving. It was found that the cover was effective in preventing significant desaturation of the clay, even over a 150-day drying period. The covered tailings did not oxidize much during the experiments. In the uncovered tailings, oxygen modelling and examination of the geochemistry show that the rate of gross oxidation and the advancement of the oxidation front decreases with time. However, pore water quality is controlled by geochemical processes other than oxidation, as reported in the field.
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  • 96
    ISSN: 1588-2837
    Keywords: V2O5−ZrO2 catalyst ; oxidation ; o-xylene ; temperature stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract It has been established that at high temperatures (above 450°C) the V2O5−ZrO2 catalyst exhibits a higher selectivity in the oxidation ofo-xylene to phthalic anhydride than does the conventional V2O5−TiO2(a) catalyst. The catalyst selectivity is found to increase with respect to partial oxidation ofo-xylene, the valuable by-product maleic anhydride being obtained. Studies by different physicochemical methods have shown that V2O5−ZrO2 undergoes no significant phase and structural changes under high-temperature conditions.
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  • 97
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    Reaction kinetics and catalysis letters 66 (1999), S. 97-104 
    ISSN: 1588-2837
    Keywords: Heterogeneous catalysis ; oxidation ; temperature hysteresis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The temperature hysteresis observed in the oxidation of CO on both supported and unsupported catalysts can be explained by the local overheating of active centers rather than by transitions from one steady state to another.
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  • 98
    ISSN: 1588-2837
    Keywords: Catalyst ; ceramic foam ; molten salt ; Nox ; oxidation ; soot
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Diesel soot is combusted simultaneously by two reactions: combustion with NO2 and combustion with O2 with the aid of a molten salt catalyst. Both reaction pathways should always be considered to avoid misinterpretation of experimental data.
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  • 99
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    Reaction kinetics and catalysis letters 68 (1999), S. 285-289 
    ISSN: 1588-2837
    Keywords: Enthalpy ; chain propagation ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A calculation of the enthalpies of elementary steps of the intra- and intermolecular chain propagation for model oxidation reactions of ethers, esters, ketones and hydrocarbons has been carried out. The heats of the intermolecular and intramolecular transfer of free valence with participation of peroxy radicals and C−H bond of the oxygen-containing compounds are shown to be comparable.
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  • 100
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    Reaction kinetics and catalysis letters 68 (1999), S. 325-330 
    ISSN: 1588-2837
    Keywords: vitrification ; glass structure ; oxidation ; solid phase kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The capture of oxygen molecules by deep traps during oxygen diffusion in butanol glasses has been studied at 77 K as the kinetics of thetert-butyl radical oxidation. Slow glass formation in the samples increases the concentration of deep traps in the matrix. The total value of nonrelaxed free volume has no effect on the concentration of deep traps. It is assumed that trap formation is due to the formation of certain molecular structures below room temperature, most probably, with dissolved gas molecules.
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