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  • oxidation  (216)
  • Springer  (216)
  • 1995-1999  (216)
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    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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  • 2
    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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  • 3
    ISSN: 1432-072X
    Keywords: Key wordsNitrospira moscoviensis ; Non-marine ; bacteria ; Obligate chemolithoautotroph ; Nitrite ; oxidation ; Nitrate reduction ; 16S rRNA gene sequences
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract A gram-negative, non-motile, non-marine, nitrite-oxidizing bacterium was isolated from an enrichment culture initiated with a sample from a partially corroded area of an iron pipe of a heating system in Moscow, Russia. The cells were 0.9–2.2 μm × 0.2–0.4 μm in size. They were helical- to vibroid-shaped and often formed spirals with up to three turns 0.8–1.0 μm in width. The organism possessed an enlarged periplasmic space and lacked intracytoplasmic membranes and carboxysomes. The cells tended to excrete extracellular polymers, forming aggregates. The bacterium grew optimally at 39°C and pH 7.6– 8.0 in a mineral medium with nitrite as sole energy source and carbon dioxide as sole carbon source. The optimal nitrite concentration was 0.35 mM. Nitrite was oxidized to nitrate stoichiometrically. The doubling time was 12 h in a mineral medium with 7.5 mM nitrite. The cell yield was low; only 0.9 mg protein/l was formed during oxidation of 7.5 mM nitrite. Under anoxic conditions, hydrogen was used as electron donor with nitrate as electron acceptor. Organic matter (yeast extract, meat extract, peptone) supported neither mixotrophic nor heterotrophic growth. At concentrations as low as 0.75 g organic matter/l or higher, growth of nitrite-oxidizing cells was inhibited. The cells contained cytochromes of the b- and c-type. The G+C content of DNA was 56.9 ± 0.4 mol%. The chemolithoautotrophic nitrite-oxidizer differed from the terrestrial members of the genus Nitrobacter with regard to morphology and substrate range and equaled Nitrospira marina in both characteristics. The isolated bacterium is designated as a new species of the genus Nitrospira. Comparative analysis of 16S rRNA gene sequences revealed a moderate phylogenetic relationship to Nitrospira marina, leptospirilla, Thermodesulfovibrio yellowstonii, "Magnetobacterium bavaricum," and the isolate OPI-2. Initial evidence is given that these organisms represent a new phylum of the domain bacteria.
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  • 4
    ISSN: 1432-072X
    Keywords: Key words Fumarase ; Syntrophy ; Propionate ; oxidation ; Fumarate fermentation ; Anaerobic oxidation ; Iron-sulfur cluster
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Fumarase from the syntrophic propionate-oxidizing bacterium strain MPOB was purified 130-fold under anoxic conditions. The native enzyme had an apparent molecular mass of 114 kDa and was composed of two subunits of 60 kDa. The enzyme exhibited maximum activity at pH 8.5 and approximately 54° C. The K m values for fumarate and l-malate were 0.25 mM and 2.38 mM, respectively. Fumarase was inactivated by oxygen, but the activity could be restored by addition of Fe2+ and β-mercaptoethanol under anoxic conditions. EPR spectroscopy of the purified enzyme revealed the presence of a [3Fe-4S] cluster. Under reducing conditions, only a trace amount of a [4Fe-4S] cluster was detected. Addition of fumarate resulted in a significant increase of this [4Fe-4S] signal. The N-terminal amino acid sequence showed similarity to the sequences of fumarase A and B of Escherichia coli (56%) and fumarase A of Salmonella typhimurium (63%).
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  • 5
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    Archives of microbiology 163 (1995), S. 352-356 
    ISSN: 1432-072X
    Keywords: Key wordsThiobacillus ferrooxidans ; Sulfide ; oxidation ; Sulfur colloids ; Bioleaching
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Thiobacillus ferrooxidans was cultivated on 100-nm-thick synthetic pyrite (FeS2) films. The steps of biooxidation were studied with high-resolution transmission electron microscopy. The crystallized sulfide was transformed into colloidal sulfur (4–70 nm, depending on the age of the cell and the degree of substrate oxidation; 70 nm initially and 4 nm after oxidation of the pyrite substrate), which was taken up and distributed over an organic capsule around the bacteria. This colloidal sulfur acted as intermediate energy storage and was transferred by contact to daughter cells not directly attached to the sulfide substrate.
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  • 6
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    Archives of microbiology 167 (1997), S. 106-111 
    ISSN: 1432-072X
    Keywords: Key wordsNitrosomonas ; Anaerobic ammonia ; oxidation ; Anaerobic cell growth ; Nitrogen dioxide ; Nitric oxide ; Nitrous oxide ; Dinitrogen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Nitrosomonas eutropha, an obligately lithoautotrophic bacterium, was able to nitrify and denitrify simultaneously under anoxic conditions when gaseous nitrogen dioxide (NO2) was supplemented to the atmosphere. In the presence of gaseous NO2, ammonia was oxidized, nitrite and nitric oxide (NO) were formed, and hydroxylamine occurred as an intermediate. Between 40 and 60% of the produced nitrite was denitrified to dinitrogen (N2). Nitrous oxide (N2O) was shown to be an intermediate of denitrification. Under an N2 atmosphere supplemented with 25 ppm NO2 and 300 ppm CO2, the amount of cell protein increased by 0.87 mg protein per mmol ammonia oxidized, and the cell number of N. eutropha increased by 5.8 × 109 cells per mmol ammonia oxidized. In addition, the ATP and NADH content increased by 4.3 μmol ATP (g protein)–1 and 6.3 μmol NADH (g protein)–1 and was about the same in both anaerobically and aerobically grown cells. Without NO2, the ATP content decreased by 0.7 μmol (g protein)–1, and the NADH content decreased by 1.2 μmol (g protein)–1. NO was shown to inhibit anaerobic ammonia oxidation.
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  • 7
    ISSN: 1432-072X
    Keywords: Key words Syntrophy ; Fumarate reduction ; Propionate ; oxidation ; Anaerobic growth ; Electron transport chain
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The growth of the syntrophic propionate-oxidizing bacterium strain MPOB in pure culture by fumarate disproportionation into carbon dioxide and succinate and by fumarate reduction with propionate, formate or hydrogen as electron donor was studied. The highest growth yield, 12.2 g dry cells/mol fumarate, was observed for growth by fumarate disproportionation. In the presence of hydrogen, formate or propionate, the growth yield was more than twice as low: 4.8, 4.6, and 5.2 g dry cells/mol fumarate, respectively. The location of enzymes that are involved in the electron transport chain during fumarate reduction in strain MPOB was analyzed. Fumarate reductase, succinate dehydrogenase, and ATPase were membrane-bound, while formate dehydrogenase and hydrogenase were loosely attached to the periplasmic side of the membrane. The cells contained cytochrome c, cytochrome b, menaquinone-6 and menaquinone-7 as possible electron carriers. Fumarate reduction with hydrogen in membranes of strain MPOB was inhibited by 2-(heptyl)-4-hydroxyquinoline-N-oxide (HOQNO). This inhibition, together with the activity of fumarate reductase with reduced 2,3-dimethyl-1,4-naphtoquinone (DMNH2) and the observation that cytochrome b of strain MPOB was oxidized by fumarate, suggested that menequinone and cytochrome b are involved in the electron transport during fumarate reduction in strain MPOB. The growth yields of fumarate reduction with hydrogen or formate as electron donor were similar to the growth yield of Wolinella succinogenes. Therefore, it can be assumed that strain MPOB gains the same amount of ATP from fumarate reduction as W. succinogenes, i.e. 0.7 mol ATP/mol fumarate. This value supports the hypothesis that syntrophic propionate-oxidizing bacteria have to invest two-thirds of an ATP via reversed electron transport in the succinate oxidation step during the oxidation of propionate. The same electron transport chain that is involved in fumarate reduction may operate in the reversed direction to drive the energetically unfavourable oxidation of succinate during syntrophic propionate oxidation since (1) cytochrome b was reduced by succinate and (2) succinate oxidation was similarly inhibited by HOQNO as fumarate reduction.
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  • 8
    ISSN: 1432-072X
    Keywords: Key wordsParacoccus denitrificans ; Sulfide ; oxidation ; Sulfide-quinone reductase ; Cytochrome ; bc complex ; Flavocytochrome c
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Reduction of exogenous ubiquinone and of cytochromes by sulfide in membranes of the chemotrophic bacterium Paracoccus denitrificans GB17 was studied. For sulfide-ubiquinone reductase activity, K m values of 26 ± 4 and 3.1 ± 0.6 μM were determined from titrations with sulfide and decyl-ubiquinone, respectively. A maximal rate of up to 0.3 μmol decyl-ubiquinone reduced (mg protein)–1 min–1 was estimated. The reaction was sensitive to quinone-analogous inhibitors, but insensitive to cyanide. Reduction of cytochromes by sulfide was monitored with an LED-array spectrophotometer. Under oxic conditions, reduction rates and extents of reduction were lower than those under anoxic conditions. Reoxidation of cytochromes was oxygen-dependent and cyanide-sensitive. The multiphasic behavior of transient reduction of cytochrome b with limiting amounts of sulfide reflects that sulfide, in addition to acting as an electron donor, is a slowly binding inhibitor of cytochrome c oxidase. The initial peak of cytochrome b reduction is dependent on electron flow to an oxidant, either oxygen or ferricyanide, and is stimulated by antimycin A. This oxidant-induced reduction of cytochrome b suggests that electron transport from sulfide in P. denitrificans GB17 employs the cytochrome bc 1 complex via the quinone pool.
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  • 9
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    Journal of polymers and the environment 3 (1995), S. 199-203 
    ISSN: 1572-8900
    Keywords: Chemiluminescence ; oxidation ; stability ; acrylonitrile-butadiene-styrene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Energy, Environment Protection, Nuclear Power Engineering , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The thermal oxidative stability of various formulations based on emulsion-grade ABS was studied by the chemiluminescence technique. Emulsion products were found to be essentially less stable than ionic mass polymerization resins. Among the antioxidants studied, Santonox R is clearly more efficient than Irganox 1076 and Irganox 3114, and its superiority is reflected primarily in improved induction period values. The introduction of Tinuvin 770 and Tinuvin 328 UV stabilizers into emulsion resins does not change the durability of the products. In mixtures where both Irganox 1076 and UV stabilizers are present, a certain antagonistic effect was noted at high UV stabilizer concentrations.
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  • 10
    ISSN: 1572-8757
    Keywords: porous carbons ; activation ; oxidation ; surface oxygen groups ; LTPD
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract A styrene/divinylbenzene copolymer has been used as precursor for making porous carbons with bimodal pore size distributions (i.e., with both microporosity and mesoporosity). Pretreatment of the as-received copolymer by mild oxidation in air, significantly increased the carbon yield after carbonization. Reactivity studies of the polymer-based chars to CO2 clearly show the influences of some important factors such as carbonization temperature, heating rate, soak time on char reactivities. Bimodal porous carbons were prepared by carbonization of the preoxidized styrene/divinylbenzene copolymer in N2, followed by activation in CO2 at different temperatures to different levels of burnoff. The pore structures of the porous carbons produced have been characterized by various techniques such as gas adsorption and mercury porosimetry. The surfaces of the porous carbons produced, and a commercial carbon adsorbent, have been modified with HNO3 and H2O2 treatment at various conditions. Characterization of the surface oxygen functionality, both quantitatively and qualitatively, has been achieved using techniques such as Linear Temperature Programed Desorption (LTPD) and selective neutralization of bases.
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  • 11
    ISSN: 1572-8773
    Keywords: acidophilic ; strain ; oxidation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    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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  • 12
    ISSN: 1572-879X
    Keywords: synergistic effect ; carbon monoxide ; oxidation ; mixed oxides ; iron oxide ; tin oxide ; manganese oxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Based on the comparative evaluation of the catalytic activity of Fe2O3, Mn2O3 and SnO2 and their mixed oxides (Fe2O3+SnO2) and (Mn2O3+SnO2), it is shown that the system (Mn2O3+SnO2) shows strong synergistic effects during CO oxidation reaction. Such effects are not observed for the analogous system (Fe2O3+SnO2). Based on the calcination and reduction behaviour of these two mixed oxide systems and the redox potentials of the involved cations, the possible reasons for the observance of synergistic effects for the (Mn2O3+SnO2) system are discussed.
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  • 13
    ISSN: 1572-879X
    Keywords: perovskite ; La1−xSrxFeO3−δ ; dehydrogenation ; oxidation ; ethane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Catalysts of the composition La1−xSrxFeO3−δ, 0⩽x ⩽1, have been tested for the oxidative dehydrogenation of ethane in the temperature range 300–800°C. The catalyst is active above 400°C, giving a maximum yield of 37% ethylene at 650°C. Above 650°C, synthesis gas was formed together with methane, suggesting that the reforming reaction and thermal cracking of ethane took place. The catalytic data are compared to conductivity measurements on the same material, and a good correlation between the activity and p-type conductivity has been found. In the phase diagram for the system LaFeO3-SrFeO3−δ, a phase separation to two types of (La, Sr)FeO3−δ perovskites was observed in the La/Sr binary composition in the temperature range below 800°C. The phase separation can elucidate the dependency of the catalytic activity on its p-type conductivity.
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  • 14
    ISSN: 1572-879X
    Keywords: non-uniform surface ; kinetics ; ethanol ; oxidation ; molybdenum oxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Temkin's theory of rates of catalytic reactions on non-uniform surfaces is extended to the MoO3-catalyzed oxidation of ethanol to acetaldehyde. Two types of sites are assumed to be present, an oxygen atom site that can be modeled with uniform properties and a metal atom site characterized by non-uniform properties both for ethanol chemisorption to an ethoxide intermediate and the conversion of this intermediate to acetaldehyde. The rate-limiting step is the cleavage of a C-H bond in the absorbed ethoxide intermediate. Non-uniform surface kinetics leads to a kinetic rate expression of the form $$v = kP_{C_2 H_5 OH}^{1 - m} P_{O_2 }^{(1 - m)/4} P_{H_2 O}^{ - (1 - m)/2} $$ . Such a rate expression, withm=0.14, is shown to provide a good fit to kinetic data for the selective oxidation of ethanol on a silica supported molybdenum oxide catalyst.
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  • 15
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    Catalysis letters 39 (1996), S. 205-208 
    ISSN: 1572-879X
    Keywords: oxidation ; hydroxyapatite ; carbon monoxide ; inhibition ; tetrachloromethane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The introduction of tetrachloromethane (TCM) into the feedstream of CO and O2 inhibits the formation of CO2 on hydroxyapatite. TCM interacts with the surface of hydroxyapatite to form its chlorinated analogue, chlorapatite, which suppresses the oxidation of CO to CO2. Thus, in the oxidative coupling of methane the beneficial effects of the addition of TCM to the feedstream result, at least in part, from the suppression of the further oxidation of CO.
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  • 16
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    Catalysis surveys from Japan 3 (1999), S. 27-35 
    ISSN: 1572-8803
    Keywords: oxidation ; oxygen ; alkane ; N‐hydroxyphthalimide ; radical catalyst
    Source: Springer Online Journal Archives 1860-2000
    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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  • 17
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    Cellulose 5 (1998), S. 153-164 
    ISSN: 1572-882X
    Keywords: cellulose ; TEMPO ; polyglucuronic acid ; degree of polymerization ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Various cellulose samples were oxidized by 2,2,6,6,-tetramethylpipelidine-1-oxyl radical (TEMPO)-NaBr-NaClO systems, and the effects of oxidation conditions on chemical structures and degrees of polymerization of the products obtained were studied. In the case of regenerated and mercerized celluloses, almost all C6 primary alcohol groups were selectively oxidized to carboxyl groups, and water-soluble polyglucuronic acid (cellouronic acid) sodium salts were obtained almost quantitatively; the degrees of polymerization were influenced greatly by the amount of TEMPO added, and the oxidation time and temperatures. Cellouronic acids prepared from mercerized linter and kraft pulps had size exclusion chromatograms with two separate peaks due to higher and lower molecular weight fractions. On the other hand, only small amounts of carboxyl groups were introduced into native cellulose samples. Since polyglucuronic acids prepared from cellulose by the TEMPO–NaBr– NaClO systems regularly consist of the glucuronic acid repeating unit, differing from the conventional water-soluble cellulose derivatives, they may open new fields of cellulose utilization.
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  • 18
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    Journal of thermal analysis and calorimetry 53 (1998), S. 263-267 
    ISSN: 1572-8943
    Keywords: kinetics ; molybdenum sulphide ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract This paper reports on the results attained in the determination of the mechanism of oxidation of molybdenum sulphide under non-isothermal conditions in an air atmosphere. The mechanism of the process was determined by simultaneous DTA-TG-DTG, and the kinetic parameters of the reactions involved were obtained according to the methods of Kissinger and Ozawa.
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  • 19
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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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  • 20
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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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  • 21
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    Catalysis surveys from Japan 2 (1998), S. 31-44 
    ISSN: 1572-8803
    Keywords: porous heteropoly compounds ; Pt-promoted heteropoly compounds ; shape selectivity ; water-tolerant catalyst ; hydrogenation ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract This paper attempts to review recent works on catalysis of porous heteropoly compounds. The salts of heteropolyacids having Keggin structure with large cations like Cs+ are porous materials. For Cs hydrogen salts, the pore width can be controlled by the Cs content. Cs2.5H0.5PW12O40 has the largest amount of protons on the surface among the acidic Cs salts and possesses pores with bimodal distribution in the micro and meso region. Efficient performances were demonstrated for acid-catalyzed reactions such as skeletal isomerization of η-butane in solid-gas system, alkylation and acylation in solid-liquid system, and hydrolysis and hydration in solid-water system. A microporous salt, Cs2.2H0.8PW12O40, exhibited reactant shape selectivity towards direct decomposition of esters. Furthermore, an ultramicroporous bifunctional catalyst, Pt–Cs2.1H0.9PW12O40 of which the pore width is around 5 Å, exhibits reactant shape selectivity for hydrogenation of alkenes and oxidation of hydrocarbons, and product shape selectivity for skeletal isomerization of η-butane.
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  • 22
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    Catalysis surveys from Japan 2 (1998), S. 121-132 
    ISSN: 1572-8803
    Keywords: zeolite ; metallosilicate ; atom-planting ; modification ; catalysis ; acidity ; shape-selective alkylation ; oxidation ; hydrogen peroxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Atom-planting, a useful method to prepare some metallosilicates having zeolitic structure, was proposed. By treatment of highly siliceous zeolite with metal chloride vapor at selected temperature, metal cation could be introduced into the defect sites (hydroxyl nests) of zeolite framework. By the atom-planting method, some metallosilicates which are difficult to be synthesized by hydrothermal synthesis could be prepared. The vapor phase shape-selective alkylation of ethylbenzene with ethanol, and the liquid phase selective oxidation with hydrogen peroxide on the metallosilicates prepared by atom-planting method were reviewed.
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  • 23
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    International journal of thermophysics 16 (1995), S. 1481-1487 
    ISSN: 1572-9567
    Keywords: electrical resistivity ; high temperature ; thermal conductivity ; oxidation ; zirconium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract The thermal conductivity and electrical resistivity of zirconium-1 wt% niobium samples were measured before and after the process of their oxidation in air. A special procedure was used to dissolve the gas and to smooth out its concentration in the alloy. The basic experiments were performed under high vacuum under steady-state temperature conditions. The temperature range was 300–1600 K. for the pure alloy and 300–1100 K for the samples containing oxygen. It was found that the thermal conductivity—oxygen concentration relation reverses its sign from negative at low and middle temperatures to positive at temperatures above 900 K. The relation between the electrical resistivity and the oxygen content does not show this feature. The Lorenz function was found to have an anomalous temperature dependence.
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  • 24
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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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  • 25
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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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  • 26
    ISSN: 1572-879X
    Keywords: TiO2 ; heterogeneous photocatalysis ; oxidation ; substituted toluenes ; zeolites
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Photocatalytic oxidation of substituted toluenes was investigated on irradiated TiO2 and TiO2 combined with HY15 and HY20 zeolites. In all cases the oxidation occurred in the first step exclusively on either one substituent or the other, but never on both simultaneously. In the presence of a zeolite, photooxidation conversion was higher than that obtained without zeolite.
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  • 27
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    Catalysis letters 37 (1996), S. 79-87 
    ISSN: 1572-879X
    Keywords: methanol ; oxidation ; copper ; electron spectroscopy
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The role of preadsorbed oxygen present at Cu(111), Cu(110) and polycrystalline surfaces in the oxidation of methanol has been investigated by X-ray and electron energy loss spectroscopies. In addition to the well established formation of methoxy species and its subsequent decomposition and desorption as formaldehyde, a second reaction pathway to surface formate is present. The latter is temperature dependent being undetectable at 260 K at a polycrystalline surface but occurs at a significant rate at 295 K and above. The limitations of experimental data for methanol oxidation by temperature programmed desorption and molecular beam techniques are discussed.
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  • 28
    ISSN: 1572-879X
    Keywords: oxidation ; cyclohexene ; polyoxometalate-intercalated hydrotalcite
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Cyclohexene was oxidized with molecular oxygen over transition-metal-substituted polyoxometalate-intercalated hydrotalcites to produce 2-cyclohexene-1-one and 2-cyclohexene-1-ol with high selectivity under mild reaction conditions.
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  • 29
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    Catalysis letters 34 (1995), S. 31-40 
    ISSN: 1572-879X
    Keywords: palladium ; PdO ; alumina ; methane ; oxidation ; carbon ; XPS ; ellipsometry ; structure sensitivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Samples of palladium supported onγ-alumina and a palladium foil were used as catalysts for methane oxidation at 550° C. The samples were quenched quickly in the reaction chamber to room temperature in flowing Ar and then transferred in vacuo for XPS analysis. Structure sensitivity was manifest from an increase in PdO stability and a decrease in carbon deposition relative to Pd with increasing particle size. The results were compared with recent ellipsometric data.
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  • 30
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    Catalysis letters 52 (1998), S. 25-29 
    ISSN: 1572-879X
    Keywords: metallosilicate ; mesoporous ; MCM-41 ; Mo-MCM-41 ; catalysis ; oxidation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Mo-incorporated MCM-41 has been prepared by direct hydrothermal synthesis. XRD and N2-adsorption measurements showed the characteristics of MCM-41. IR, FT-Raman and UV-VIS DR spectroscopic analyses gave the evidences for the incorporation of Mo in the framework of MCM-41. They are found to be stable and active for cyclohexanol and cyclohexane oxidation reactions with H2O2 as oxidant. Activity of this system has been compared with that of Ti-MCM-41 and molybdena impregnated on pure siliceous MCM-41.
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  • 31
    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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  • 32
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    Cellulose 2 (1995), S. 265-272 
    ISSN: 1572-882X
    Keywords: Hydrogen peroxide ; oxycellulose ; bleaching ; oxidation
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    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Peroxides are important bleaching agents, industrially, for cellulosic products. They are also used in detergents. Peroxides can degrade cellulose as well as decolorize it and remove stains. Both free radicals and perhydroxyl anions have been suggested as the intermediates in the reactions occurring between cellulosic products and hydrogen peroxide. The proposed mechanisms are reviewed with emphasis primarily on cotton cellulose. Further work is required to establish unequivocally the mechanism of degradation and decolorization of cellulose products.
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  • 33
    ISSN: 1572-8765
    Keywords: carbonado ; diamond ; oxidation
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of carbonado type synthesized polycrystalline diamonds produced from graphite together with catalytic Ni-Mo alloy doped with TiB2 and BNcub was investigated. It was found that the addition of these boron compounds increases the oxidation resistance of the carbonado type synthesized polycrystalline diamonds. The oxidation mechanism acting on the carbonado type synthesized polycrystalline diamonds and the role of boron compounds in increasing the resistance to the oxygen reaction are discussed.
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  • 34
    ISSN: 1572-879X
    Keywords: Fischer-Tropsch synthesis ; cobalt catalysts ; deactivation ; oxidation ; reduction ; promoters ; rhenium
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The influence of water on alumina-supported cobalt catalysts has been studied. The deactivation of supported Co catalysts was studied in a fixed-bed reactor using synthesis gas feeds containing different concentrations of water vapour. Supporting model studies were carried out using H2O/H2 feeds in conjunction with XPS and gravimetry. Rapid deactivation occurs on Re-promoted CO/Al2O3 catalysts when H2/CO/H2O feeds are used, whereas unpromoted CO/Al2O3 shows more stable activity. The results from the gravimetric studies suggest that only a small fraction of the bulk cobalt metal initially present reoxidizes to cobalt oxide during reaction. However, the XPS results indicate significant reoxidation of surface cobalt atoms or highly dispersed cobalt phases, which is likely to be the cause of the observed deactivation. Rhenium is shown to have a marked effect on the extent of reoxidation of alumina-supported cobalt catalysts.
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  • 35
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    Catalysis letters 37 (1996), S. 213-216 
    ISSN: 1572-879X
    Keywords: titanium silicalites ; oxidation ; amines ; hydrogen peroxide
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Titanium silicalite molecular sieves, TS-1 and TS-2 having MFI and MEL structures, respectively, catalyze the oxidation of secondary amines to the corresponding hydroxylamines using hydrogen peroxide as the oxidant. Higher concentrations of H2O2 lead to further oxidation of hydroxylamine to nitrone. Diffuse reflectance spectroscopy shows the formation of a titanium peroxo complex upon addition of hydrogen peroxide to the TS-1 catalyst. The titanium peroxo complex oxidizes the substrate and reforms to a titanyl group.
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  • 36
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    Catalysis letters 40 (1996), S. 47-50 
    ISSN: 1572-879X
    Keywords: Baeyer-Villiger ; titanium silicate molecular sieve ; oxidation ; rearrangement ; titanium peroxo ; triphase
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Titanium silicate molecular sieve TS-1 has been found to be an efficient catalyst for Baeyer-Villiger (BV) oxidation of cyclic and aromatic ketones under triphase conditions (solid catalyst along with two immiscible liquid reactants in the absence of any cosolvent), using dilute H2O2. Reactions studied are the oxidation of cyclohexanone and acetophenone. Whereas in the case of cyclohexane,ε-caprolactone, a BV product along with hydroxy and diketones is formed, in the case of acetophenone, phenyl acetate, a BV product along witho- andp-hydroxyacetophenone is formed. The acidic nature of titanium peroxo species, stabilised by water, is proposed to be responsible for such reactions under triphasic reaction conditions.
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  • 37
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    Catalysis letters 36 (1996), S. 31-36 
    ISSN: 1572-879X
    Keywords: ethanol ; kinetics ; oxidation ; oxydehydrogenation ; platinum ; structure sensitivity
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The effect of the platinum particle size was investigated for the catalytic oxidative dehydrogenation of aqueous ethanol to ethanal at a temperature of 303 K, an ethanol concentration of 260 mol m−3, a partial oxygen pressure 60 kPa, a pH of 9, and an ethanal and ethanoate concentration of 20 mol m−3. A particle size effect on the turnover frequency was observed but only for particle sizes smaller than 2 nm. Hence, the reaction shows a limited structure sensitivity.
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  • 38
    ISSN: 1572-879X
    Keywords: oxidation ; metalloporphyrins ; hydroperoxide decomposition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A new family of metalloporphyrin complexes having perfluoroalkyl groups in the meso-positions of the ring are active catalysts for the oxidation of isobutane to tert-butyl alcohol, TBA, and for the decomposition of tert-butyl hydroperoxide to TBA. This discovery extends the limited number of meso-substituents that can be used to enhance catalytic activity and fits the postulate that groups that withdraw electrons from the porphyrin periphery give rise to active catalysts for alkane oxidation. The perfluoroalkyl groups also confer oxidative stability, hydrophobicity and lower cost to the catalyst.
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  • 39
    ISSN: 1572-879X
    Keywords: fluorination ; alumina ; platinum catalysts ; oxidation ; oxidation of benzene
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Platinum supported on fluorinated alumina is more active for the total oxidation of benzene than is the catalyst with the same Pt loading supported on hydrophilic unfluorinated alumina. The Pt-F/alumina catalyst contains well-dispersed small Pt particles, in contrast to Pt/alumina. The high dispersion is a consequence of a strong metal-support interaction.
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  • 40
    ISSN: 1572-879X
    Keywords: platinum ; EXAFS ; catalysis ; catalyst deactivation ; oxidation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract With a new set‐up for in situ EXAFS spectroscopy the state of a carbon‐supported platinum catalyst during aqueous alcohol oxidation has been observed. The catalyst deactivation during platinum‐catalysed cyclohexanol oxidation is caused by platinum surface oxide formation. The detected Pt–O co‐ordination at 2.10 Å during exposure to nitrogen‐saturated cyclohexanol solution is different from what is observed for the pure oxidised platinum surface (2.06 Å).
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  • 41
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    Catalysis surveys from Japan 3 (1999), S. 55-60 
    ISSN: 1572-8803
    Keywords: acetic acid ; oxidation ; Pd ; heteropoly acid ; ethylene
    Source: Springer Online Journal Archives 1860-2000
    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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  • 42
    ISSN: 1572-879X
    Keywords: palladium metal ; oxidation ; toxic organics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract In water, metallic palladium was found to catalyze the deep oxidation of a wide variety of functional organics by dioxygen at 80–90°C in the presence of carbon monoxide. Several classes of organic compounds were examined: benzene, phenol and substituted phenols, aliphatic and aromatic halogenated compounds, organophosphorus, and organosulfur compounds. In every case, deep oxidation to carbon monoxide, carbon dioxide, and water occurred in high yields, resulting in up to several hundred turnovers over a 24 h period. Since the heterogeneous catalyst can be removed by simple filtration, simultaneous water purification and contaminant destruction becomes feasible. For those substrates that are insoluble in pure water, a mixture of water and perfluorobutyric acid was successfully employed as the solvent.
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  • 43
    ISSN: 1572-879X
    Keywords: model catalysts ; spin coating ; Pt colloid ; AFM ; XPS ; Si wafer ; particle size ; oxidation ; reduction
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Platinum particles of 2 nm diameter have been immobilised on oxidised silicon wafers by spin coating with colloidal solutions and characterised by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The coverage and dispersion of the Pt colloids on the Si wafer are controlled by varying the concentration and the spin speed. Under optimal conditions mono-dispersed Pt colloids on silicon wafers are prepared. For the Pt colloids immobilised on the Si wafer, the majority of the stabilising ligands are removed through a reduction (with H2 at 200°C) or an oxidation (in air at 300°C) procedure. AFM showed that particle sizes are retained after the reduction procedure, while significant sintering occurs after oxidation. The mechanism of ligand removal was studied using an in situ XPS reaction cell.
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  • 44
    ISSN: 1572-879X
    Keywords: catalysis ; combustion ; oxidation ; formic acid ; STM ; molecular beams ; surface diffusion ; surface reactivity ; active sites ; reconstruction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Using a combination of STM and molecular beam reactor data we summarise some important features of a model reaction (formic acid oxidation on Cu(110)) which is of general significance to surface reactivity and to catalysis. Three such features are highlighted here. The first concerns the role of weakly held species (possibly physisorbed) in surface reactions. These species, although of very short lifetime on the surface, can, nevertheless, diffuse over long distances to “find” a sparse distribution of active sites. Thus a very low coverage of oxygen on the surface of Cu(110) increases the sticking probability of all the formic acid molecules which strike the surface to high value (0.82), even though the clean surface is relatively unreactive. The important concept here is the “diffusion circle” or “collection zone” which represents the area of surface visited by the molecule in its short sojourn in the weakly held state. The second theme concerns the concept of the “flexible surface”. We show that the involvement of surface atoms in reactions directs the structure and reactivity for a particular reaction. For formic acid oxidation the liberation of Cu atoms during the removal of oxygen as water leads to gross restructuring of the surface and can lead to “compression” of one reactant (the oxygen in this case) into a lower area, higher local coverage, unreactive state (the c(6×2) oxygen structure). Thirdly, and finally, it is proposed that, for many surface reactions, the surface acts in an analogous way to a solvent, supporting a “dissolved” (highly mobile and fluxional) phase of intermediates at low coverage, which crystallise out above a critical coverage (the 2D “solubility limit”).
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  • 45
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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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  • 46
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    Catalysis letters 56 (1998), S. 199-202 
    ISSN: 1572-879X
    Keywords: cerium ; gas carbonic ; propane ; oxidation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The interaction between CO2 and CeO2 and its role in the surface reactivity of alumina-supported cerium oxide has been studied by programmed thermodesorption (TPD) of CO2 and FTIR spectroscopy. The performance of Ce/Al2O3 systems was then analyzed for the propane oxidation in presence of CO2. The results have shown that the catalytic activity decreased when carbonate species are formed at the surface of CeO2. This behavior was attributed to the presence of CO2 from three different sources: contamination before use, during the handling of the samples, contamination proceeding from the reactants and from CO2 produced by the reaction itself.
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  • 47
    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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  • 48
    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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  • 49
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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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  • 50
    ISSN: 1572-9508
    Keywords: X-ray ; calibration ; filters ; interference ; oxidation
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    Topics: Physics
    Notes: Abstract We report on UV/Visible transmission measurements of aluminum coated Lexan filters designed as UV blocking filters for soft x-ray detectors. Transmission of the filters in the 2300-8000 Å wavelength range is significantly higher than expected. It cannot be accounted for applying a simple slab model of the transmission and adopting material properties reported in the literature. We show that this is due to interference effects which are strongly dependent on the filter geometry, and to oxidation of exposed aluminum surfaces and/or chemical interaction with the plastic support. The results of this work have led to the redesign of the Advanced X-ray Astrophysics Facility High Resolution Camera UV blocking filters.
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  • 51
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    Journal of sol gel science and technology 12 (1998), S. 35-48 
    ISSN: 1573-4846
    Keywords: yttrium acetate precursor ; particle coating ; oxidation ; corrosion ; Inconel
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract “Sol paint” that yields yttrium-based compounds was prepared by mixing four chemical ingredients, yttrium acetate tetrahydrate precursor, diethanolamine, isopropyl alcohol, and hydrochloric acid, and then applied as oxidation/corrosion resistant coatings for Inconel 625 substrates. Annealing the coatings at 500°C developed a coalescent microstructure of coarse particles consisting of amorphous yttrium carbonate as the major component and crystalline yttrium oxide (Y2O3) as the minor one. At 700°C, the yttrium carbonate was transformed into Y2O3 by decarbonation. Increasing the annealing temperature to 900°C led to the formation of the YCrO3 phase yielded by interaction between Y2O3 and the Cr2O3 which had arisen from the oxidation of the underlying Inconel; the YCrO3 phase created a particle coating with a densified microstructure. There were two key factors in mitigating the degree of oxidation of Inconel at 900°C in air: (1) an uptake of oxygen by Y2O3 in the coatings, and (2) a densified coating layer that suppresses the diffusion and permeation of oxygen through it. Furthermore, inhibiting the rate of NaCl-caused corrosion was not only due to the excellent coverage of particle coatings over the entire surfaces of the substrates, but also may be associated with a good adherence of the coatings to the substrates.
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  • 52
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    Oxidation of metals 44 (1995), S. 265-308 
    ISSN: 1573-4889
    Keywords: oxidation ; corrosion ; high temperatures ; erosion ; wear
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract There are several engineering systems which require materials of construction to tolerate elevated temperatures, and aggressive environments of one kind or another; and where, furthermore, the performance of the system is limited by the materials capability. This paper reviews a number of these systems, drawn principally from the electric power industry, and describes both the current approaches to improving the materials capability, and potential directions for research and development for the future. Particular emphasis is given to cases where the problems related to oxidation and high-temperature corrosion are of major importance.
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  • 53
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    Oxidation of metals 44 (1995), S. 339-374 
    ISSN: 1573-4889
    Keywords: analytical techniques ; Fe, Cr, Fe−Cr alloys, Ni, Al, β-NiAl ; oxidation ; transport processes
    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 considers the application of analytical techniques (particularly AES, SIMS, RHEED, laser Raman, Mössbauer, TEM, EELS) to high-temperature oxidation studies. Specific systems reviewed include NiO on Ni, oxides on Fe, Cr and their alloys, and Al2O3 on Al and β-NiAl. The often complementary information provided by the various techniques leads to a better understanding of oxide growth mechanisms on an atomic sale, interfacial segregation phenomena, and the role of reactive elements in modifying transport processes in oxides.
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    Oxidation of metals 45 (1996), S. 153-181 
    ISSN: 1573-4889
    Keywords: oxidation ; 18O diffusion ; nickel ; stress effects on diffusion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract This study deals with the influence of various mechanical loadings (fatigue, creep, creep-fatigue) on oxygen diffusion in a particular system, oxidizing nickel. A distinction between the behavior of the oxide layer and underlying nickel was noted during the first step of oxidation at 550°C, in PO 2=1 atm. Mechanical loading causes a decrease of the oxygen mobility through the oxide scale (factor of 103). The oxide thicknesses on nickel undergoing mechanical loadings are different than for an unloaded sample, due to distinct contributions of the oxygen and nickel fluxes in the growing oxide. In the substrate, the ingress of oxygen becomes easier with a constant tensile load (creep). The intergranular-oxygen diffusion coefficient, Di, is increased by a factor of 102 with respect to other samples. In creep, oxygen diffusion takes place along grain boundaries of a structure with smaller grains than in unstrained Ni. A short fatigue period during creep-fatigue decreases the sensitivity of nickel to intergranular-oxygen diffusion.
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  • 55
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    Oxidation of metals 47 (1997), S. 247-258 
    ISSN: 1573-4889
    Keywords: Ni3Al-base alloy ; sputtering ; nanocrystalline coating ; oxidation ; scale adhesion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Isothermal and cyclic oxidation resistance at 1000°C in air were investigated for a cast Cr-containing Ni3Al-base alloy and its sputtered nanocrystalline coating. The results indicated that both the cast Ni3Al alloy and its sputtered coating exhibit excellent isothermal oxidation resistance as a result of the formation of Al2O3 scales. However, the cast alloy possesses very poor cyclic oxidation resistance because of the spallation of the initially formed Al2O3 scale during cooling and subsequent formation of NiO. On the contrary, the sputtered Ni3(AlCr) nanocrystalline coating exhibits very good cyclic oxidation resistance due to the significant improvement of the adhesion of Al2O3.
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  • 56
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    Oxidation of metals 47 (1997), S. 259-275 
    ISSN: 1573-4889
    Keywords: laser surface alloying ; aluminum ; superalloys ; 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 high-temperature oxidation resistance of laser-surface-alloyed Incoloy 800H with Al has been investigated. Several samples have been exposed to 1000°C in air and subsequently analyzed by optical microscopy, SEM, and electron microprobe X-ray fluorescence spectroscopy in order to determine their microstructure and composition. The results show that the laser-treated materials have a considerably higher oxidation resistance than the nontreated materials due to the formation of an Al-rich layer close to the surface, which acts as a barrier against oxygen diffusion into the bulk.
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  • 57
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    Oxidation of metals 47 (1997), S. 381-410 
    ISSN: 1573-4889
    Keywords: Ni-Base superalloys ; Astroloy ; Waspaloy ; Udimet 720 ; oxidation ; chromia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Several commercially available Ni-base superalloys were exposed isothermally in air at temperatures between 750° and 1000°C and also under cyclic conditions at 1000°C. The kinetics of oxidation were determined and the scales were analyzed by electron microscopy and X-ray diffraction. Thin adherent chromia-rich scales formed on the alloys at 750°C after 1000 hr. Although Waspaloy showed the lowest weight gain in this test, it also showed the deepest internal corrosion due to oxidation of the grain-boundary carbides. At temperatures up to 1000°C the external scales were also chromia-rich but there was greater internal corrosion. Titanium in the alloys oxidized, diffusing through the chromia scale to form faceted rutile (TiO2) grains at the surface as well as forming TiO2 and TiN internally. The amount of rutile at the oxide surface increased with temperature and alloy Ti concentration. Alumina formed as discrete internal oxides below the chromia scale, although Astroloy when oxidized isothermally at 1000°C developed a semicontinuous internal layer of alumina due to its higher Al content. Under cyclic conditions Astroloy formed a thicker, less-protective scale of transition oxides probably due to its lower Cr content.
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  • 58
    ISSN: 1573-4889
    Keywords: oxidation ; Incoloy 909 ; superalloy ; scale ; high temperature ; kinetics
    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 of an Fe-38Ni-13Co-4.7Nb-1.5Ti-0.4Si superalloy (Incoloy 909 type alloy), was investigated at temperatures between 1000 K and 1400 K in Ar-(1, 10%)H20 atmosphere using metallographic, electron probe microanalysis, and X-ray diffraction techniques. The oxide scales consist of an external scale and an internal scale which has an intergranular scale (above 1200 K) and an intergranular scale. The oxide phases in each scale are identified asα-Fe2,O3 (below 1200 K) or FeO (above 1300 K) and CoO · Fe2O3 and FeO · Nb2O5, respectively. The morphologies, the oxide phases and the oxidation rates do not depend on the partial pressure of H2O in the range between one and ten percent in Ar gas. The rate constants for the intergranular-scale formation in this alloy are about one-tenth as large as those in Fe-36%Ni alloy reported previously. At all the temperatures the scales grow according to a parabolic rate law and the apparent activation energies for the processes are estimated.
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  • 59
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    Oxidation of metals 47 (1997), S. 445-464 
    ISSN: 1573-4889
    Keywords: oxidation ; Fe-Cr-Al alloy ; water vapor ; ESCA ; RHEED
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Fe-21.5 wt. %Cr-5.6 wt. %Al oxidation, at 1000°C, in dry or wet oxygen shows that steam has an influence on the oxide-scale growth mechanism. Steam modifies the kinetics of early-stage oxidation. In dry oxygen, an initial fast linear regime is observed during one hour. Under wet conditions, weight-gain curves follow the same parabolic regime over the entire oxidation test. The scale structure strongly depends on the presence of steam in the gaseous environment. With dry oxygen, the scale is composed mainly ofα-Al2O3 after the initial formation ofγ-Al2O3 identified by ESCA and RHEED. The kinetics transient stage corresponds to the necessary time for the internal part of the initialγ-Al2O3 scale to transform into a continuousα-Al2O3 diffusion barrier. Under wet oxygen conditions, transient oxides are identified as (Mg, Fe) (Cr, Al)2O4, MgAl2O4 (orthorhombic), Al2O3 (hexagonal), these oxides transform into MgAl2O4 (cubic), Cr3O4, Fe2O3,α-Al2O3, with time. When water vapor does not change drastically oxidation kinetics, the induced presence of iron and chromium in the oxide scale could be responsible for weakening the protectiveness of alumina scales.
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    Oxidation of metals 47 (1997), S. 507-524 
    ISSN: 1573-4889
    Keywords: alloys ; high temperature ; oxidation ; transient state
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The initial transient high-temperature oxidation stage for binary alloys forming the most-stable oxide has been examined by means of a numerical procedure based on the finite-difference method. At variance with previous models, the present treatment takes into account the effect of the rate of the reaction at the scale/gas interface over the corrosion kinetics. The calculations concerning the transient stage are developed either using the general parabolic rate law to represent the overall scaling kinetics or using the rate law of the reaction at the scale/gas interface as a boundary condition without imposing any particular rate law to the overall process. A correct analysis of the oxidation behavior of binary alloys during the transient stage must take into account the kinetics effect of the rate of the surface reaction. The concentration of the most-reactive element at the alloy/scale interface changes regularly with time, decreasing gradually from the initial bulk value to its final steady-state value. The present results are in good agreement with those obtained by means of an approximate analytical model developed previously.
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  • 61
    ISSN: 1573-4889
    Keywords: high temperatures ; oxidation ; transient state
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The transient state in the oxidation of solid solutions of a most-noble componentA in a most-reactive componentB (beta phase) for binaryA-B alloys presenting a limited reciprocal solubility of the two metals has been examined assuming that theirB content is sufficient for the exclusive growth of externalBO scales. Above a criticalB content of the alloy theBO scales may grow directly on the surface of the beta phase, while below this limit they can only form over a layer ofB-depleted solid solution ofB inA (alpha phase), which appears after a critical time. An approximate analytical expression for the profile of concentration ofB in the alloy has been adopted to calculate the flux ofB in the metal. Moreover, the effect of the reaction between the gas and the external oxide surface has been taken into account using a procedure developed by Wagner for the oxidation of pure metals. The corrosion kinetics as well as all the parameters involved, such as the concentration ofB at the alloy-scale interface, have been calculated as functions of the corrosion time. The results show that, as time proceeds, the instantaneous parabolic rate constant increases and the concentration ofB at the alloy-scale interface decreases, both tending gradually to their corresponding steady-state values. It is also predicted that if the rate of transformation of the beta phase in the alpha phase after the alloy reaches the composition of equilibrium at the interface with the oxide is lower than the corresponding rate of displacement of the alloy surface due to scale growth, the corrosion of beta phase alloys may eventually lead to the formation of two phase mixtures of alpha phase andBO which are expected to grow at much larger rates than in the presence of a uniform continuous alpha layer.
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  • 62
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    Oxidation of metals 48 (1997), S. 1-39 
    ISSN: 1573-4889
    Keywords: Ni-base ODS superalloys ; oxidation ; initial stages of oxidation ; alumina ; chromia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Mechanically-alloyed Ni-base ODS superalloys currently receive attention for application in future gas turbines because they exhibit outstanding mechanical properties at high temperatures. They also protect themselves against oxidation by forming chromia and/or alumina scales. However, little attention has been given so far to the initial stages of oxidation of Ni-base ODS superalloys, containing Cr as well as Al in considerable amounts. In the current work, oxidation at 1150°C was studied for different holding times up to 200 hr for the commercial materials MA6000 and PM3030 which contain. Al in increasing amounts. MA 754, a chromia former, was investigated as a reference. It was shown that for the potential alumina formers MA6000 and PM3030 the continuity and therefore protectiveness of the secondary Al2O3 at later stages is indeed determined by the initial stages of oxidation.
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  • 63
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    Oxidation of metals 48 (1997), S. 129-141 
    ISSN: 1573-4889
    Keywords: decarburization ; nickel ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A commercial-grade nickel containing small amounts of carbon, manganese, and silicon was exposed to air for periods up to 288 hr at 1050°C to study the effect of oxidation on the formation of oxides of these impurity elements. Exposure of nickel to air led to decarburization. The maximum amount of decarburization occurred during the initial period of air exposure and the loss in carbon was more in the metal with a smaller section size. Decarburization in the metal produced voids in the oxide scale due to the formation of CO2 gas. It has been shown further that CO and/or CO2 gas bubbles, which form in high purity nickel on grain boundaries during exposure to air at elevated temperatures, cannot exist in commercial-grade nickel where manganese is present as an impurity. Instead, oxides of manganese form in the grain boundaries as well as in the matrix. This is because manganese oxide is more stable than CO or CO2 gas.
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  • 64
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    Keywords: oxidation ; kinetics ; iron ; iron-nitride
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of α-Fe and ɛ-Fe2N1−z at 573 K and 673 K in O2 at 1 atm was investigated by thermogravimetrical analysis, X-ray diffraction, light-optical microscopy, scanning electron microscopy and electron probe X-ray microanalysis. Upon oxidation at 573 K and 673 K, on α-Fe initially α-Fe2O3 develops, whereas on ɛ-Fe2N1−z initially Fe3O4 develops. In an early stage of oxidation the oxidation rate of ɛ-Fe2N1−z appears to be much larger than of α-Fe. This can be attributed largely to an effective surface area available for oxygen uptake, which is much larger for ɛ-Fe2N1−z than for α-Fe due to the porous structure of ɛ-Fe2N1−z as prepared by gaseous nitriding of iron. The development of a magnetite layer in-between the hematite layer and the α-Fe substrate, at a later stage of oxidation, enhances layer-growth kinetics. After 100 min oxidation at 673 K the (parabolic) oxidation rates for α-Fe and ɛ-Fe2N1−z become about equal, indicating that on both substrates the oxide growth is controlled by the same rate limiting step which is attributed to short-circuit diffusion of iron cations. Oxidizing ɛ-Fe2N1−z increases the nitrogen concentration in the remaining ɛ-iron nitride, because the outward flux of iron cations, necessary for oxide growth, leads to an accumulation of nitrogen atoms left behind.
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    Oxidation of metals 48 (1997), S. 201-214 
    ISSN: 1573-4889
    Keywords: titanium-aluminum alloys ; niobium ; intermetallics ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In a recent study, CO2 has been reported to enhance the oxidation rate of binary titanium-aluminum alloys. The detrimental effect of CO2 was not, however, observed in a ternary alloy containing niobium. In this paper, possible explanations for these observations are examined. First, results from the literature regarding the effects of niobium in improving the resistance of titanium-aluminum alloys are briefly reviewed. Second, a thermodynamic analysis which offers a possible explanation for the beneficial effect of niobium in eliminating the CO2-enhanced oxidation of titanium-aluminum alloys is presented.
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  • 66
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    Oxidation of metals 48 (1997), S. 215-224 
    ISSN: 1573-4889
    Keywords: nanocrystallization ; oxidation ; mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Many mechanisms for the effect of reactive elements on the selective oxidation and scale adhesion of alloys have been proposed. However, nanocrystallization (or microcrystallization) has recently been found to have almost the same effect as that of reactive elements. This note reviews the effect of nanocrystallization on the selective oxidation and adhesion of Al2O3 scale with particular reference to the author's own results.
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  • 67
    ISSN: 1573-4889
    Keywords: oxidation ; titanium ; rutile ; scale ; high temperature ; kinetics
    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 behavior of pure titanium has been investigated in the temperature range of 1000 K to 1300 K in CO2 or Ar-10%CO2. Optical microscopy, electron probe microanalyses, and X-ray measurements on the oxide scales formed during oxidation indicate that their structures are nearly independent of temperature and the corrosion atmosphere. The scales consisted of two layers, an external one and an internal one, having a rutile (TiO2) structure. The parabolic rate law was confirmed for growth of the external scale and the permeation depth of oxygen in titanium with apparent activation energies of 266 and 226 kJ/mol, respectively. The rate-determining diffusion species in the oxidation processes are discussed.
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  • 68
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    Keywords: zirconium ; X-ray diffraction ; oxidation ; phase analysis ; texture
    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 of zirconium at high temperature (T〉 400°C) leads to reaction products of two allotropic oxide (ZrO2 monoclinic and ZrO2 tetragonal). The distribution and proportion of these two phases were studied as a function of time and space by X-ray diffraction techniques. Quantitative analyses are possible after some corrections, and we demonstrate the presence of a phase gradient in the oxide scale. The interest of this nondestructive method is then discussed.
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  • 69
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    Oxidation of metals 48 (1997), S. 357-380 
    ISSN: 1573-4889
    Keywords: chromium ; copper ; binary alloys ; two-phase alloys ; oxidation ; high temperatures
    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 in air of three two phase Cu-Cr alloys with nominal Cr contents of 25, 50, and 75 wt. % was studied at 700–900°C. The alloys corroded nearly parabolically, except at 900°C, when the corrosion rates decreased with time more rapidly than predicted by the parabolic rate law. The corrosion rate decreased for higher Cr contents in the alloy under constant temperature and generally increased with temperature for the same alloy composition. The scales were complex and consisted in most cases of an outermost copper oxide layer free from chromium and an inner layer composed of a matrix of copper oxide or of the double oxide Cu2Cr2O4, often containing particles of chromium metal surrounded by chromia and then by the double oxide. Metallic copper was also frequently mixed with chromia. Cr-rich regions tended to form continuous chromia layers at the base of the scale, especially at the highest temperature. No chromium depletion was observed in the alloy.
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  • 70
    ISSN: 1573-4889
    Keywords: iron ; oxidation ; CeO2 coating ; in situ ; growth stress ; residual stress ; texture ; X ray diffraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In situ XRD stress determinations have been performed during oxidation of pure iron (p(O2=2 × 10−3 Pa,T=800°C)). The compressive stress, initially present in the substrate due to surface preparation, is completely released at 400°C. Under the test conditions, the in situ compressive-stress level determined in the FeO scale during oxidation is not strongly dependent upon the presence of a ceria coating. On blank and coated specimens, the compressive stress varies from −400 ± 80 MPa to −150 ± 100 MPa during 30 hr oxidation. The decrease is quicker at the beginning of the test performed on blank specimens. Epitaxial relationships between the wüstite scale and iron (under low-pressure starting conditions) caused thein situ compressive stress in the oxide scale to be two times greater compared to the usual test conditions. This indicates that epitaxial relationships can be a source of stress in an oxide scale that ceria coatings may lower compressive stresses.
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    Oxidation of metals 48 (1997), S. 527-551 
    ISSN: 1573-4889
    Keywords: chloridation ; oxidation ; Fe-Cr alloys ; Ni-Cr alloys
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The chloridation-oxidation behavior of Fe-Cr (0–25 wt. %Cr) and Ni-Cr (0–20 wt.%Cr) alloys was studied at 800°C in three different H2-HCl-H2O(ν) environments. In a low-HCI and low-H2O(ν) environment, where Cr2O3 is thermodynamically stable, the corrosion resistance of the Fe-Cr alloys increased with increasing Cr content in the alloys. In a high-HCl and high-H2O(ν) environment, where FeCr2O4 is stable and CrCl2 is metastable, the corrosion resistance of the Fe-Cr alloys depended similarly on the Cr content. Low-Cr-Fe-Cr alloys exhibited large weight losses, while Fe-Cr alloys with higher than 19 wt. %Cr showed good corrosion resistance. In an environment of high-HCl in the absence of H2O(ν), the evaporative corrosion rate was fast and limited by gas phase diffusion, and independent of the Cr content in the Fe-Cr alloys. Ni and Ni-Cr alloys generally showed good corrosion resistance in the environments of high H2O(ν) because of the low NiCl2 vapor pressure and formation of a protective Cr2O3 scale. However, in the environment of high HCl in the absence of H2O(ν), selective formation and evaporation of CrCl2 occur, which results in Cr depletion and networks of voids for even a high-Cr Ni-Cr alloy.
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    Oxidation of metals 48 (1997), S. 553-596 
    ISSN: 1573-4889
    Keywords: chloridation ; oxidation ; HCl ; high-temperature alloys ; high-temperature corrosion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Chloridation-oxidation studies of nine commercial high-temperature alloys were carried out at 800°C in three different H2-HCl-H2O(ν) environments: (A) both low HCl and H2O(ν) partial pressures, where either Cr2O3 or FeCr2O4 is stable, (B) both high HCl and H2O(ν) partial pressures, where FeCrO4 is stable and CrCl2 is metastable, and (C) high HCl partial pressure in the absence of H2O(ν), where either CrCl2 or Cr2O3 is stable. Although alloy 600 has the lowest Cr content of these nine alloys, it showed excellent corrosion resistance in all three environments because of its high Ni content. Alloy 304, with the lowest Ni content of the nine alloys, exhibited poor corrosion resistance in the environment C, fair resistance in the environment B and good resistance in the environment A. Alloy 800 showed very good resistance in Environment A, and fair corrosion resistance in Environment B; however, it suffered linear weight-loss kinetics when exposed to Environment C The alloys 617, 214, HR-160, X, 230 and 86 have good corrosion resistance in Environments A and B because of their relatively high contents of oxide-scale-forming elements Cr and/or Al. In Environment C, chlorine dramatically decreased the adhesion of the scale on the surface, and aluminum in alloys 617 and 214 hardly showed its usual beneficial effect in combating corrosion, nor does silicon in alloy HR-160. Different corrosion mechanisms are proposed for the alloys in the different environments.
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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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    Journal of sol gel science and technology 8 (1997), S. 443-449 
    ISSN: 1573-4846
    Keywords: coatings ; protection of metals ; oxidation ; corrosion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Sol-gel derived films can be deposited on metals to improve their resistance to oxidation and corrosion or to modify their surface properties. However, practical applications are limited by problems intrinsic to sol-gel processing or specific of coating/metal systems. Coatings aimed to improve oxidation and wet corrosion resistance have been the most studied. The results published in the literature show that sol-gel coatings may offer good protection against oxidation. More difficult is to achieve a protection against wet corrosion. An important aspect of the application of the sol-gel method for coating metallic objects is also the deposition technique.
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    Journal of materials synthesis and processing 6 (1998), S. 191-195 
    ISSN: 1573-4870
    Keywords: Transmission electron microscopy observation ; interfacial microstructure ; oxidation ; ZrC ; cubic ZrO2 ; amorphous carbon film
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Microstructure at the interface of ZrC and ZrO2 formed by oxidation of a single crystal of ZrC with 100 faces at 600°C at an oxygen pressure of 2 kPa was observed by high-resolution transmission electron microscopy and scanning electron microscopy. The ZrO2 scale was shown to consist of two subscales, zones 1 and 2. The interfacial area in zone 1 was composed of regular lattice fringes corresponding to the 111, 200, and 220 lattices of cubic ZrO2 (c-ZrO2) crystallites 2 to 10 nm in size and an amorphous phase. The growth of crystallites occurred in zone 2, which visualized the interface of zones 1 and 2. Black thin films reminiscent of zone 1 were successfully separated, which were composed of amorphous carbon in which c-ZrO2 particles 2 to 20 nm in size were included.
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    Journal of materials synthesis and processing 6 (1998), S. 335-338 
    ISSN: 1573-4870
    Keywords: PbZrO3 ; oxidation ; nonstoichiometry
    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 reports the results of work function (WF) changes of undoped PbZrO3 during subsequent isothermal oxidation and reduction experiments at 500°C in the p(O2) range between 10 and 2.1 × 104 Pa. The results, obtained during three consecutive runs, indicate that heating at 500°C leads to continuous changes of surface properties resulting in a complex WF vs. time characteristic. The WF changes during the first oxidation are determined by a p(O2)-induced structural transition. The second oxidation results in two competitive processes, such as rapid increase of oxygen non-stoichiometry followed by a structural transition. Finally, the third oxidation is determined by changes of oxygen nonstoichiometry.
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    Journal of materials synthesis and processing 6 (1998), S. 373-377 
    ISSN: 1573-4870
    Keywords: Zirconia ; oxidation ; preparation
    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 reports surface electrical properties of zirconia studied using work function measurements in the temperature range 297–1173 K during oxidation. It was found that surface preparation procedures, such as grinding and polishing, result in a change of its reactivity with oxygen. The effects produced by the preparation can be removed during thermal treatment at 1473 K.
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    Oxidation of metals 43 (1995), S. 157-172 
    ISSN: 1573-4889
    Keywords: oxidation ; NiAl ; ion implantation ; 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 influence of Y-ion implantation on the oxidation of β-NiAl single crystals has been investigated using SEM, TEM, and STEM. Y ions having an energy of 70 keV were implanted with a concentration of 5×1016 ions/cm2. The oxidation experiments were performed in air at 1223 K. Y-ion implantation resulted in a 45-nm disordered layer. Oxidation of Y-implanted β-NiAl leads to the formation of a fine-grain layer, consisting of γ-Al2O3 containing Y and a θ-Al2O3 layer. After further oxidation the metastable Al2O3 transformed into α-Al2O3, which started at the metal-oxide interface. Y-Al-garnet (YAG) particles were observed and Y segregation to α-Al2O3 grain boundaries has been detected.
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  • 79
    ISSN: 1573-4889
    Keywords: oxidation ; reactive-element effects ; electrodeposition ; Y2O3 ; oxide film
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Thin Y2O3 films were deposited by the electrochemical deposition-pyrolysis process on Fe−25Cr and Fe−25Cr−10Al alloys. The influence of the films on the oxidation behavior of the alloys was studied at 850°C and 1000°C. The results showed that Y2O3 films remarkably decreased the oxidation rate of Cr2O3-forming alloys and spallation of the scales, but they did not decrease the oxidation rate of the Al2O3-forming alloys, although they do reduce the spallation of Al2O3 scales. Y2O3 films remarkably change the morphology of the scales on both alloys, depending on the oxidation temperatures. These results show that the reactive-element effects of Y2O3 films on the Cr2O3 formers and Al2O3 formers are different.
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  • 80
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    Oxidation of metals 43 (1995), S. 185-215 
    ISSN: 1573-4889
    Keywords: copper ; oxidation ; direct current ; uninterrupted mode ; interrupted mode
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Oxidation kinetics of copper in the temperature range of 973–1173 K atP O 2=21.27 kPa exhibit enhancement and deceleration in the rates with changing polarity compared to normal oxidation under interrupted mode of directcurrent application. These conditions are achieved by connecting the oxidizing copper covered with an initially formed thin oxide film to the positive and negative terminal of a dc source, respectively. However, the influence of direction of the current is found to be opposite under uninterrupted mode of impressed current flow in the same temperature range. The effect of short-circuiting the metal to the outer oxide/air interface on the reaction kinetics is also reported. The rate of oxide-scale growth under normal condition, and two different modes of current applications as well as with shorting circuitry attachment conform to the parabolic growth law. The results pertaining to the two different modes of impressed current have been discussed considering both the phenomena of electrolysis of the oxide electrolyte and the polarization at the two phase boundaries. The enhancement and the reduction in rates under uninterrupted impressed current conditions are explained on the basis of increased and decreased average defect concentrations, respectively, within the oxide layer. The acceleration and deceleration in the rates under interrupted mode of current flow have been explained in the light of sustenance of a steeper and flatter electrochemical-potential gradient of defects, respectively, across the growing-oxide layer. The possible different responses of the metal/oxide and oxide/air interfaces to the impressed current brought into play by two different modes of current application, have enabled to display a better insight on the mechanistic aspects of scale growth under the influence of an externally applied current.
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  • 81
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    Oxidation of metals 43 (1995), S. 237-261 
    ISSN: 1573-4889
    Keywords: manganese ; oxidation ; ceria ; coating ; air ; low oxygen pressure ; high temperature ; manganosite ; transport mechanism ; iron ; CeFeO3 structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The kinetics, scale composition, and growth mechanism of ceria-coated and blank specimens of manganese oxidation in air were examined. The scale growth obeys the parabolic rate law at 700°C for all specimens. Lower parabolic rate constants for coated specimens are attributed to the presence of a CeO2 external scale. It constitutes a limiting factor of the oxygen activity at the gas-oxide interface. This lower-oxygen activity leads to a less-metal-deficient state of the scale. Due to this, the inner-MnO scale becomes more adherent to the substrate. Preheating at 700°C, in hydrogen (PO 2=10−24 atm), was performed in order to be placed in the MnO stability domain and try to introduce cerium in the manganese-oxide scale. This pretreatment promotes macroscopic bonding in the layer formed during subsequent oxidation in air. It ensures a better scale adherence. A new diffusional-transport mechanism in manganosite is proposed in accordance with all experimental observations of the literature and with the cerium-manganese-oxygen system studied in the present work. This model considers the high Mn3+ stability in octahedral sites of the MnO oxygen ion body. Low-oxygen partial pressure conditions permit the formation of an adherent inner-MnO scale on coated specimens. A CeO2 scale formed above the MnO scale; MnO is present as a minor component in this scale and it is located mainly at the internal interface. The difficulties in forming the cerium-orthomanganite are attributed to the very high stability of MnO related to this wide range of nonstoichiometry and to the low manganese diffusivity through the cerium-containing scale.
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  • 82
    ISSN: 1573-4889
    Keywords: oxidation ; chromium coating ; laser ; oxygen diffusion
    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 of a chromium PVD coating on pure iron by a continuous 5-kW CO2 laser beam in pure oxygen at 700°C for 20 min was compared with classical furnace oxidation. Laser oxidation induces faster oxidation kinetics, especially at the beginning of oxidation, without modifying the oxide nature (Cr2O3) and morphology. Oxygen-isotopic-exchange tests show that oxygen grain-boundary diffusion does not depend on the oxidation conditions, at least after 12 min oxidation. The effec of the laser treatment is discussed with respect to oxide nucleation, metastable-oxide formation, and oxide-formation-entropy evolution. The oxidation kinetics follow a parabolic law, and the oxide-growth mechanism was attributed to countercurrent oxygen and chromium diffusion along grain boundaries. Oxygen diffusion occurred by oxygen interstitials. The oxidation constant calculated from grain-boundary diffusion in the chromia scale is smaller than the experimental oxidation constant, suggesting the presence of particular short circuits (e.g., microcracks).
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  • 83
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    Oxidation of metals 43 (1995), S. 317-328 
    ISSN: 1573-4889
    Keywords: microcrystalline ; rehealing ; oxide scales ; superalloys ; 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 The rehealing ability of the protective oxide scales formed on a microcrystalline coating of the Ni-base superalloy K38G has been studied. The results indicated that the oxide scales on the coating may be rehealed when the original scales are destroyed, and the coating still has excellent resistance against high-temperature oxidation. When the original Al2O3 oxide scales spall, mixed-oxide scales of both (Al, Cr)2O3 and TiO2 can form on the surface. The mixed scales are very protective and adherent.
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  • 84
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    Oxidation of metals 43 (1995), S. 263-277 
    ISSN: 1573-4889
    Keywords: Fe−Cr−Ni alloy ; oxidation ; silica ; spallation
    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 determine the effect of alloy grain size on the oxidation properties of silica-coated austenitic Fe-18Cr-20Ni stainless steel, both coarse-grain (100-μm grain size) and fine-grain (5-μm grain size) forms of the alloy were produced. A 1-μm-thick vitreous silica coating was deposited by chemicalvapor deposition on the alloys, which were subjected to isothermal and cyclic oxidation in air at 900°C. The coarse-grain alloys underwent widespread oxidation below the silica coating, leading to extensive coating spallation. This was attributed to the inability of the alloy to supply a sufficient outward flux of chromium to prevent oxygen penetration through microcracks in the silica coating. Due to an abundance of chromium available at the surface of the finegrain alloy, chromia formed in the microcracks within the silica layer. As a result, the silica-coated, fine-grain alloy demonstrated superior oxidation resistance and excellent adhesion of the coating.
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  • 85
    ISSN: 1573-4889
    Keywords: Ni−Cr−Al−Ti−Si bond-coating alloy ; phase stability ; oxidation ; interdiffusion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A novel, low-expansion experimental Ni−Cr−Al−Ti−Si bond-coating alloy was investigated in the as-cast state concerning its phase stability, oxidation resistance in air, and interdiffusion with single-crystal IN-100 at 900, 1000, and 1100°C. Isothermal oxidative thermogravimetry was employed up to 500 hr. Interdiffusion was compared to a commercial Ni−Co−Cr−Al−Y alloy on IN-100. Oxidized Ni−Cr−Al−Ti−Si specimens and diffusion couples were characterized by metallography, SEM, EDX, XRD, and XRF. The Ni−Cr−Al−Ti−Si alloy provides good oxidation resistance in air at least up to 1000°C. The alloy is an alumina former. Due to its coarse microstructure, other oxides (e.g., rutile) may form and considerably dominate the oxidation behavior. The kinetics of oxidation were correlated with temperature, formation of phases, and morphology of oxides. Interdiffusion fluxes between Ni−Cr−Al−Ti−Si and IN-100 were mainly directed to the superalloy. They were faster than in Ni−Co−Cr−Al−Y/IN-100 diffusion couples.
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  • 86
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    Oxidation of metals 43 (1995), S. 379-394 
    ISSN: 1573-4889
    Keywords: two-phase alloys ; oxidation ; scale structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The main possible modes of the high-temperature corrosion of binary two-phase alloys by a single oxidant under gas-phase pressures sufficient to corrode only the most-reactive alloy component are examined to compare their behavior with that of single-phase alloys. In the absence of important diffusion processes of the metal components in the alloy, the scale structures expected are different from those typical of single-phase alloys. Moreover, when diffusion in the alloy becomes important, these systems may develop an outer single-phase layer depleted in the most-reactive component, which may lead to different possible scale structures. The conditions for the transition between the various oxidation modes as well as the effect of the various parameters of kinetic, thermodynamic, and structural nature over the corrosion behavior of two-phase alloys are also examined.
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  • 87
    ISSN: 1573-4889
    Keywords: oxidation ; reactive-element effect ; reactive-element oxysulfide ; reactive-element oxide ; reactive-element orthochromite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Nickel-base alloys of nominal composition Ni-25 Wt.% Cr-(0-0.6 Wt.%) RE (RE=Y, La, and Ce) were prepared by conventional arc-melting Ni, Cr, and Y metal. The microstructure of the alloys was characterized by using electron diffraction and X-ray energy dispersive spectroscopy (XEDS) to determine the structure, morphology, and distribution of second-phase particles. Selected alloys were oxidized at 900°C and 1000°C in 1-atm air, and the resultant oxide scales were characterized using the same analytical techniques. The experimentally determined electron-diffraction data were compared with a JCPDF-EDD database, and several compounds were matched. The observed phases were RE oxysulfide, cerium orthochromite-CeCrO3, yttria-Y2O3, yttrium orthochromite-YCrO3, and Ni5Y. The significance of these observations is discussed with respect to the current level of knowledge on the role of sulfur in the reactive-element effect. The ability of the reactive elements to getter sulfur is examined with respect to the thermodynamic stability of the oxysulfide species.
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  • 88
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    Oxidation of metals 43 (1995), S. 395-409 
    ISSN: 1573-4889
    Keywords: microcrystalline film ; TiAl intermetallic compound ; oxidation
    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 behavior of a cast TiAl intermetallic compound and its sputtered microcrystalline film was investigated at 700–900°C in static air. At 700°C, both the cast alloy and its sputtered microcrystalline film exhibited excellent oxidation resistance. No scale spallation was observed. However, at 800–900°C, the oxidation kinetics for the cast TiAl alloy followed approximately a linear rate law, which indicates that it has poor oxidation resistance over this temperature range. The poor oxidation resistance of TiAl was due to the formation of an Al2O3+TiO2 scale which spalled extensively during cooling. Nevertheless, the sputtered, TiAl-microcrystalline film exhibited very good oxidation resistance. The oxidation kinetics followed approximately the parabolic rate law at all temperatures. Although the composition of the scales was the same as that of scales formed on the cast alloy, the scales formed on the sputtered microcrystalline-TiAl film are adherent strongly to the substrate. No scale spallation was found at 700–850°C, while a small amount of spallation was observed only at 900°C. This indicates that microcrystallization can improve the oxidation resistance of the TiAl alloy.
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  • 89
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    Oxidation of metals 43 (1995), S. 509-526 
    ISSN: 1573-4889
    Keywords: oxidation ; kinetics ; tantalum ; oxide ; suboxide ; impurities ; diffusion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The kinetics, structural aspects, and phase morphologies were studied for tantalum oxidation in air from 600 to 1000°C for samples of different purity (99.15%, 99.76%, and 99.95% Ta). Regardless of purity, tantalum oxidation in the temperature range of 600–800°C as a rule is governed by a linear rate law. From 900 to 1000°C the initial-stage oxidation is governed by the parabolic rate law, which changes to the linear rate law with time. TGA, XRD, SEM, and AES methods were used. The, effect of purity on tantalum oxidation was shown to be determined by the mechanism of intermediate-oxide formation. They are TaO z (Ta2O) at 600–800°C and TaO at 900–1000°C. The final product of oxidation was β-Ta2O5.
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  • 90
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    Oxidation of metals 43 (1995), S. 527-542 
    ISSN: 1573-4889
    Keywords: Co−Nb alloys ; high temperature ; oxidation
    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 of two Co−Nb alloys containing 15 and 30 wt.% Nb has been studied at 600–800° C in H2−CO2 mixtures providing an oxygen pressure of 10−24 atm at 600°C and 10−20 atm at 700 and 800°C, below the dissociation pressure of cobalt oxide. At 600 and 700°C both alloys showed only a region of internal oxidation composed, of a mixture of alpha cobalt and of niobium oxides (NbO2 and Nb2O5) and at 700°C also the double oxide CoNb2O6, which formed from the Nb-rich Co3Nb phase. No Nb-depleted layer formed in the alloy at the interface with the region of internal oxidation at these temperatures. Upon oxidation at 800°C a transition between internal and external oxidation of niobium was observed, especially for Co−30Nb. This corrosion mode is associated with the development of a single-phase, Nb-depleted region at the surface of the alloy. The corrosion mechanism of these alloys is examined with special reference to the effect of the low solubility of niobium in cobalt and to the relation between the microstructures of the alloys and of the scales.
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  • 91
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    Oxidation of metals 44 (1995), S. 177-209 
    ISSN: 1573-4889
    Keywords: sulfidation ; oxidation ; common and refractory metals and alloys ; amorphous alloys
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The role of defect and transport properties of transition metal sulfides on the kinetics and mechanism of high-temperature sulfide corrosion of metals and alloys is discussed. It has been shown, that due to the very high concentration of defects in common metal sulfides, not only pure metals but also conventional high-temperature alloys (chromia and alumina formers) undergo very rapid degradation in highly sulfidizing environments. Refractory metals, on the other hand, are highly resistant to sulfide corrosion, their sulfidation rates being comparable with the oxidation rate of chromium. Pioneering work of Douglasset al. has shown that alloying of common metals by niobium or molybdenum, and in particular combined alloying by molybdenumand aluminum, dramatically decreases the sulfidation rate. A novel Fe−30Mo−9Al alloy has been proved to be highly resistant to sulfide corrosion, its sulfidation rate being comparable with that of pure molybdenum. Even better resistance to highly-sulfidizing environments show new amorphous Al−Mo and Al−Mo−Si alloys, these materials also being simultaneously oxidation resistant. Thus, new prospects have been created for the development of a new generation of coating materials, resistant to multicomponent sulfidizing-oxidizing atmospheres, often encountered in many branches of modern technology.
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  • 92
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    Oxidation of metals 44 (1995), S. 399-415 
    ISSN: 1573-4889
    Keywords: Ni−Nb alloys ; high temperature ; oxidation
    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 of two Ni−Nb alloys containing 15 and 30 wt.% Nb has been studied at 600–800° C in H2−CO2 mixtures providing an oxygen pressure of 10−24 atm at 600° C and 10−20 atm O2 at 700 and 800° C, these pressures being less than the dissociation pressure of nickel oxide. The scales formed on both alloys at 600 and 700° C show only a region of internal oxidation composed of a mixture of alpha nickel and niobium oxides (Nb2O5 or/and NbO2), which formed from both the metal phases present, i.e., Ni8Nb and Ni3Nb. Only small, or even no, Nb depletion was observed in the alloys close to the interface with the zone of internal oxidation at these temperatures. On the contrary, samples of both alloys corroded at 800° C produced a continuous external scale of niobium oxides without internal oxidation. The corrosion mechanism of these alloys is examined with special reference to the effect of the low solubility of niobium in nickel.
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  • 93
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    Oxidation of metals 44 (1995), S. 505-525 
    ISSN: 1573-4889
    Keywords: ODS alloys ; oxidation ; scale adherence ; surface roughness ; porosity
    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 three oxide-dispersion-strengthened (ODS) alloys, viz., MA 956, ODM 751, and PM 2000, has been examined in air at 1200°C for exposure times up to 4800 hr. During exposure all the alloys formed an external scale of alpha alumina (α-Al2O3). The growth rate of alumina on MA 956 was significantly faster than that formed on ODM 751 resulting in an oxide layer which was about twice as thick after 4800 hr. The oxide-grain morphology on MA 956 was essentially equiaxed containing irregularly shaped, titanium-rich particles, whereas the oxide formed on ODM 751 was slightly finer, distinctly columnar and contained elongated yttrium-rich particles. Spalling of the oxide layer occurred after approximately 2400 hr on MA 956, whereas only slight spalling occurred on ODM 751 even after the longest exposure time. Experiments revealed that the initial surface roughness of PM 2000 can contribute significantly to spalling by enabling the growth of highly convoluted scale layers which are mechanically unstable under compressive stresses (buckling). Internal porosity is also observed in all three alloys after exposure. The pores were generally spherical with small Ti-, Al-, Y-rich particles distributed over their internal surfaces. The amount of porosity increases to a maximum and then slowly decreases.
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  • 94
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    Oxidation of metals 45 (1996), S. 507-527 
    ISSN: 1573-4889
    Keywords: oxidation ; sulfidation ; oxides ; sulfides ; Ti ; Ti-6Al-4V alloy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Pure titanium and Ti-6Al-4V were exposed at 750°C in an H2/H2O/H2S PO 2≈10−18 Pa and PS 2≈10−1 Pa), H2/H2O (PO 2≈10−18 Pa) and air environments for up to 240 hr. The corrosion kinetics, obtained by the discontinuous gravimetric method, showed that the sulfidation/oxidation kinetics were linear for Ti and linear-parabolic for Ti-6Al-4V in the H2/H2O/H2S environment. Both materials obeyed parabolic rate laws in the H2/H2O atmosphere after a transient period, and linear-parabolic rate laws in air. After exposure to the H2/H2O/H2S atmosphere, the titanium specimen displayed a double scale of TiO2 with an intervening TiS2 film between the double-layered scale of TiO2 and the substrate. Ti-6Al-4V also contained a double layer of TiO2 together with a stratum consisting of Al2S3, TiS2 and vanadium sulfide at the junction of the inner TiO2 layer and substrate. Some Al2O3 precipitated in the external portion of the outer TiO2 layer. Following oxidation in the low-PO 2 atmosphere a double-layered oxide of TiO2 scale formed on both Ti and Ti-6Al-4V. The scale on Ti-6Al-4V also contained an α-Al2O3 film situated between the outer and inner (TiO2) layers. For both materials, multilayered-scale formation characterized air oxidation. In detail a multilayered oxide scale of TiO2 formed on the air-oxidized Ti, while a multilayered oxide scale with alternating layers of Al2O3/TiO2 developed on Ti-6Al-4V oxidized in air.
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  • 95
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    Oxidation of metals 45 (1996), S. 487-505 
    ISSN: 1573-4889
    Keywords: sulfidation ; oxidation ; gasification ; austenitic steel alloys
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The major use of high-temperature steel alloys in gasifiers is in heat exchangers for cooling hot syngas, consisting mainly of CO and H2 with lesser amounts of H2O and CO2 and minor quantities of H2S and HCl. Metal temperatures range from 250 to 600°C, gas temperatures from 250 to 1200°C. Because of rapid cooling the composition of the gas does not change with temperature. Therefore the gas is not in equilibrium at the metal surface. Calculations show that such gases have lower oxygen and sulfur pressures than equilibrated gases at the same temperature. This makes the results of previous laboratory studies less appropriate for predicting mixed oxidant corrosion in gasifiers. For this reason the present study was carried out using nonequilibrium gas mixtures, similar to gases, produced in entrained-slagging gasifiers. Most corrosion experiments were carried out at 540°C, as this is a common temperature for superheaters and hot-gas cleanup systems. Iron-base model alloys containing 35% Ni, 20% Cr, and various minor alloying additions were studied. Three corrosion regimes were identified over the range of conditions studied, depending on the sulfur-to-oxygen pressure ratio of the gas and the alloy composition. At high PS 2/PO 2 ratios a somewhat protective FeCr2S4 scale formed on all alloys. Below this layer internal oxidation and sulfidation occurred at a slow rate. At lower PS 2/PO 2 ratios nonprotective Fe(Ni, Cr)S external scales formed. These allow rapid internal oxidation of the chromium in the alloy, resulting in high corrosion rates. Under the same conditions very low corrosion rates are obtained when silicon is added to the alloy, because the presence of SiO2 precipitates makes the internal-oxidation layer protective. Thus, the same corrosion model is operative in all three corrosion regimes: external sulfidation of iron and nickel, together with internal oxidation of chromium and other strong-oxide formers.
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  • 96
    ISSN: 1573-4889
    Keywords: oxidation ; copper ; Li-doped copper ; Cr-doped copper ; short-circuiting ; Mott's parabola ; Wagner's parabola
    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 shorting circuitry attachment between metal-oxide and oxideoxygen interfaces on the oxidation kinetics of copper, lithium-doped copper (Li: 400 ppm), and chromium-doped copper (Cr: 12 ppm) have been studied in dry air $$(P_{O_2 } = 21.27kPa)$$ in the temperature range of 523–1073 K. Oxide film or scale growth under short-circuiting as well as under normal oxidation conditions conforms to the parabolic rate law. The oxidation kinetics under short-circuiting resulted in decreased rates for Cu and Li-doped Cu up to a temperature of 773 K, while Cr-doped Cu exhibited an enhancement in rate compared to its normal oxidation in the same temperature range. However, above 873 K, all three systems under shorting circuitry attachment exhibited enhanced rates compared to their normal oxidation rates in conformity to the existing theoretical model. Use of additional resistances in series in the outer short-circuit Pt path have clearly established that below 773 K Mott's fieldinduced migration plays the most important role, while at elevated temperatures Wagner's electrochemical potential-gradient factor acts as the main driving force in the scale-growth process. The results have been interpreted on the basis of average defect concentration, the electrochemical potential gradient, electrical field gradient, and transport coefficient in the Cu2O layer.
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  • 97
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    Oxidation of metals 46 (1996), S. 109-127 
    ISSN: 1573-4889
    Keywords: oxidation ; Ni3Al base alloy ; chromium ; cobalt ; titanium
    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 behavior of Ni3Al+2.90 wt.% Cr, Ni3Al+3.35 wt% Co, and Ni3Al+2.99 wt.% Ti alloys was studied in 1 atm of air at 1000, 1100, and 1200°C. Isothermal tests revealed parabolic kinetics for all three alloys at all temperatures. Cyclic oxidation for 28 two-hour cycles produced little spallation at 1000°C, but caused partial spallation at 1100°C. Especially, at 1200°C severe spallation in all three alloys was observed. Although additions of Cr, Co, or Ti to Ni3Al alloys slightly increased the isothermal-oxidation resistance, the additions tended to decrease the cyclic-oxidation resistance. The major difference in the oxidation of the three alloys compared with the oxidation of pure Ni3Al alloys was the existence of small α-Al2O3 particles in the middle of the α-Al2O3 scale and the formation of irregularly shaped Kirkendall voids at the alloy-scale interface.
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    Oxidation of metals 46 (1996), S. 255-285 
    ISSN: 1573-4889
    Keywords: electron diffraction ; intermetallic ; oxidation ; TEM ; titanium aluminide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The early stages of TiAl oxidation at 900°C and 1000°C in air have been investigated by transmission electron microscopy (TEM). The investigations revealed that at the beginning of oxidation, i.e., after 4 min, TiO2 and Al2O3 grow in a preferential orientation on the γ-TiAl substrate. After 4 h of oxidation an oxide scale structure can already be found similar to that known from long-term oxidation. In addition, besides α-Al2O3, the formation of a second aluminum oxide phase and of titanium nitrides is observed. The processes at the metal-oxide interface of oxidation in the early stages, consisting of a repeated cycle of Al2O3 formation, Al2O3 dissolution, outward migration of Al through the scale, and reprecipitation of Al2O3 in the outer scale, are described by a model. The four stages observed in the kinetics of TiAl oxidation are explained on the basis of the results obtained and the structure of the oxide scale.
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  • 99
    ISSN: 1573-4889
    Keywords: binary alloys ; oxidation ; transient state ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The initial transient stage in the oxidation of binary alloys forming scales exclusively composed of the most stable oxide is examined by means of a simplified approach which avoids the numerical integration of the diffusion equation for the transport of the metal components in the alloy. At variance with previous solutions to this problem obtained by means of numerical methods, this treatment takes into account also the effect of the gas-scale reaction at the outer surface of the oxide. The concentration of the most-reactive component at the alloy surface changes gradually with time from the initial bulk value towards the corresponding steady-state value without involving any minimum, while the overall rate of the reaction presents a gradual transition from an initial nearly linear towards final parabolic behavior.
    Type of Medium: Electronic Resource
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  • 100
    Electronic Resource
    Electronic Resource
    Springer
    Oxidation of metals 47 (1997), S. 69-89 
    ISSN: 1573-4889
    Keywords: duplex-layer formation ; dynamic oxygen-diffusion path ; Ni-Cr alloy ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The results of an investigation of oxidation of a Ni-1 at.% Cr alloy are presented. Photolithographic marker experiments revealed that the markers were found to reside at the interface between a predominantly columnar outer NiO layer and a very fine grain inner layer of NiO, indicating that substantial oxygen ingress had occurred through the columnar scale. New oxide growth at the metal-oxide interface requires the oxidant to be transported across the oxide layer. Since the measured diffusion rate of oxygen ions along grain boundaries and through the lattice is much too slow to account for the observed microstructural growth (∼1: 1 ratio of inner and outer layers), it is necessary to postulate that the oxidant traverses the scale along some type of short-circuit path other than grain boundaries. Extensive formation of elongated pores and pipelike channels was observed along columnar oxide grain boundaries. Thus, it appears that the transport of oxygen occurs via voids (pores) formed by vacancy coalescence at the columnar grain boundaries. These pores appear to open and close continuously. Formation of new fine-grained oxide in these pores was observed to have sometimes completely resealed the void, suggesting a dynamic nature of the voids.
    Type of Medium: Electronic Resource
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