WorldWideScience

Sample records for temperature oxidation co-oxidation

  1. Chemical engineering design of CO oxidation catalysts

    Science.gov (United States)

    Herz, Richard K.

    1987-01-01

    How a chemical reaction engineer would approach the challenge of designing a CO oxidation catalyst for pulsed CO2 lasers is described. CO oxidation catalysts have a long history of application, of course, so it is instructive to first consider the special requirements of the laser application and then to compare them to the characteristics of existing processes which utilize CO oxidation catalysts. All CO2 laser applications require a CO oxidation catalyst with the following characteristics: (1) active at stoichiometric ratios of O2 and CO, (2) no inhibition by CO2 or other components of the laser environment, (3) releases no particulates during vibration or thermal cycling, and (4) long lifetime with a stable activity. In all applications, low consumption of power is desirable, a characteristic especially critical in aerospace applications and, thus, catalyst activity at low temperatures is highly desirable. High power lasers with high pulse repetition rates inherently require circulation of the gas mixture and this forced circulation is available for moving gas past the catalyst. Low repetition rate lasers, however, do not inherently require gas circulation, so a catalyst that did not require such circulation would be favorable from the standpoint of minimum power consumption. Lasers designed for atmospheric penetration of their infrared radiation utilize CO2 formed from rare isotopes of oxygen and this application has the additional constraint that normal abundance oxygen isotopes in the catalyst must not exchange with rare isotopes in the gas mixture.

  2. Characterization of Cu/CeO2/Al2O3 catalysts by temperature programmed reduction and activity for CO oxidation

    International Nuclear Information System (INIS)

    Cataluna, Renato; Baibich, Ione M.; Dallago, R.M.; Picinini, C.; Martinez-Arias, A.; Soria, J.

    2001-01-01

    The kinetic parameters for the CO oxidation reaction using copper/alumina-modified ceria as catalysts were determined. The catalysts with different concentrations of the metals were prepared using impregnation methods. In addition, the reduction-oxidation behaviour of the catalysts were investigated by temperature-programmed reduction. The activity results show that the mechanism for CO oxidation is bifunctional: oxygen is activated on the anionic vacancies of ceria surface, while carbon monoxide is adsorbed preferentially on the higher oxidation copper site. Therefore, the reaction occurs on the interfacial active centers. Temperatures-programmed Reduction patterns show a higher dispersion when cerium oxide is present. (author)

  3. Monolithic Au/CeO2 nanorod framework catalyst prepared by dealloying for low-temperature CO oxidation

    Science.gov (United States)

    Zhang, Xiaolong; Duan, Dong; Li, Guijing; Feng, Wenjie; Yang, Sen; Sun, Zhanbo

    2018-03-01

    Monolithic Au/CeO2 nanorod frameworks (NFs) with porous structure were prepared by dealloying melt-spun Al89.7Ce10Au0.3 ribbons. After calcination in O2, a 3D Au/CeO2 NF catalyst with large surface area was obtained and used for low-temperature CO oxidation. The small Au clusters/nanoparticles (NPs) were in situ supported and highly dispersed on the nanorod surface, creating many nanoscale contact interfaces. XPS results demonstrated that high-concentration oxygen vacancy and Au δ+/Au0 co-existed in the calcined sample. The Au/CeO2 nanorod catalyst calcined at 400 °C exhibited much higher catalytic activity for CO oxidation compared with the dealloyed sample and bare CeO2 nanorods. Moreover, its complete reaction temperature was as low as 91 °C. The designed Au/CeO2 NF catalyst not only possessed extreme sintering resistance but also exhibited high performance owing to the enhanced interaction between the Au clusters/NPs and CeO2 nanorod during calcination.

  4. A high-throughput study of the redox properties of Nb-Ni oxide catalysts by low temperature CO oxidation: Implications in ethane ODH

    KAUST Repository

    Laveille, Paco; Biausque, Gregory; Zhu, Haibo; Basset, Jean-Marie; Caps, Valerie

    2013-01-01

    CO oxidation is used as a probe reaction to evaluate the redox properties of catalysts for the low temperature oxidative dehydrogenation (ODH) of ethane. Three series of Nb1-x-NixO nanocomposites with various Nb contents (x = 1, 0.95, 0.90, 0.85, 0.80) are prepared by a sol-gel route based on citrate and tested in a 16 parallel fixed-bed unit. Reductive and oxidative pre-treatments are shown to influence both the activity and the stability of the catalysts in CO oxidation. The extent of this effect depends on the Nb content of the composites, the Nb-rich samples being generally the most affected. However, the order of reactivity in CO oxidation is the same for the three series and is maintained whatever the conditions of the pre-treatment. It is the same as that observed in Nb1-x-NixO-catalyzed ethane ODH. © 2012 Elsevier B.V. All rights reserved.

  5. A high-throughput study of the redox properties of Nb-Ni oxide catalysts by low temperature CO oxidation: Implications in ethane ODH

    KAUST Repository

    Laveille, Paco

    2013-03-01

    CO oxidation is used as a probe reaction to evaluate the redox properties of catalysts for the low temperature oxidative dehydrogenation (ODH) of ethane. Three series of Nb1-x-NixO nanocomposites with various Nb contents (x = 1, 0.95, 0.90, 0.85, 0.80) are prepared by a sol-gel route based on citrate and tested in a 16 parallel fixed-bed unit. Reductive and oxidative pre-treatments are shown to influence both the activity and the stability of the catalysts in CO oxidation. The extent of this effect depends on the Nb content of the composites, the Nb-rich samples being generally the most affected. However, the order of reactivity in CO oxidation is the same for the three series and is maintained whatever the conditions of the pre-treatment. It is the same as that observed in Nb1-x-NixO-catalyzed ethane ODH. © 2012 Elsevier B.V. All rights reserved.

  6. Facile synthesis of PbTiO3 truncated octahedra via solid-state reaction and their application in low-temperature CO oxidation by loading Pt nanoparticles

    KAUST Repository

    Yin, Simin; Zhu, Yihan; Ren, Zhaohui; Chao, Chunying; Li, Xiang; Wei, Xiao; Shen, Ge; Han, Yu; Han, Gaorong

    2014-01-01

    Perovskite PbTiO3 (PTO) nanocrystals with a truncated octahedral morphology have been prepared by a facile solid-state reaction. Pt nanoparticles preferentially nucleated on the {111} facet of PTO nanocrystals exhibit a remarkable low-temperature catalytic activity towards CO oxidation from a temperature as low as 30 °C and achieve 100% conversion at ∼50 °C. © 2014 the Partner Organisations.

  7. Activation of surface lattice oxygen in single-atom Pt/CeO 2 for low-temperature CO oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Nie, Lei; Mei, Donghai; Xiong, Haifeng; Peng, Bo; Ren, Zhibo; Pereira Hernandez, Xavier I.; DelaRiva, Andrew; Wang, Meng; Engelhard, Mark H.; Kovarik, Libor; Datye, Abhaya K.; Wang, Yong

    2017-12-14

    While single-atom catalysts can provide high catalytic activity and selectivity, application in industrial catalysts demands long term performance and the ability to regenerate the catalysts. We have investigated the factors that lead to improved catalytic activity of a Pt/CeO2 catalyst for low temperature CO oxidation. Single-atom Pt/CeO2 becomes active for CO oxidation under lean condition only at elevated temperatures, because CO is strongly bound to ionic Pt sites. Reducing the catalyst, even under mild conditions, leads to onset of CO oxidation activity even at room temperature. This high activity state involves the transformation of mononuclear Pt species to sub-nanometer sized Pt particles. Under oxidizing conditions, the Pt can be restored to its stable, single-atom state. The key to facile regeneration is the ability to create mobile Pt species and suitable trapping sites on the support, making this a prototypical catalyst system for industrial application of single-atom catalysis.

  8. Low-temperature CO oxidation over Cu/Pt co-doped ZrO2 nanoparticles synthesized by solution combustion.

    Science.gov (United States)

    Singhania, Amit; Gupta, Shipra Mital

    2017-01-01

    Zirconia (ZrO 2 ) nanoparticles co-doped with Cu and Pt were applied as catalysts for carbon monoxide (CO) oxidation. These materials were prepared through solution combustion in order to obtain highly active and stable catalytic nanomaterials. This method allows Pt 2+ and Cu 2+ ions to dissolve into the ZrO 2 lattice and thus creates oxygen vacancies due to lattice distortion and charge imbalance. High-resolution transmission electron microscopy (HRTEM) results showed Cu/Pt co-doped ZrO 2 nanoparticles with a size of ca. 10 nm. X-ray diffraction (XRD) and Raman spectra confirmed cubic structure and larger oxygen vacancies. The nanoparticles showed excellent activity for CO oxidation. The temperature T 50 (the temperature at which 50% of CO are converted) was lowered by 175 °C in comparison to bare ZrO 2 . Further, they exhibited very high stability for CO reaction (time-on-stream ≈ 70 h). This is due to combined effect of smaller particle size, large oxygen vacancies, high specific surface area and better thermal stability of the Cu/Pt co-doped ZrO 2 nanoparticles. The apparent activation energy for CO oxidation is found to be 45.6 kJ·mol -1 . The CO conversion decreases with increase in gas hourly space velocity (GHSV) and initial CO concentration.

  9. CO oxidation on PdO surfaces

    DEFF Research Database (Denmark)

    Hirvi, Janne T.; Kinnunen, Toni-Jani J.; Suvanto, Mika

    2010-01-01

    Density functional calculations were performed in order to investigate CO oxidation on two of the most stable bulk PdO surfaces. The most stable PdO(100) surface, with oxygen excess, is inert against CO adsorption, whereas strong adsorption on the stoichiometric PdO(101) surface leads to favorable...... oxidation via the Langmuir–Hinshelwood mechanism. The reaction with a surface oxygen atom has an activation energy of 0.66 eV, which is comparable to the lowest activation energies observed on metallic surfaces. However, the reaction rate may be limited by the coverage of molecular oxygen. Actually...... adsorption, following the Eley–Rideal mechanism and taking advantage of the reaction tunnel provided by the adjacent palladium atom, has an activation energy of only 0.24 eV. The reaction mechanism and activation energy for the palladium activated CO oxidation on the most stable PdO(100)–O surface...

  10. CO oxidation on gold nanoparticles: Theoretical studies

    DEFF Research Database (Denmark)

    Remediakis, Ioannis; Lopez, Nuria; Nørskov, Jens Kehlet

    2005-01-01

    We present a summary of our theoretical results regarding CO oxidation on both oxide-supported and isolated gold nanoparticles. Using Density Functional Theory we have studied the adsorption of molecules and the oxidation reaction of CO on gold clusters. Low-coordinated sites on the gold...... nanoparticles can adsorb small inorganic molecules such as O2 and CO, and the presence of these sites is the key factor for the catalytic properties of supported gold nanoclusters. Other contributions, induced by the presence of the support, can provide parallel channels for the reaction and modulate the final...

  11. Trends in the Catalytic CO Oxidation Activity of Nanoparticles

    DEFF Research Database (Denmark)

    Nørskov, Jens Kehlet; Falsig, Hanne; Larsen, Britt Hvolbæk

    2008-01-01

    Going for gold: Density functional calculations show how gold nanoparticles are more active catalysts for CO oxidation than other metal nanoparticles. The high catalytic activity of nanosized gold clusters at low temperature is found to be related to the ability of low-coordinate metal atoms...

  12. Metal Phosphate-Supported Pt Catalysts for CO Oxidation

    Directory of Open Access Journals (Sweden)

    Xiaoshuang Qian

    2014-12-01

    Full Text Available Oxides (such as SiO2, TiO2, ZrO2, Al2O3, Fe2O3, CeO2 have often been used to prepare supported Pt catalysts for CO oxidation and other reactions, whereas metal phosphate-supported Pt catalysts for CO oxidation were rarely reported. Metal phosphates are a family of metal salts with high thermal stability and acid-base properties. Hydroxyapatite (Ca10(PO46(OH2, denoted as Ca-P-O here also has rich hydroxyls. Here we report a series of metal phosphate-supported Pt (Pt/M-P-O, M = Mg, Al, Ca, Fe, Co, Zn, La catalysts for CO oxidation. Pt/Ca-P-O shows the highest activity. Relevant characterization was conducted using N2 adsorption-desorption, inductively coupled plasma (ICP atomic emission spectroscopy, X-ray diffraction (XRD, transmission electron microscopy (TEM, CO2 temperature-programmed desorption (CO2-TPD, X-ray photoelectron spectroscopy (XPS, and H2 temperature-programmed reduction (H2-TPR. This work furnishes a new catalyst system for CO oxidation and other possible reactions.

  13. Gold nanoparticles supported on magnesium oxide for CO oxidation

    Science.gov (United States)

    Carabineiro, Sónia Ac; Bogdanchikova, Nina; Pestryakov, Alexey; Tavares, Pedro B.; Fernandes, Lisete Sg; Figueiredo, José L.

    2011-06-01

    Au was loaded (1 wt%) on a commercial MgO support by three different methods: double impregnation, liquid-phase reductive deposition and ultrasonication. Samples were characterised by adsorption of N2 at -96°C, temperature-programmed reduction, high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction. Upon loading with Au, MgO changed into Mg(OH)2 (the hydroxide was most likely formed by reaction with water, in which the gold precursor was dissolved). The size range for gold nanoparticles was 2-12 nm for the DIM method and 3-15 nm for LPRD and US. The average size of gold particles was 5.4 nm for DIM and larger than 6.5 for the other methods. CO oxidation was used as a test reaction to compare the catalytic activity. The best results were obtained with the DIM method, followed by LPRD and US. This can be explained in terms of the nanoparticle size, well known to determine the catalytic activity of gold catalysts.

  14. Gold nanoparticles supported on magnesium oxide for CO oxidation

    Directory of Open Access Journals (Sweden)

    Bogdanchikova Nina

    2011-01-01

    Full Text Available Abstract Au was loaded (1 wt% on a commercial MgO support by three different methods: double impregnation, liquid-phase reductive deposition and ultrasonication. Samples were characterised by adsorption of N2 at -96°C, temperature-programmed reduction, high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction. Upon loading with Au, MgO changed into Mg(OH2 (the hydroxide was most likely formed by reaction with water, in which the gold precursor was dissolved. The size range for gold nanoparticles was 2-12 nm for the DIM method and 3-15 nm for LPRD and US. The average size of gold particles was 5.4 nm for DIM and larger than 6.5 for the other methods. CO oxidation was used as a test reaction to compare the catalytic activity. The best results were obtained with the DIM method, followed by LPRD and US. This can be explained in terms of the nanoparticle size, well known to determine the catalytic activity of gold catalysts.

  15. Preparation and characterization of mesoporous TiO{sub 2}-sphere-supported Au-nanoparticle catalysts with high activity for CO oxidation at ambient temperature

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Lili; Huang, Shouying; Zhu, Baolin; Zhang, Shoumin; Huang, Weiping, E-mail: hwp914@nankai.edu.cn [Nankai University, College of Chemistry, The Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), and Tianjin Key Lab of Metal and Molecule-based Material Chemistry (China)

    2016-11-15

    Mesoporous TiO{sub 2}-sphere-supported Au-nanoparticles (Au/m-TiO{sub 2}-spheres) catalysts have been synthesized by a simple method using tetrabutyl titanate as TiO{sub 2} precursor and characterized with XRD, BET, ICP, SEM, TEM, UV-Vis DRS, XPS, as well as FT-IR. The samples with the size in the range of 200–400 nm were almost perfectly spherical. The average diameter of pores was about 3.6 nm, and the mesopore size distribution was in the range of 2–6 nm with a narrow distribution. When the catalyst was calcined at 300 °C, the Au NPs with the size ca. 5 nm were highly dispersed on the surfaces of m-TiO{sub 2} spheres and partially embedded in the supports. Remarkably, the specific surface area of the Au/m-TiO{sub 2}-spheres was as high as 117 m{sup 2} g{sup −1}. The CO-adsorbed catalyst showed an apparent IR adsorption peak at 1714 cm{sup −1} that matched with bridging model CO. It means the catalysts should be of high catalytic activity for the CO oxidation due to they could adsorb and activate CO commendably. When Au-content was 0.48 wt.%, the Au/m-TiO{sub 2}-spheres could convert CO completely into CO{sub 2} at ambient temperature.

  16. On the mechanism of hydrogen-promoted gold-catalyzed CO oxidation

    KAUST Repository

    Quinet, Elodie

    2009-12-10

    The kinetics of CO oxidation, H2 oxidation and preferential CO oxidation (PrOx) over Au/Al2O3 catalysts have been investigated. The catalysts with the smallest particles (∼2 nm) are the most active for all three reactions. As previously observed, the presence of H2 greatly promotes CO oxidation, which becomes faster than CO-free H2 oxidation at low temperature. From these results and on the basis of previous works, we propose a complete PrOx mechanism. The reaction involves Au-OOH, Au-OH and Au-H intermediates, also involved in H2 oxidation, and benefits from the presence of low-coordination sites. © 2009 Elsevier Inc. All rights reserved.

  17. On the mechanism of hydrogen-promoted gold-catalyzed CO oxidation

    KAUST Repository

    Quinet, Elodie; Piccolo, Laurent; Morfin, Franck; Avenier, Priscilla; Diehl, Fabrice; Caps, Valerie; Rousset, Jean Luc

    2009-01-01

    The kinetics of CO oxidation, H2 oxidation and preferential CO oxidation (PrOx) over Au/Al2O3 catalysts have been investigated. The catalysts with the smallest particles (∼2 nm) are the most active for all three reactions. As previously observed, the presence of H2 greatly promotes CO oxidation, which becomes faster than CO-free H2 oxidation at low temperature. From these results and on the basis of previous works, we propose a complete PrOx mechanism. The reaction involves Au-OOH, Au-OH and Au-H intermediates, also involved in H2 oxidation, and benefits from the presence of low-coordination sites. © 2009 Elsevier Inc. All rights reserved.

  18. Design of a core–shell Pt–SiO2 catalyst in a reverse microemulsion system: Distinctive kinetics on CO oxidation at low temperature

    KAUST Repository

    Al Mana, Noor

    2016-06-28

    The mechanism of formation of Pt@SiO2 as a model of core–shell nanoparticles via water-in-oil reverse microemulsions was studied in detail. By controlling the time of growth of Pt precursors, Pt(OH)x, after hydrolysis in NH3 aq. before adding SiO2 precursor (TEOS), Pt nanoparticles with a narrow size distribution were produced, from ultrafine metal nanoparticles (<1 nm) to 6 nm nanocrystals. Separately, the thickness of SiO2 was controllably synthesized from 1 to 15 nm to yield different Pt@SiO2 materials. The Pt@SiO2 core–shell catalysts exhibited a higher rate of CO oxidation by one order of magnitude with a positive order regarding CO pressure. The SiO2 shell did not perturb the Pt chemical nature, but it provided different coverage of CO in steady-state CO oxidation. © 2016 Elsevier Inc.

  19. Facile Synthesis of Gold Nanorice Enclosed by High- Index Facets and Its Application for CO Oxidation

    International Nuclear Information System (INIS)

    Zheng, Y.; Tao, J.; Liu, H.; Zeng, J.; Yu, T.; Ma, Y.; Moran, C.; Wu, L.; Zhu, Y.; Liu, J.; Xia, Y.

    2011-01-01

    A facile method for generating Au nanorice enclosed by high-index facets in high purity. The nanorice shows much higher catalytic activity for CO oxidation than multiply twinned particles of Au enclosed by {111} facets at temperatures below 300 C.

  20. CO oxidation on Alsbnd Au nano-composite systems

    Science.gov (United States)

    Rajesh, C.; Majumder, C.

    2018-03-01

    Using first principles method we report the CO oxidation behaviour of Alsbnd Au nano-composites in three different size ranges: Al6Au8, Al13Au42 and a periodic slab of Alsbnd Au(1 1 1) surface. The clusters prefer enclosed structures with alternating arrangement of Al and Au atoms, maximising Auδ-sbnd Alδ+ bonds. Charge distribution analysis suggests the charge transfer from Al to Au atoms, corroborated by the red shift in the density of states spectrum. Further, CO oxidation on these nano-composite systems was investigated through both Eley - Rideal and Langmuir Hinshelwood mechanism. While, these clusters interact with O2 non-dissociatively with an elongation of the Osbnd O bond, further interaction with CO led to formation of CO2 spontaneously. On contrary, the CO2 evolution by co-adsorption of O2 and CO molecules has a transition state barrier. On the basis of the results it is inferred that nano-composite material of Alsbnd Au shows significant promise toward effective oxidative catalysis.

  1. Catalytic activity trends of CO oxidation – A DFT study

    DEFF Research Database (Denmark)

    Jiang, Tao

    theoretical study of CO oxidation with experimental studies. The latter shows promoted catalytic activity when gold particle size decreases to 5 nm. Oxidizing CO by N2O was found to involve a CO␣O transition state, with atomic O adsorbed on the gold B5 sites and CO on the corners. On the other hand, CO...... and experiment were found to be the same. The experiment findings are in good agreement with our theoretical calculations. The second part of the thesis focuses on improving the convergence property of Quasi-Newton algorithm. The eigenvalues of the Hessian matrix of 54 atoms bulk Cu model are calculated......, and the sizes of eigenvalues follow power-law distribution. It is found that the anharmonicity of the weak modes lead to poor Newton step and poor Hessian update in BFGS type Quasi-Newton algorithm, which slow down the geometry optimization. Line search that fulfills Wolff conditions is then applied to improve...

  2. CO oxidation catalyzed by Pt-embedded graphene: A first-principles investigation

    KAUST Repository

    Liu, Xin; Sui, Yanhui; Duan, Ting; Meng, Changong; Han, Yu

    2014-01-01

    We addressed the potential catalytic role of Pt-embedded graphene in CO oxidation by first-principles-based calculations. We showed that the combination of highly reactive Pt atoms and defects over graphene makes the Pt-embedded graphene a superior mono-dispersed atomic catalyst for CO oxidation. The binding energy of a single Pt atom onto monovacancy defects is up to -7.10 eV, which not only ensures the high stability of the embedded Pt atom, but also vigorously excludes the possibility of diffusion and aggregation of embedded Pt atoms. This strong interfacial interaction also tunes the energy level of Pt-d states for the activation of O2, and promotes the formation and dissociation of the peroxide-like intermediate. The catalytic cycle of CO oxidation is initiated through the Langmuir-Hinshelwood mechanism, with the formation of a peroxide-like intermediate by the coadsorbed CO and O2, by the dissociation of which the CO2 molecule and an adsorbed O atom are formed. Then, another gaseous CO will react with the remnant O atom and make the embedded Pt atom available for the subsequent reaction. The calculated energy barriers for the formation and dissociation of the peroxide-like intermediate are as low as 0.33 and 0.15 eV, respectively, while that for the regeneration of the embedded Pt atom is 0.46 eV, indicating the potential high catalytic performance of Pt-embedded graphene for low temperature CO oxidation.

  3. Insights into the dominant factors of porous gold for CO oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Kameoka, Satoshi, E-mail: kameoka@tagen.tohoku.ac.jp; Miyamoto, Kanji [Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan); Tanabe, Toyokazu [Kanagawa University, Yokohama 221-8686 (Japan); Tsai, An Pang [Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan); National Institute of Materials Science (NIMS), Tsukuba 305-0047 (Japan)

    2016-01-21

    Three different porous Au catalysts that exhibit high catalytic activity for CO oxidation were prepared by the leaching of Al from an intermetallic compound, Al{sub 2}Au, with 10 wt. %-NaOH, HNO{sub 3}, or HCl aqueous solutions. The catalysts were investigated using Brunauer-Emmett-Teller measurements, synchrotron X-ray powder diffraction, hard X-ray photoelectron spectroscopy, field emission scanning electron microscopy, and transmission electron microscopy (TEM). Broad diffraction peaks generated during the leaching process correlated with high activity for all the porous Au catalysts. CO oxidation catalyzed by porous Au leached with NaOH and HNO{sub 3} is considered to be dominated by different mechanisms at low (< 320 K) and high (> 370 K) temperatures. Activity in the low-temperature region is mainly attributed to the perimeter interface between residual Al species (AlO{sub x}) and porous Au, whereas activity in the high-temperature region results from a high density of lattice defects such as twins and dislocations, which were evident from diffraction peak broadening and were observed with high-resolution TEM in the porous Au leached with NaOH. It is proposed that atoms located at lattice defects on the surfaces of porous Au are the active sites for catalytic reactions.

  4. Insights into the dominant factors of porous gold for CO oxidation

    International Nuclear Information System (INIS)

    Kameoka, Satoshi; Miyamoto, Kanji; Tanabe, Toyokazu; Tsai, An Pang

    2016-01-01

    Three different porous Au catalysts that exhibit high catalytic activity for CO oxidation were prepared by the leaching of Al from an intermetallic compound, Al 2 Au, with 10 wt. %-NaOH, HNO 3 , or HCl aqueous solutions. The catalysts were investigated using Brunauer-Emmett-Teller measurements, synchrotron X-ray powder diffraction, hard X-ray photoelectron spectroscopy, field emission scanning electron microscopy, and transmission electron microscopy (TEM). Broad diffraction peaks generated during the leaching process correlated with high activity for all the porous Au catalysts. CO oxidation catalyzed by porous Au leached with NaOH and HNO 3 is considered to be dominated by different mechanisms at low (< 320 K) and high (> 370 K) temperatures. Activity in the low-temperature region is mainly attributed to the perimeter interface between residual Al species (AlO x ) and porous Au, whereas activity in the high-temperature region results from a high density of lattice defects such as twins and dislocations, which were evident from diffraction peak broadening and were observed with high-resolution TEM in the porous Au leached with NaOH. It is proposed that atoms located at lattice defects on the surfaces of porous Au are the active sites for catalytic reactions

  5. Chemisorption of CO and mechanism of CO oxidation on supported platinum nanoclusters

    KAUST Repository

    Allian, Ayman Daoud; Takanabe, Kazuhiro; Fujdala, Kyle L.; Hao, Xianghong; Truex., Timothy J.; Cai, Juan; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

    2011-01-01

    Kinetic, isotopic, and infrared studies on well-defined dispersed Pt clusters are combined here with first-principle theoretical methods on model cluster surfaces to probe the mechanism and structural requirements for CO oxidation catalysis

  6. Synthesis and characterization of pure and (Ce, Zr, Ag) doped mesoporous CuO-Fe{sub 2}O{sub 3} as highly efficient and stable nanocatalysts for CO oxidation at low temperature

    Energy Technology Data Exchange (ETDEWEB)

    Said, Abd El-Aziz A., E-mail: aasaid55@yahoo.com; Abd El-Wahab, Mohamed M.M.; Goda, Mohamed N.

    2016-12-30

    Highlights: • Highly active and stable Fe-Cu mixed oxides were prepared by co-precipitation method. • Addition of CuO to Fe{sub 2}O{sub 3} increases the chemisorbed oxygen, the conductivity and S{sub BET}. • Activation energy of CO oxidation significantly decreased via doping with foreign ions. - Abstract: A series of single and mixed oxide nanocatalysts of mesoporous CuO-Fe{sub 2}O{sub 3} with different CuO contents (1–50 wt.%) were prepared by a co-precipitation method and further promoted by trace amounts of CeO{sub 2}, ZrO{sub 2} and Ag{sub 2}O (0.1–0.5 wt.%) dopants. The original and calcined catalysts were characterized by TG, DTA, XRD, TEM, VSM, N{sub 2} sorption analysis, surface chemisorbed oxygen and DC electrical conductivity measurements. The catalytic performance of these nanocatalysts toward CO oxidation was studied using a conventional fixed bed flow type reactor. The results revealed that the addition of 1–20 wt.% CuO to Fe{sub 2}O{sub 3} monotonically increases the specific surface area, the amount of surface chemisorbed oxygen, electrical conductivity and catalytic activity of the nanocatalysts. In addition, the catalytic activity indicated that Fe-Cu mixed oxide nanocatalyst promoted with the three dopants (CeO{sub 2}, ZrO{sub 2} and Ag{sub 2}O) exhibited the highest catalytic activity with a total conversion of CO into CO{sub 2} at 100 °C. Moreover, the activation energy of CO oxidation decreased from 38.4 to 23.1 kJmol{sup −1} upon treating the catalyst containing 20 wt.% CuO with the three dopants. Finally the effects of various operational parameters were also studied.

  7. Impact of SO2 and NO on CO Oxidation under Post-Flame Conditions

    DEFF Research Database (Denmark)

    Glarborg, Peter; Kubel, Dorte; Dam-Johansen, Kim

    1996-01-01

    An experimental and theoretical study of the effect of SO2 on moist CO oxidation with and without NO present was carried out under plug-flow conditions. The H/S/O thermochemistry and reaction subset was revised and a chemical kinetic model established that provide a good description of the effect...... of SO2 and NO on CO oxidation as well as the SO2/SO3 ratio in the products....

  8. Nanoroses of nickel oxides: Synthesis, electron tomography study, and application in CO oxidation and energy storage

    KAUST Repository

    Fihri, Aziz

    2012-04-11

    Nickel oxide and mixed-metal oxide structures were fabricated by using microwave irradiation in pure water. The nickel oxide self-assembled into unique rose-shaped nanostructures. These nickel oxide roses were studied by performing electron tomography with virtual cross-sections through the particles to understand their morphology from their interior to their surface. These materials exhibited promising performance as nanocatalysts for CO oxidation and in energy storage devices. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Time resolved FTIR study of the catalytic CO oxidation under periodic variation of the reactant concentration

    Energy Technology Data Exchange (ETDEWEB)

    Kritzenberger, J; Wokaun, A [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-06-01

    Oxidation of CO over palladium/zirconia catalyst obtained from an amorphous Pd{sub 25}Zr{sub 75} precursor was investigated by time resolved FTIR spectroscopy. Sine wave shaped modulation of the reactant concentration, i.e. variation of CO or O{sub 2} partial pressure, was used to induce variations of the IR signals of product (CO{sub 2}) and unconverted reactant (CO), which were detected in a multi-pass absorption cell. The phase shift {phi} between external perturbation and variation of the CO{sub 2} signal was examined in dependence on temperature (100{sup o}C{<=}T{<=}350{sup o}C) and modulation frequency (1.39x10{sup -4}Hz{<=}{omega}{<=}6.67x10{sup -2}Hz). From the phase shift values, a simple Eley-Rideal mechanism is excluded, and the rate limiting step of the Langmuir-Hinshelwood mechanism for the CO oxidation may be identified. Adsorption and possible surface movement of CO to the actual reaction site determine the rate of the CO oxidation on the palladium/zirconia catalyst used in our study. The introduction of an external perturbation is a first step towards the application of two-dimensional infrared spectroscopy to heterogeneous catalyzed reactions. (author) 3 figs., 4 refs.

  10. Improvement of sulfur resistance of Pd/Ce-Zr-Al-O catalysts for CO oxidation

    Science.gov (United States)

    Shin, Haebin; Baek, Minsung; Ro, Youngsoo; Song, Changyeol; Lee, Kwan-Young; Song, In Kyu

    2018-01-01

    Two kinds of mesoporous ceria-zirconia-alumina supports were prepared by a single-step epoxide-driven sol-gel method (SGCZA) and by a co-precipitation method (PCZA). Palladium catalysts supported on these materials were then prepared by a wet impregnation method (Pd/SGCZA and Pd/PCZA). The prepared catalysts were applied to the CO oxidation reaction before and after sulfur aging. XRD and N2 adsorption-desorption analyses revealed that these two catalysts retained different physicochemical properties. Pd/SGCZA had higher surface area and larger pore volume than Pd/PCZA before and after sulfur aging. TPR (Temperature-programmed reduction), CO chemisorption, FT-IR, and XPS analyses showed that the catalysts were differently influenced by sulfur species. Pd/SGCZA formed less sulfate and retained higher palladium dispersion than Pd/PCZA after sulfur aging. In the CO oxidation, Pd/PCZA showed better activity than Pd/SGCZA before sulfur aging. However, Pd/SGCZA showed higher CO conversion than Pd/PCZA after sulfur aging. We concluded that Pd/SGCZA was less poisoned by sulfur species than Pd/PCZA.

  11. Alloying Au surface with Pd reduces the intrinsic activity in catalyzing CO oxidation

    KAUST Repository

    Qian, Kun

    2016-03-30

    © 2016. Various Au-Pd/SiO2 catalysts with a fixed Au loading but different Au:Pd molar ratios were prepared via deposition-precipitation method followed by H2 reduction. The structures were characterized and the catalytic activities in CO oxidation were evaluated. The formation of Au-Pd alloy particles was identified. The Au-Pd alloy particles exhibit enhanced dispersions on SiO2 than Au particles. Charge transfer from Pd to Au within Au-Pd alloy particles. Isolated Pd atoms dominate the surface of Au-Pd alloy particles with large Au:Pd molar ratios while contiguous Pd atoms dominate the surface of Au-Pd alloy particles with small Au:Pd molar ratios. Few synergetic effect of Au-Pd alloy occurs on catalyzing CO oxidation under employed reaction conditions. Alloying Au with Pd reduces the intrinsic activity in catalyzing CO oxidation, and contiguous Pd atoms on the Au-Pd alloy particles are capable of catalyzing CO oxidation while isolated Pd atoms are not. These results advance the fundamental understandings of Au-Pd alloy surfaces in catalyzing CO oxidation.

  12. Modelling of elementary kinetics of H2 and CO oxidation on ceria pattern cells

    International Nuclear Information System (INIS)

    Patel, HC; Tabish, AN; Aravind, PV

    2015-01-01

    Elementary kinetic mechanisms of fuel oxidation on ceria have not been dealt with in detail in literature. An elementary kinetic model is developed considering charge transfer and adsorption steps for electrochemical H 2 and CO oxidation on ceria. The reaction chemistry is solved by fitting previously obtained impedance spectra for H 2 and CO oxidation on ceria. The rate determining step is found to be the charge transfer rather than the adsorption for both H 2 and CO. A method is presented to extend the kinetics obtained from pattern anodes to macroscopic simulations in which the activation overvoltage can be calculated on the basis of elementary kinetics.

  13. Comparison of sol-gel prepared catalysts for CO oxidation and N2O decomposition reactions.

    OpenAIRE

    Euesden, Claire

    2002-01-01

    This thesis comprises analysis for two types of catalysis: CO oxidation and N2O decomposition; related by their research in sol-gel catalysis. The CO oxidation work was undertaken on behalf of Servomex plc in order to understand how their catalyst-based sensor (Tfx 1750) worked and why it failed when exposed to coal power station flue streams within its two-year guarantee period. This research will show, by means of many analytical techniques and catalytic tests: 1. A comparison of the Servom...

  14. Using Iron-Manganese Co-Oxide Filter Film to Remove Ammonium from Surface Water.

    Science.gov (United States)

    Zhang, Ruifeng; Huang, Tinglin; Wen, Gang; Chen, Yongpan; Cao, Xin; Zhang, Beibei

    2017-07-19

    An iron-manganese co-oxide filter film (MeO x ) has been proven to be a good catalyst for the chemical catalytic oxidation of ammonium in groundwater. Compared with groundwater, surface water is generally used more widely and has characteristics that make ammonium removal more difficult. In this study, MeO x was used to remove ammonium from surface water. It indicated that the average ammonium removal efficiency of MeO x was greater than 90%, even though the water quality changed dramatically and the water temperature was reduced to about 6-8 °C. Then, through inactivating microorganisms, it showed that the removal capability of MeO x included both biological (accounted for about 41.05%) and chemical catalytic oxidation and chemical catalytic oxidation (accounted for about 58.95%). The investigation of the characterizations suggested that MeO x was formed by abiotic ways and the main elements on the surface of MeO x were distributed homogenously. The analysis of the catalytic oxidation process indicated that ammonia nitrogen may interact with MeO x as both ammonia molecules and ammonium ions and the active species of O₂ were possibly • O and O₂ - .

  15. PtRu colloid nanoparticles for CO oxidation in microfabricated reactors

    DEFF Research Database (Denmark)

    Klerke, Asbjørn; Saadi, Souheil; Toftegaard, Maja Bøg

    2006-01-01

    The catalytic activity of PtRu colloid nanoparticles for CO oxidation is investigated in microfabricated reactors. The measured catalytic performance describes a volcano curve as a function of the Pt/Ru ratio. The apparent activation energies for the different alloy catalysts are between 21 and 1...

  16. CO oxidation catalyzed by ag nanoparticles supported on SnO/CeO2

    KAUST Repository

    Khan, Inayatali; Sajid, Nida K M; Badshah, Amin; Wattoo, Muhammad Hamid Sarwar; Anjum, Dalaver H.; Nadeem, Muhammad Amtiaz

    2015-01-01

    by the XRD technique due to sintering inside the 3D array channels of CeO2 during the calcination process. The Ag-Sn/CeO2 (4%) catalyst was the most efficient and exhibited 100% CO oxidation at 100 °C due to small particle size and strong electronic

  17. Structure sensitivity in CO oxidation by a single Au atom supported on ceria

    NARCIS (Netherlands)

    Song, W.; Hensen, E.J.M.

    2013-01-01

    The mechanism of CO oxidation by a CeO2(110)-supported gold atom has been investigated by DFT calculations. A novel stable surface structure has been identified in which one surface O atom of ceria migrates toward the isolated Au atom, resulting in a surface Au–O species that can react with CO.

  18. Effects of p-substituents on electrochemical CO oxidation by Rh porphyrin-based catalysts.

    Science.gov (United States)

    Yamazaki, Shin-ichi; Yamada, Yusuke; Takeda, Sahori; Goto, Midori; Ioroi, Tsutomu; Siroma, Zyun; Yasuda, Kazuaki

    2010-08-21

    Electrochemical CO oxidation by several carbon-supported rhodium tetraphenylporphyrins with systematically varied meso-substituents was investigated. A quantitative analysis revealed that the p-substituents on the meso-phenyl groups significantly affected CO oxidation activity. The electrocatalytic reaction was characterized in detail based on the spectroscopic and X-ray structural results as well as electrochemical analyses. The difference in the activity among Rh porphyrins is discussed in terms of the properties of p-substituents along with a proposed reaction mechanism. Rhodium tetrakis(4-carboxyphenyl)porphyrin (Rh(TCPP)), which exhibited the highest activity among the porphyrins tested, oxidized CO at a high rate at much lower potentials (means that CO is electrochemically oxidized by this catalyst when a slight overpotential is applied during the operation of a proton exchange membrane fuel cell. This catalyst exhibited little H(2) oxidation activity, in contrast to Pt-based catalysts.

  19. Monodisperse Pt atoms anchored on N-doped graphene as efficient catalysts for CO oxidation: A first-principles investigation

    KAUST Repository

    Liu, Xin; Sui, Yanhui; Duan, Ting; Meng, Changgong; Han, Yu

    2015-01-01

    We performed first-principles based calculations to investigate the electronic structure and the potential catalytic performance of Pt atoms monodispersed on N-doped graphene in CO oxidation. We showed that N-doping can introduce localized defect states in the vicinity of the Fermi level of graphene which will effectively stabilize the deposited Pt atoms. The binding energy of a single Pt atom onto a stable cluster of 3 pyridinic N (PtN3) is up to -4.47 eV, making the diffusion and aggregation of anchored Pt atoms difficult. Both the reaction thermodynamics and kinetics suggest that CO oxidation over PtN3 would proceed through the Langmuir-Hinshelwood mechanism. The reaction barriers for the formation and dissociation of the peroxide-like intermediate are determined to be as low as 0.01 and 0.08 eV, respectively, while that for the regeneration is only 0.15 eV, proving the potential high catalytic performance of PtN3 in CO oxidation, especially at low temperatures. The Pt-d states that are up-shifted by the Pt-N interaction account for the enhanced activation of O2 and the efficient formation and dissociation of the peroxide-like intermediate.

  20. Copper atoms embedded in hexagonal boron nitride as potential catalysts for CO oxidation: A first-principles investigation

    KAUST Repository

    Liu, Xin

    2014-01-01

    We addressed the electronic structure of Cu atoms embedded in hexagonal boron nitride (h-BN) and their catalytic role in CO oxidation by first-principles-based calculations. We showed that Cu atoms prefer to bind directly with the localized defects on h-BN, which act as strong trapping sites for Cu atoms and inhibit their clustering. The strong binding of Cu atoms at boron vacancy also up-shifts the energy level of Cu-d states to the Fermi level and promotes the formation of peroxide-like intermediate. CO oxidation over Cu atoms embedded in h-BN would proceed through the Langmuir-Hinshelwood mechanism with the formation of a peroxide-like complex by reaction of coadsorbed CO and O2, with the dissociation of which the a CO2 molecule and an adsorbed O atom are formed. Then, the embedded Cu atom is regenerated by the reaction of another gaseous CO with the remnant O atom. The calculated energy barriers for the formation and dissociation of peroxide complex and regeneration of embedded Cu atoms are as low as 0.26, 0.11 and 0.03 eV, respectively, indicating the potential high catalytic performance of Cu atoms embedded in h-BN for low temperature CO oxidation. © the Partner Organisations 2014.

  1. Activity of carbon supported Pt3Ru2 nanocatalyst in CO oxidation

    Directory of Open Access Journals (Sweden)

    KSENIJA DJ. POPOVIĆ

    2009-08-01

    Full Text Available The electrocatalytic activity of Pt3Ru2/C nanocatalyst toward the electro-oxidation of bulk CO was examined in acid and alkaline solution at ambient temperature using the thin-film, rotating disk electrode (RDE method. The catalyst was characterized by XRD analysis. The XRD pattern revealed that the Pt3Ru2/C catalyst consisted of two structures, i.e., Pt–Ru-fcc and Ru-hcp (a solid solution of Ru in Pt and a small amount of Ru or a solid solution of Pt in Ru. Electrocatalytic activities were measured by applying potentiodynamic and steady state techniques. The oxidation of CO on the Pt3Ru2/C catalyst was influenced by pH and anions from the supporting electrolytes. The Pt3Ru2/C was more active in alkaline than in acid solution, as well as in perchloric than in sulfuric acid. Comparison of CO oxidation on Pt3Ru2/C and Pt/C revealed that the Pt3Ru2/C was more active than Pt/C in acid solution, while both catalysts had a similar activity in alkaline solution.

  2. Theoretical evidence of PtSn alloy efficiency for CO oxidation.

    Science.gov (United States)

    Dupont, Céline; Jugnet, Yvette; Loffreda, David

    2006-07-19

    The efficiency of PtSn alloy surfaces toward CO oxidation is demonstrated from first-principles theory. Oxidation kinetics based on atomistic density-functional theory calculations shows that the Pt3Sn surface alloy exhibits a promising catalytic activity for fuel cells. At room temperature, the corresponding rate outstrips the activity of Pt(111) by several orders of magnitude. According to the oxidation pathways, the activation barriers are actually lower on Pt3Sn(111) and Pt3Sn/Pt(111) surfaces than on Pt(111). A generalization of Hammer's model is proposed to elucidate the key role of tin on the lowering of the barriers. Among the energy contributions, a correlation is evidenced between the decrease of the barrier and the strengthening of the attractive interaction energy between CO and O moieties. The presence of tin modifies also the symmetry of the transition states which are composed of a CO adsorbate on a Pt near-top position and an atomic O adsorption on an asymmetric mixed PtSn bridge site. Along the reaction pathways, a CO2 chemisorbed surface intermediate is obtained on all the surfaces. These results are supported by a thorough vibrational analysis including the coupling with the surface phonons which reveals the existence of a stretching frequency between the metal substrate and the CO2 molecule.

  3. CO oxidation catalyzed by ag nanoparticles supported on SnO/CeO2

    KAUST Repository

    Khan, Inayatali

    2015-01-01

    Ag-Sn/CeO2 catalysts were synthesized by the co-precipitation method with different Ag-Sn wt.% loadings and were tested for the oxidation of CO. The catalysts were characterized by powder X-ray diffractometry (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), energy dispersive X-ray spectroscopy (EDS), and selected area electron diffraction (SAED) techniques. UV-Vis measurements were carried out to elucidate the ionic states of the silver particles, and the temperature-programmed reduction (TPR) technique was employed to check the reduction temperature of the catalyst supported on CeO2. There are peaks for silver crystallites in the X-ray diffraction patterns and the presence of SnO was not well evidenced by the XRD technique due to sintering inside the 3D array channels of CeO2 during the calcination process. The Ag-Sn/CeO2 (4%) catalyst was the most efficient and exhibited 100% CO oxidation at 100 °C due to small particle size and strong electronic interaction with the SnO/CeO2 support. © 2015 Sociedade Brasileira de Química.

  4. Study of nano-structured ceria for catalytic CO oxidation

    Czech Academy of Sciences Publication Activity Database

    Valechha, D.; Lokhande, S.; Klementová, Mariana; Šubrt, Jan; Rayalu, S.; Labhsetwar, N.

    2011-01-01

    Roč. 21, č. 11 (2011), s. 3718-3725 ISSN 0959-9428 Institutional research plan: CEZ:AV0Z40320502 Keywords : mesoporous CeO2 * titania * alumina * oxides Subject RIV: CA - Inorganic Chemistry Impact factor: 5.968, year: 2011

  5. Catalytic membranes for CO oxidation in fuel cells

    Science.gov (United States)

    Sandi-Tapia, Giselle; Carrado Gregar, Kathleen; Kizilel, Riza

    2010-06-08

    A hydrogen permeable membrane, which includes a polymer stable at temperatures of about 200 C having clay impregnated with Pt or Au or Ru or Pd particles or mixtures thereof with average diameters of less than about 10 nanometers (nms) is disclosed. The membranes are useful in fuel cells or any device which requires hydrogen to be separated from carbon monoxide.

  6. Effects of Water Molecule on CO Oxidation by OH: Reaction Pathways, Kinetic Barriers, and Rate Constants.

    Science.gov (United States)

    Zhang, Linyao; Yang, Li; Zhao, Yijun; Zhang, Jiaxu; Feng, Dongdong; Sun, Shaozeng

    2017-07-06

    The water dilute oxy-fuel combustion is a clean combustion technology for near-zero emission power; and the presence of water molecule could have both kinetic and dynamic effects on combustion reactions. The reaction OH + CO → CO 2 + H, one of the most important elementary reactions, has been investigated by extensive electronic structure calculations. And the effects of a single water molecule on CO oxidation have been studied by considering the preformed OH(H 2 O) complex reacts with CO. The results show little change in the reaction pathways, but the additional water molecule actually increases the vibrationally adiabatic energy barriers (V a G ). Further thermal rate constant calculations in the temperature range of 200 to 2000 K demonstrate that the total low-pressure limit rate constant for the water assisted OH(H 2 O) + CO → CO 2 + H 2 O + H reaction is 1-2 orders lower than that of the water unassisted one, which is consistent with the change of V a G . Therefore, the hydrated radical OH(H 2 O) would actually slow down the oxidation of CO. Meanwhile, comparisons show that the M06-2X/aug-cc-pVDZ method gives a much better estimation in energy and thus is recommended to be employed for direct dynamics simulations.

  7. Reaction rate oscillations during catalytic CO oxidation: A brief overview

    Science.gov (United States)

    Tsotsis, T. T.; Sane, R. C.

    1987-01-01

    It is not the intent here to present a comprehensive review of the dynamic behavior of the catalytic oxidation of CO. This reaction is one of the most widely studied in the field of catalysis. A review paper by Engel and Ertl has examined the basic kinetic and mechanistic aspects, and a comprehensive paper by Razon and Schmitz was recently devoted to its dynamic behavior. Those interested in further study of the subject should consult these reviews and a number of general review papers on catalytic reaction dynamics. The goal is to present a brief overview of certain interesting aspects of the dynamic behavior of this reaction and to discuss a few questions and issues, which are still the subject of study and debate.

  8. Pt atoms stabilized on hexagonal boron nitride as efficient single-atom catalysts for CO oxidation: A first-principles investigation

    KAUST Repository

    Liu, Xin

    2015-01-01

    Taking CO oxidation as a probe, we investigated the electronic structure and reactivity of Pt atoms stabilized by vacancy defects on hexagonal boron nitride (h-BN) by first-principles-based calculations. As a joint effect of the high reactivity of both a single Pt atom and a boron vacancy defect (PtBV), the Pt-N interaction is -4.40 eV and is already strong enough to prohibit the diffusion and aggregation of the stabilized Pt atom. Facilitated by the upshifted Pt-d states originated from the Pt-N interaction, the barriers for CO oxidation through the Langmuir-Hinshelwood mechanism for formation and dissociation of peroxide-like intermediate and the regeneration are as low as 0.38, 0.10 and 0.04 eV, respectively, suggesting the superiority of PtBV as a catalyst for low temperature CO oxidation.

  9. Effect of phase interaction on catalytic CO oxidation over the SnO_2/Al_2O_3 model catalyst

    International Nuclear Information System (INIS)

    Chai, Shujing; Bai, Xueqin; Li, Jing; Liu, Cheng; Ding, Tong; Tian, Ye; Liu, Chang; Xian, Hui; Mi, Wenbo; Li, Xingang

    2017-01-01

    Highlights: • Activity for CO oxidation is greatly enhanced by interaction between SnO_2 and Al_2O_3. • Interaction between SnO_2 and Al_2O_3 phases can generate oxygen vacancies. • Oxygen vacancies play an import role for catalytic CO oxidation. • Sn"4"+ cations are the effective sites for catalytic CO oxidation. • Langmuir-Hinshelwood model is preferred for catalytic CO oxidation. - Abstract: We investigated the catalytic CO oxidation over the SnO_2/Al_2O_3 model catalysts. Our results show that interaction between the Al_2O_3 and SnO_2 phases results in the significantly improved catalytic activity because of the formation of the oxygen vacancies. The oxygen storage capacity of the SnO_2/Al_2O_3 catalyst prepared by the physically mixed method is nearly two times higher than that of the SnO_2, which probably results from the change of electron concentration on the interface of the SnO_2 and Al_2O_3 phases. Introducing water vapor to the feeding gas would a little decrease the activity of the catalysts, but the reaction rate could completely recover after removal of water vapor. The kinetics results suggest that the surface Sn"4"+ cations are effective CO adsorptive sites, and the surface adsorbed oxygen plays an important role upon CO oxidation. The reaction pathways upon the SnO_2-based catalysts for CO oxidation follow the Langmuir-Hinshelwood model.

  10. Formic Acid Modified Co3O4-CeO2 Catalysts for CO Oxidation

    Directory of Open Access Journals (Sweden)

    Ruishu Shang

    2016-03-01

    Full Text Available A formic acid modified catalyst, Co3O4-CeO2, was prepared via facile urea-hydrothermal method and applied in CO oxidation. The Co3O4-CeO2-0.5 catalyst, treated by formic acid at 0.5 mol/L, performed better in CO oxidation with T50 obtained at 69.5 °C and T100 obtained at 150 °C, respectively. The characterization results indicate that after treating with formic acid, there is a more porous structure within the Co3O4-CeO2 catalyst; meanwhile, despite of the slightly decreased content of Co, there are more adsorption sites exposed by acid treatment, as suggested by CO-TPD and H2-TPD, which explains the improvement of catalytic performance.

  11. Synthesis of highly efficient Mn2O3 catalysts for CO oxidation derived from Mn-MIL-100

    Science.gov (United States)

    Zhang, Xiaodong; Li, Hongxin; Hou, Fulin; Yang, Yang; Dong, Han; Liu, Ning; Wang, Yuxin; Cui, Lifeng

    2017-07-01

    In this work, metal-organic frameworks (MOFs) Mn-MIL-100 were first prepared, which were next used as templates to obtain the irregular porous Mn2O3 cubes through calcination with air at different temperature. The catalysts were characterized by N2 adsorption-desorption, X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), H2-temperature program reduction (H2-TPR) and X-ray photoelectron spectroscopic (XPS). The catalytic activity for CO oxidation over Mn2O3 catalysts was investigated. It was found that calcination temperature had a strong effect on the structure and catalytic activity of Mn2O3 catalyst. Mn2O3 catalyst obtained by calcined at 700 °C (Mn2O3-700) showed a smaller specific surface area, but displayed a high catalytic activity and excellent stability with a complete CO conversion temperature (T98) of 240 °C, which was attributed to the unique structure, a high quantity of surface active oxygen species, smaller particle size, oxygen vacancies and good low temperature reduction behavior. The effect of water vapor on catalytic activity was also examined. The introduction of water vapor to the feedstock induced a positive effect on CO oxidation over Mn2O3-700 catalyst. Furthermore, no obvious drop is observed in activity over catalysts even in the presence of water vapor during 48 h.

  12. Electrochemical performance of 3D porous Ni-Co oxide with electrochemically exfoliated graphene for asymmetric supercapacitor applications

    International Nuclear Information System (INIS)

    Kim, Dae Kyom; Hwang, Minsik; Ko, Dongjin; Kang, Jeongmin; Seong, Kwang-dong; Piao, Yuanzhe

    2017-01-01

    Graphical abstract: The paper reported the Ni-Co oxide/electrochemically exfoliated graphene nanocomposites with 3D porous nano-architectures (NC-EEG) using a simple low temperature solution method combined with a thermal annealing treatment. 3D porous architectures provide large surface areas and shorten electron diffusion pathways for high performance asymmetric supercapacitors. Display Omitted -- Highlights: •A simple low temperature solution method was used for preparing NC-EEG. •Graphene sheets were obtained by electrochemically exfoliation process. •A high capacity of NC-EEG in a three-electrode system, as high as 649 C g −1 , was recorded. •Asymmetric supercapacitor based on NC-EEG exhibited excellent energy density and power density. -- Abstract: Ni-Co oxide, one of the binary metal oxides, has many advantages for use in high-performance supercapacitor electrode materials due to its relatively high electronic conductivity and improved electrochemical performance. In this work, Ni-Co oxide/electrochemically exfoliated graphene nanocomposites (NC-EEG) are successfully synthesized using a simple low temperature solution method combined with a thermal annealing treatment. Graphene sheets are directly obtained by an electrochemical exfoliation process with graphite foil, which is very simple, environmentally friendly, and has a relatively short reaction time. This electrochemically exfoliated graphene (EEG) can improve the electrical conductivity of the Ni-Co oxide nanostructures. The as-prepared NC-EEG nanocomposites have 3D porous architectures that can provide large surface areas and shorten electron diffusion pathways. Electrochemical properties were performed by cyclic voltammetry and galvanostatic charge/discharge in a 6 M KOH electrolyte. The NC-EEG nanocomposites exhibited a high capacity value of 649 C g −1 at a current density of 1.0 A g −1 . The asymmetric supercapacitors, manufactured on the basis of NC-EEG nanocomposites as a positive

  13. Understanding Trends in Catalytic Activity: The Effect of Adsorbate-Adsorbate Interactions for CO Oxidation Over Transition Metals

    DEFF Research Database (Denmark)

    Grabow, Lars; Larsen, Britt Hvolbæk; Nørskov, Jens Kehlet

    2010-01-01

    Using high temperature CO oxidation as the example, trends in the reactivity of transition metals are discussed on the basis of density functional theory (DFT) calculations. Volcano type relations between the catalytic rate and adsorption energies of important intermediates are introduced...... and the effect of adsorbate-adsorbate interaction on the trends is discussed. We find that adsorbate-adsorbate interactions significantly increase the activity of strong binding metals (left side of the volcano) but the interactions do not change the relative activity of different metals and have a very small...... influence on the position of the top of the volcano, that is, on which metal is the best catalyst....

  14. Stabilization of Palladium Nanoparticles on Nanodiamond-Graphene Core-Shell Supports for CO Oxidation.

    Science.gov (United States)

    Zhang, Liyun; Liu, Hongyang; Huang, Xing; Sun, Xueping; Jiang, Zheng; Schlögl, Robert; Su, Dangsheng

    2015-12-21

    Nanodiamond-graphene core-shell materials have several unique properties compared with purely sp(2) -bonded nanocarbons and perform remarkably well as metal-free catalysts. In this work, we report that palladium nanoparticles supported on nanodiamond-graphene core-shell materials (Pd/ND@G) exhibit superior catalytic activity in CO oxidation compared to Pd NPs supported on an sp(2) -bonded onion-like carbon (Pd/OLC) material. Characterization revealed that the Pd NPs in Pd/ND@G have a special morphology with reduced crystallinity and are more stable towards sintering at high temperature than the Pd NPs in Pd/OLC. The electronic structure of Pd is changed in Pd/ND@G, resulting in weak CO chemisorption on the Pd NPs. Our work indicates that strong metal-support interactions can be achieved on a non-reducible support, as exemplified for nanocarbon, by carefully tuning the surface structure of the support, thus providing a good example for designing a high-performance nanostructured catalyst. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Fluxing template-assisted synthesis of sponge-like Fe2O3 microspheres toward efficient catalysis for CO oxidation

    Science.gov (United States)

    Li, Wenge; Hu, Yanjie; Jiang, Hao; Jiang, Yi; Wang, Yang; Huang, Su; Biswas, Pratim; Li, Chunzhong

    2018-06-01

    Constructing a porous architecture is a considerable strategy to enhance the catalytic activity of metal oxides catalysts for CO oxidation. In this work, we have developed porous sponge-like Fe2O3 microspheres by employing a facile aerosol spray pyrolysis. The NaNO3 salt in the spray solution plays a crucial role as a fluxing sacrifice template in the formation of the sponge-like structure, in which a high surface area of 216.2 m2 g-1 and an average pore size of 4 nm are obtained. This novel Fe2O3 catalyst exhibits an improved catalytic activity compared to usual iron oxides catalysts. Nearly 50% CO conversion at a relatively low temperature of 200 °C and 100% CO conversion at 300 °C at a space velocity of 60 000 ml h-1 g-1 are achieved. Furthermore, it displays an outstanding catalytic stability without distinct decay for 1000 min in a continuous stream at 300 °C. In addition to the effect of plentiful adsorption sites for the gas reactant, the promoted catalytic performance is also attributed to the function of abundant OH groups rooted in the large surface of the sponge-like structure, which induces faster reaction rate of CO oxidation via a bicarbonate route.

  16. Nanosized spinel oxide catalysts for CO-oxidation prepared via CoMnMgAl quaternary hydrotalcite route

    Energy Technology Data Exchange (ETDEWEB)

    Mokhtar, M., E-mail: mmoustafa@kau.edu.s [Chemistry Department, Faculty of Science, King Abdulaziz University, 21589 Jeddah, P.O. Box 80203 (Saudi Arabia); Basahel, S.N.; Al-Angary, Y.O. [Chemistry Department, Faculty of Science, King Abdulaziz University, 21589 Jeddah, P.O. Box 80203 (Saudi Arabia)

    2010-03-18

    Catalytic activity of the Co-Mn-Mg-Al mixed oxide spinel catalysts was examined in CO oxidation by O{sub 2}. The prepared catalysts were characterized by chemical analysis (ICP), infrared spectroscopy (FTIR), thermal analysis (TG, DTG), powder X-ray diffraction (XRD), surface area measurements, and scanning electron microscopy (SEM).The calcined hydrotalcite-like precursor was composed of spinel-like Co-Mn-Mg-Al mixed oxide as the only XRD crystalline phases. The nanosized spinel oxide catalysts produced by calcination of hydrotalcites showed higher S{sub BET} than CoMn-hydrotalcite samples as calcination led to dehydroxylation and carbonate decomposition of anions in interlayer spaces. All the catalysts showed 100% CO conversion at high temperature even those calcined at 800 {sup o}C. A catalyst with Co/Mn = 4 and calcined at 500 {sup o}C showed 100% CO conversion at 160 {sup o}C. Moreover, this catalyst exhibited quite good durability without deactivation in 60 h stability test.

  17. Promotion effect of palladium on Co{sub 3}O{sub 4} incorporated within mesoporous MCM-41 silica for CO Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Hassan, Hassan M.A., E-mail: hassan.hassan@suezuniv.edu.eg [Department of Chemistry, Faculty of Science, Suez University, Suez (Egypt); Institut fur Anorganische Chemie und Strukturchemie, Heinrich-Heine Universitat, Dusseldorf (Germany); Betiha, Mohamed A. [Egyptian Petroleum Research Institute, Cairo 11727, Nasr City, Cairo (Egypt); Elshaarawy, Reda F.M. [Department of Chemistry, Faculty of Science, Suez University, Suez (Egypt); Institut fur Anorganische Chemie und Strukturchemie, Heinrich-Heine Universitat, Dusseldorf (Germany); Samy El-Shall, M. [Department of Chemistry, Virginia Commonwealth University Richmond, VA 23284-2006 (United States)

    2017-04-30

    Highlights: • Co{sub 3}O{sub 4} incorporated MCM-41 materials were successfully synthesized using MWI direct approach. • Co3{sup +} cation is considered as favorable site for CO adsorption resulted in promote the CO oxidation. • The loading of Pd species resulted in enhancement of activity for CO oxidation. - Abstract: Co{sub 3}O{sub 4} incorporated within mesoporous MCM-41 silica have been successfully synthesized and promoted with Pd nanoparticles through a microwave irradiation (MWI) approach. Powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), N{sub 2}-physisorped, X-ray photoelectron spectroscopy (XPS), temperature program reduction of hydrogen (H{sub 2}-TPR), temperature program desorption of oxygen (O{sub 2}-TPD) and high resolution transmission electron microscopy (HRTEM) were adapted to characterize these prepared catalysts. Carbon monoxide oxidation as a model reaction was then used to assess the catalytic performance of these materials. In the light of H{sub 2}-TPR and XPS results, revealed that the coexisting of Co{sup 3+} and Co{sup 2+} species as well as surface Co{sup 3+}/Co{sup 2+} ratio within the hexagonal mesoporous of MCM-41, could create an ideal environment to accomplish most extreme catalytic activity. On the other hand, the enhanced CO oxidation by Pd nanoparticles deposition has been explained in the light of the enhancement of the redox ability and tuning the electronic structure of Co{sub 3}O{sub 4}, which improved the O{sub 2} activation and reduced the adsorption ability of CO simultaneously, which significantly boosted the catalytic performance of CO oxidation. This work provides insights into factors that could lead to improved low temperature CO oxidation performance in Pd-based catalysts.

  18. Reaction mechanism of CO oxidation on Cu2O(111): A density functional study

    Science.gov (United States)

    Sun, Bao-Zhen; Chen, Wen-Kai; Xu, Yi-Jun

    2010-10-01

    The possible reaction mechanisms for CO oxidation on the perfect Cu2O(111) surface have been investigated by performing periodic density functional theoretical calculations. We find that Cu2O(111) is able to facilitate the CO oxidation with different mechanisms. Four possible mechanisms are explored (denoted as MER1, MER2, MLH1, and MLH2, respectively): MER1 is CO(gas)+O2(ads)-->CO2(gas) MER2 is CO(gas)+O2(ads)-->CO3(ads)-->O(ads)+CO2(gas) MLH1 refers to CO(ads)+O2(ads)-->O(ads)+CO2(ads) and MLH2 refers to CO(ads)+O2(ads)-->OOCO(ads)-->O(ads)+CO2(ads). Our transition state calculations clearly reveal that MER1 and MLH2 are both viable; but MER1 mechanism preferentially operates, in which only a moderate energy barrier (60.22 kJ/mol) needs to be overcome. When CO oxidation takes place along MER2 path, it is facile for CO3 formation, but is difficult for its decomposition, thereby CO3 species can stably exist on Cu2O(111). Of course, the reaction of CO with lattice O of Cu2O(111) is also considered. However, the calculated barrier is 600.00 kJ/mol, which is too large to make the path feasible. So, we believe that on Cu2O(111), CO reacts with adsorbed O, rather than lattice O, to form CO2. This is different from the usual Mars-van Krevene mechanism. The present results enrich our understanding of the catalytic oxidation of CO by copper-based and metal-oxide catalysts.

  19. Synthesis, Characterization and Shape-Dependent Catalytic CO Oxidation Performance of Ruthenium Oxide Nanomaterials: Influence of Polymer Surfactant

    Directory of Open Access Journals (Sweden)

    Antony Ananth

    2015-08-01

    Full Text Available Ruthenium oxide nano-catalysts supported on mesoporous γ-Al2O3 have been prepared by co-precipitation method and tested for CO oxidation. The effect of polyethylene glycol (PEG on the properties of the catalyst was studied. Addition of the PEG surfactant acted as a stabilizer and induced a change in the morphology of ruthenium oxide from spherical nanoparticles to one-dimensional nanorods. Total CO conversion was measured as a function of morphology at 175 °C and 200 °C with 1.0 wt.% loading for PEG-stabilized and un-stabilized catalysts, respectively. Conversion routinely increased with temperature but in each case, the PEG-stabilized catalyst exhibited a notably higher catalytic activity as compared to the un-stabilized equivalent. It can be assumed that the increase in the activity is due to the changes in porosity, shape and dispersion of the catalyst engendered by the use of PEG.

  20. Pt/SnO2-based CO-oxidation catalysts for long-life closed-cycle CO2 lasers

    Science.gov (United States)

    Schryer, David R.; Upchurch, Billy T.; Hess, Robert V.; Wood, George M.; Sidney, Barry D.; Miller, Irvin M.; Brown, Kenneth G.; Vannorman, John D.; Schryer, Jacqueline; Brown, David R.

    1990-01-01

    Noble-metal/tin-oxide based catalysts such as Pt/SnO2 have been shown to be good catalysts for the efficient oxidation of CO at or near room temperature. These catalysts require a reductive pretreatment and traces of hydrogen or water to exhibit their full activity. Addition of Palladium enhances the activity of these catalysts with about 15 to 20 percent Pt, 4 percent Pd, and the balance SnO2 being an optimum composition. Unfortunately, these catalysts presently exhibit significant decay due in part to CO2 retention, probably as a bicarbonate. Research on minimizing the decay in activity of these catalysts is currently in progress. A proposed mechanism of CO oxidation on Pt/SnO2-based catalysts has been developed and is discussed.

  1. Co-oxidation of carcinogenic polycyclic aromatic hydrocarbons with some biologically active compounds (BAC)

    Energy Technology Data Exchange (ETDEWEB)

    Gubergrits, M.Y.

    1978-09-01

    Oxidation of benzo(a)pyrene (BP) initiated by UV or gamma irradiation was promoted by benz(a)anthracene and 7,12-dimethylbenz(a)anthracene (DMBA) and inhibited by pyrene, dibenz(a,c)anthracene, and asymmetric benz(a)antharacene. The effects of these BAC commonly occurring together with BP in industrial wastes, increased with their concentrations. Phenol and 3-methylcholanthrene strongly promoted BP oxidation when present at low concentrations and inhibited it at high concentrations. Consistent promoting effect was also observed in BP co-oxidation with adipic acid, ..cap alpha..-naphthoflavon, and vitamin E, whereas succinic, azelaic, ferulic, gallic, and chlorogenic acids, rutin, and vitamin C acted as inhibitors. Most saturated dicarboxylic acids studied did not affect BP oxidation at 1:1 acid-BP molar ratio. The kinetics of 7,12-DMBA photooxidation inhibition by some metabolic intermediates, e.g., DMBA endo-peroxide, were also studied.

  2. Structured mesoporous Mn, Fe, and Co oxides: Synthesis, physicochemical, and catalytic properties

    Science.gov (United States)

    Maerle, A. A.; Karakulina, A. A.; Rodionova, L. I.; Moskovskaya, I. F.; Dobryakova, I. V.; Egorov, A. V.; Romanovskii, B. V.

    2014-02-01

    Structured mesoporous Mn, Fe, and Co oxides are synthesized using "soft" and "hard" templates; the resulting materials are characterized by XRD, SEM, TEM, BET, and TG. It is shown that in the first case, the oxides have high surface areas of up to 450 m2/g that are preserved after calcination of the material up to 300°C. Even though, the surface area of the oxides prepared by the "hard-template" method does not exceed 100 m2/g; it is, however, thermally stable up to 500°C. Catalytic activity of mesoporous oxides in methanol conversion was found to depend on both the nature of the transition metal and the type of template used in synthesis.

  3. Communication: CO oxidation by silver and gold cluster cations: Identification of different active oxygen species

    International Nuclear Information System (INIS)

    Popolan, Denisia M.; Bernhardt, Thorsten M.

    2011-01-01

    The oxidation of carbon monoxide with nitrous oxide on mass-selected Au 3 + and Ag 3 + clusters has been investigated under multicollision conditions in an octopole ion trap experiment. The comparative study reveals that for both gold and silver cations carbon dioxide is formed on the clusters. However, whereas in the case of Au 3 + the cluster itself acts as reactive species that facilitates the formation of CO 2 from N 2 O and CO, for silver the oxidized clusters Ag 3 O x + (n= 1-3) are identified as active in the CO oxidation reaction. Thus, in the case of the silver cluster cations N 2 O is dissociated and one oxygen atom is suggested to directly react with CO, whereas a second kind of oxygen strongly bound to silver is acting as a substrate for the reaction.

  4. Communication: CO oxidation by silver and gold cluster cations: Identification of different active oxygen species

    Science.gov (United States)

    Popolan, Denisia M.; Bernhardt, Thorsten M.

    2011-03-01

    The oxidation of carbon monoxide with nitrous oxide on mass-selected Au3+ and Ag3+ clusters has been investigated under multicollision conditions in an octopole ion trap experiment. The comparative study reveals that for both gold and silver cations carbon dioxide is formed on the clusters. However, whereas in the case of Au3+ the cluster itself acts as reactive species that facilitates the formation of CO2 from N2O and CO, for silver the oxidized clusters Ag3Ox+ (n = 1-3) are identified as active in the CO oxidation reaction. Thus, in the case of the silver cluster cations N2O is dissociated and one oxygen atom is suggested to directly react with CO, whereas a second kind of oxygen strongly bound to silver is acting as a substrate for the reaction.

  5. Synthesis and Characterization of 1D Ceria Nanomaterials for CO Oxidation and Steam Reforming of Methanol

    Directory of Open Access Journals (Sweden)

    Sujan Chowdhury

    2011-01-01

    Full Text Available Novel one-dimensional (1D ceria nanostructure has been investigated as a promising and practical approach for the reforming of methanol reaction. Size and shape of the ceria nanomaterials are directly involved with the catalytic activities. Several general synthesis routes as including soft and hard template-assemble phenomenon for the preparation of 1D cerium oxide are discussed. This preparation phenomenon is consisting with low cost and ecofriendly. Nanometer-sized 1D structure provides a high-surface area that can interact with methanol and carbon-monoxide reaction. Overall, nanometer-sized structure provides desirable properties, such as easy recovery and regeneration. As a result, the use of 1D cerium has been suitable for catalytic application of reforming. In this paper, we describe the 1D cerium oxide syntheses route and then summarize their properties in the field of CO oxidation and steam reforming of methanol approach.

  6. Water dissociation and CO oxidation over Au/anatase catalyst. A DFT-D2 study

    Science.gov (United States)

    Saqlain, Muhammad Adnan; Hussain, Akhtar; Siddiq, Muhammad; Leitão, Alexandre A.

    2018-03-01

    With the help of DFT-D2 methodology, we have investigated the adsorption of water on clean anatase(001) and Au/anatase(001). In the former case, adsorption energies of H2O differ to small extent computed employing GGA = PW91 and DFT-D2 methods. While the GGA = PW91 predicts that water would desorb close to 650 K on the TiO2 surface, the DFT-D2 predicts that desorption is most likely to occur above 700 K. A comparison of water adsorption on TiO2 and Au/TiO2 surfaces shows that the TiO2 prefers dimer adsorption whereas the Au/TiO2 prefers monomer adsorption. We found that the diffusion of surface hydroxyls on to the Au cluster from the Au/TiO2 periphery is unlikely and it seems that the CO oxidation would occur at the Au/TiO2 boundary. The results show that water dissociation and CO oxidation steps occur easily on Au/TiO2 indicating that this could be good alternative catalyst for water gas shift reaction industry.

  7. Chemisorption of CO and mechanism of CO oxidation on supported platinum nanoclusters

    KAUST Repository

    Allian, Ayman Daoud

    2011-03-30

    Kinetic, isotopic, and infrared studies on well-defined dispersed Pt clusters are combined here with first-principle theoretical methods on model cluster surfaces to probe the mechanism and structural requirements for CO oxidation catalysis at conditions typical of its industrial practice. CO oxidation turnover rates and the dynamics and thermodynamics of adsorption-desorption processes on cluster surfaces saturated with chemisorbed CO were measured on 1-20 nm Pt clusters under conditions of strict kinetic control. Turnover rates are proportional to O2 pressure and inversely proportional to CO pressure, consistent with kinetically relevant irreversible O2 activation steps on vacant sites present within saturated CO monolayers. These conclusions are consistent with the lack of isotopic scrambling in C16O-18O2-16O 2 reactions, and with infrared bands for chemisorbed CO that did not change within a CO pressure range that strongly influenced CO oxidation turnover rates. Density functional theory estimates of rate and equilibrium constants show that the kinetically relevant O2 activation steps involve direct O2* (or O2) reactions with CO* to form reactive O*-O-C*=O intermediates that decompose to form CO 2 and chemisorbed O*, instead of unassisted activation steps involving molecular adsorption and subsequent dissociation of O2. These CO-assisted O2 dissociation pathways avoid the higher barriers imposed by the spin-forbidden transitions required for unassisted O2 dissociation on surfaces saturated with chemisorbed CO. Measured rate parameters for CO oxidation were independent of Pt cluster size; these parameters depend on the ratio of rate constants for O2 reactions with CO* and CO adsorption equilibrium constants, which reflect the respective activation barriers and reaction enthalpies for these two steps. Infrared spectra during isotopic displacement and thermal desorption with 12CO- 13CO mixtures showed that the binding, dynamics, and thermodynamics of CO

  8. CO Oxidation by Subnanometer AgxAu3–x Supported Clusters via Density Functional Theory Simulations

    Energy Technology Data Exchange (ETDEWEB)

    Negreiros, Fabio R.; Sementa, Luca; Barcaro, Giovanni; Vajda, S.; Apra, Edoardo; Fortunelli, Alessandro

    2012-09-07

    The activity of AgxAu3–x/MgO(100) clusters in CO oxidation is investigated computationally via systematic sampling techniques. It is found that these subnanometer species transform after ligand adsorption into reaction complexes which catalyze CO oxidation through a variety of different mechanisms, occurring via both Langmuir–Hinshelwood and Eley–Rideal paths and in some cases directly involving the oxide support. The alloyed Ag2Au1 cluster is proposed as the best catalyst in terms of efficiency and robustness.

  9. Application of Ni-Oxide@TiO₂ Core-Shell Structures to Photocatalytic Mixed Dye Degradation, CO Oxidation, and Supercapacitors.

    Science.gov (United States)

    Lee, Seungwon; Lee, Jisuk; Nam, Kyusuk; Shin, Weon Gyu; Sohn, Youngku

    2016-12-20

    Performing diverse application tests on synthesized metal oxides is critical for identifying suitable application areas based on the material performances. In the present study, Ni-oxide@TiO₂ core-shell materials were synthesized and applied to photocatalytic mixed dye (methyl orange + rhodamine + methylene blue) degradation under ultraviolet (UV) and visible lights, CO oxidation, and supercapacitors. Their physicochemical properties were examined by field-emission scanning electron microscopy, X-ray diffraction analysis, Fourier-transform infrared spectroscopy, and UV-visible absorption spectroscopy. It was shown that their performances were highly dependent on the morphology, thermal treatment procedure, and TiO₂ overlayer coating.

  10. Fabrication of CuO-doped catalytic material containing zeolite synthesized from red mud and rice husk ash for CO oxidation

    Science.gov (United States)

    Hieu Do Thi, Minh; Thinh Tran, Quoc; Nguyen, Tri; Van Nguyen Thi, Thuy; Huynh, Ky Phuong Ha

    2018-06-01

    In this study a series of the CuO-doped materials containing zeolite with varying CuO contents were synthesized from red mud (RM) and rice husk ash (RHA). The rice husk ash/red mud with the molar ratio of , and being 1.8, 2.5 and 60, respectively, were maintained during the synthetic process of materials. The characteristic structure samples were analyzed by x-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscope (TEM), Brunauer–Emmett–Teller (BET) surface area and H2 temperature program reduction (H2-TPR). The catalytic activity of samples was evaluated in CO oxidation reaction in a microflow reactor at temperature range 200 °C–350 °C. The obtained results showed that all synthetic samples there exist the A-type zeolites with the average crystal size of 15–20 nm, the specific surface area of , and pore volume of . The material synthesized from RM and RHA with the zeolite structure (ZRM, undoped CuO) could also oxidize CO completely at 350 °C, and its activity was increase significantly when doped with CuO. CuO-doped materials with the zeolite structure exhibited excellent catalytic activity in CO oxidation. The ZRM sample loading 5 wt% CuO with particle nanosize about 10–30 nm was the best one for CO oxidation with complete conversion temperature at 275 °C.

  11. ZIF-67-derived hollow nanocages with layered double oxides shell as high-Efficiency catalysts for CO oxidation

    Science.gov (United States)

    Kong, Wenpeng; Li, Jing; Chen, Yao; Ren, Yuqing; Guo, Yonghua; Niu, Shengli; Yang, Yanzhao

    2018-04-01

    Constructing non-precious hybrid metal oxides with specific morphology as cost-effective and highly efficient catalysts is a promising way for the automotive exhaust purification. In this work, we report a facile strategy for the fabrication of a unique hollow Co-Ni layered double oxides (HLDO) nanocages by using zeolitic imidazole frameworks (ZIFs) as template. The synthesis of intermediate core-shell and hollow Co-Ni layered double hydroxides (HLDH) nanoflakes as well as the corresponding Co-Ni oxides products were successfully controlled, and the formation process was also explained. Among ZIF-67-derived oxides, HLDO exhibits excellent catalytic activities (complete conversion of CO into CO2 at 118 °C) and long-term stability for CO oxidation. The remarkable catalytic activities of HLDO can be attributed to high surface area (258 m2 g-1) inherited from the HLDH, which could provide more active sites for CO oxidation. In addition, active oxygen species indicated by the O 1 s XPS spectrum and improved synergistic effect between NiO and Co3O4 reflected by H2-TPR, further explain the enhanced performance of the HLDO catalysts. The presented strategy for controlled design and synthesis of hollow multicomponent metal oxides will provide prospects in developing highly effective catalysts.

  12. Catalytic CO Oxidation over Au Nanoparticles Loaded Nanoporous Nickel Phosphate Composite

    Directory of Open Access Journals (Sweden)

    Xiaonan Leng

    2015-01-01

    Full Text Available Au/nickel phosphate-5 (Au/VSB-5 composite with the noble metal loading amount of 1.43 wt.% is prepared by using microporous VSB-5 nanocrystals as the support. Carbon monoxide (CO oxidation reaction is carried out over the sample with several catalytic cycles. Complete conversion of CO is achieved at 238°C over the catalyst at the first catalytic cycle. The catalytic activity improved greatly at the second cycle with the complete conversion fulfilled at 198°C and preserved for the other cycles. A series of experiments such as X-ray diffraction (XRD, high resolution transmission electron microscopy (HRTEM, ultraviolet-visible (UV-vis spectroscopy, and X-ray photoelectron spectroscopy (XPS are carried out to characterize the catalysts before and after the reaction to study the factors influencing this promotion at the second cycle.

  13. Solving the master equation without kinetic Monte Carlo: Tensor train approximations for a CO oxidation model

    International Nuclear Information System (INIS)

    Gelß, Patrick; Matera, Sebastian; Schütte, Christof

    2016-01-01

    In multiscale modeling of heterogeneous catalytic processes, one crucial point is the solution of a Markovian master equation describing the stochastic reaction kinetics. Usually, this is too high-dimensional to be solved with standard numerical techniques and one has to rely on sampling approaches based on the kinetic Monte Carlo method. In this study we break the curse of dimensionality for the direct solution of the Markovian master equation by exploiting the Tensor Train Format for this purpose. The performance of the approach is demonstrated on a first principles based, reduced model for the CO oxidation on the RuO 2 (110) surface. We investigate the complexity for increasing system size and for various reaction conditions. The advantage over the stochastic simulation approach is illustrated by a problem with increased stiffness.

  14. Solving the master equation without kinetic Monte Carlo: Tensor train approximations for a CO oxidation model

    Science.gov (United States)

    Gelß, Patrick; Matera, Sebastian; Schütte, Christof

    2016-06-01

    In multiscale modeling of heterogeneous catalytic processes, one crucial point is the solution of a Markovian master equation describing the stochastic reaction kinetics. Usually, this is too high-dimensional to be solved with standard numerical techniques and one has to rely on sampling approaches based on the kinetic Monte Carlo method. In this study we break the curse of dimensionality for the direct solution of the Markovian master equation by exploiting the Tensor Train Format for this purpose. The performance of the approach is demonstrated on a first principles based, reduced model for the CO oxidation on the RuO2(110) surface. We investigate the complexity for increasing system size and for various reaction conditions. The advantage over the stochastic simulation approach is illustrated by a problem with increased stiffness.

  15. Solving the master equation without kinetic Monte Carlo: Tensor train approximations for a CO oxidation model

    Energy Technology Data Exchange (ETDEWEB)

    Gelß, Patrick, E-mail: p.gelss@fu-berlin.de; Matera, Sebastian, E-mail: matera@math.fu-berlin.de; Schütte, Christof, E-mail: schuette@mi.fu-berlin.de

    2016-06-01

    In multiscale modeling of heterogeneous catalytic processes, one crucial point is the solution of a Markovian master equation describing the stochastic reaction kinetics. Usually, this is too high-dimensional to be solved with standard numerical techniques and one has to rely on sampling approaches based on the kinetic Monte Carlo method. In this study we break the curse of dimensionality for the direct solution of the Markovian master equation by exploiting the Tensor Train Format for this purpose. The performance of the approach is demonstrated on a first principles based, reduced model for the CO oxidation on the RuO{sub 2}(110) surface. We investigate the complexity for increasing system size and for various reaction conditions. The advantage over the stochastic simulation approach is illustrated by a problem with increased stiffness.

  16. Probing the transition state region in catalytic CO oxidation on Ru

    Energy Technology Data Exchange (ETDEWEB)

    Ostrom, H. [Stockholm Univ. (Sweden); Oberg, H. [Stockholm Univ. (Sweden); Xin, H. [SLAC National Accelerator Lab., Menlo Park, CA (United States); LaRue, J. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States); Beye, M. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Dell' Angela, M. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); Gladh, J. [Stockholm Univ. (Sweden); Ng, M. L. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Sellberg, J. A. [Stockholm Univ. (Sweden); SLAC National Accelerator Lab., Menlo Park, CA (United States); Kaya, S. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Mercurio, G. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); Nordlund, D. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Hantschmann, M. [Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Hieke, F. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); Kuhn, D. [Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Schlotter, W. F. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Dakovski, G. L. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Turner, J. J. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Minitti, M. P. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Mitra, A. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Moeller, S. P. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Fohlisch, A. [Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Univ. Potsdam, Potsdam (Germany); Wolf, M. [Fritz-Haber Institute of the Max-Planck-Society, Berlin (Germany); Wurth, W. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); DESY Photon Science, Hamburg (Germany); Persson, M. [The Univ. of Liverpool, Liverpool (United Kingdom); Norskov, J. K. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States); Abild-Pedersen, F. [Stanford Univ., Stanford, CA (United States); Ogasawara, H. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Pettersson, L. G. M. [Stockholm Univ. (Sweden); Nilsson, A. [Stockholm Univ. (Sweden); SLAC National Accelerator Lab., Menlo Park, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)

    2015-02-12

    Femtosecond x-ray laser pulses are used to probe the CO oxidation reaction on ruthenium (Ru) initiated by an optical laser pulse. On a time scale of a few hundred femtoseconds, the optical laser pulse excites motions of CO and O on the surface, allowing the reactants to collide, and, with a transient close to a picosecond (ps), new electronic states appear in the O K-edge x-ray absorption spectrum. Density functional theory calculations indicate that these result from changes in the adsorption site and bond formation between CO and O with a distribution of OC–O bond lengths close to the transition state (TS). After 1 ps, 10% of the CO populate the TS region, which is consistent with predictions based on a quantum oscillator model.

  17. Influence of Structure and Charge State on the Mechanism of CO Oxidation on Gold Clusters

    Science.gov (United States)

    Johnson, Grant; Burgel, Christian; Reilly, Nelly; Mitric, Roland; Kimble, Michele; Tyo, Eric; Castleman, A. W.; Bonacic-Koutecky, Vlasta

    2008-05-01

    Gas-phase reactivity experiments and high level theoretical calculations have been employed to study the interaction of both positively and negatively charged gold oxide clusters with carbon monoxide (CO). We demonstrate that for negatively charged clusters CO is oxidized to CO2 by an Eley-Ridel-like (ER-) mechanism involving the attack of CO on oxygen rather than gold. In contrast, for positively charged clusters, the oxidation reaction may also occur by a Langmuir-Hinshelwood-like (LH-) mechanism involving the initial binding of CO to a gold atom followed by subsequent migration to an oxygen site. The LH mechanism is made possible through the large energy gain associated with the adsorption of two CO molecules onto cationic gold clusters. Structure-reactivity relationships are also established which demonstrate that terminally bound oxygen atoms are the most active sites for CO oxidation. Bridge bonded oxygen atoms and molecularly bound O2 units are shown to be inert. We also establish an inverse relationship between the binding energy of CO to gold clusters and the energy of the clusters lowest unoccupied molecular orbital (LUMO).

  18. Combinatorial selection of a two-dimensional 3d-TM-tetracyanoquinodimethane (TM-TCNQ) monolayer as a high-activity nanocatalyst for CO oxidation

    DEFF Research Database (Denmark)

    Deng, Qingming; Wu, Tiantian; Chen, Guibin

    2018-01-01

    catalyzed by Sc-TCNQ (CO + O2* → OOCO*) can follow the LH mechanism with free energy barriers as low as 0.73 eV at 300 K. The second step of CO + O* → CO2 can occur with rather small energy barriers via either LH or ER mechanisms. The high activity of Sc-TCNQ can be attributed to its unique structural...... and thermodynamics of all the ten candidates (Sc-Zn), Sc-TCNQ is found to display the lowest activation energies and yield the highest catalytic activity for room temperature CO oxidation. Exploring the Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms, we find that the rate-limiting step of CO oxidation...... and electronic features by possessing high stability, optimum adsorption energies with adsorbates, and fast reaction kinetics. These results have significant implications for the synthesis of two-dimensional single atom catalysis for CO oxidation with low-cost and high activity at low temperature....

  19. Perchlorate-Coupled Carbon Monoxide (CO Oxidation: Evidence for a Plausible Microbe-Mediated Reaction in Martian Brines

    Directory of Open Access Journals (Sweden)

    Marisa R. Myers

    2017-12-01

    Full Text Available The presence of hydrated salts on Mars indicates that some regions of its surface might be habitable if suitable metabolizable substrates are available. However, several lines of evidence have shown that Mars’ regolith contains only trace levels of the organic matter needed to support heterotrophic microbes. Due to the scarcity of organic carbon, carbon monoxide (CO at a concentration of about 700 parts per million (about 0.4 Pa might be the single most abundant readily available substrate that could support near-surface bacterial activity. Although a variety of electron acceptors can be coupled to CO oxidation, perchlorate is likely the most abundant potential oxidant in Mars’ brines. Whether perchlorate, a potent chaotrope, can support microbial CO oxidation has not been previously documented. We report here the first evidence for perchlorate-coupled CO oxidation based on assays with two distinct euryarchaeal extreme halophiles. CO oxidation occurred readily in 3.8 M NaCl brines with perchlorate concentrations from 0.01 to 1 M. Both isolates were able to couple CO with perchlorate or chlorate under anaerobic conditions with or without nitrate as an inducer for nitrate reductase, which serves as a perchlorate reductase in extreme halophiles. In the presence of perchlorate, CO concentrations were reduced to levels well below those found in Mars’ atmosphere. This indicates that CO could contribute to the survival of microbial populations in hydrated salt formations or brines if water activities are suitably permissive.

  20. A ternary nanocatalyst of Ni/Cr/Co oxides with high activity and stability for alkaline glucose electrooxidation

    International Nuclear Information System (INIS)

    Gu, Yingying; Yang, Haihong; Li, Benqiang; An, Yarui

    2016-01-01

    Highlights: • Ni-Cr-Co nanomaterial was synthesized by thermal decomposition method. • Ni 4 -Cr 1 -Co 1.5 has the highest GOR activity among the prepared catalysts. • A catalytic current density of 23.8 mA × cm −2 is attained for alkaline GOR. - Abstract: A novel ternary nanocatalyst of Ni-Cr-Co oxides is synthesized as anode electro-catalysts for glucose oxidation. The nanostructure is characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM), which indicates that the catalyst particles are well dispersed with average size of 30 nm when the calcination temperature is 500 °C. The electrochemical performance is evaluated via cyclic voltammetry (CV). Compared with the bimetallic Ni-Cr and Ni-Co nanocatalysts, Ni-Cr-Co electrocatalysts exhibites more negative onset potential (0.4 V) and high oxidation peak current density (23.8 mA cm −2 ) in alkaline media towards glucose oxidation. Meanwhile, the results also show that the Ni-Cr-Co nanomaterial possesses good performance of anti-poisoning capability, reproducibility and long-time stability, which make it an excellent candidate for fuel cell electrocatalyst.

  1. In Situ Spectroscopy and Mechanistic Insights into CO Oxidation on Transition-Metal-Substituted Ceria Nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Elias, Joseph S.; Stoerzinger, Kelsey A.; Hong, Wesley T.; Risch, Marcel; Giordano, Livia [Dipartimento; Mansour, Azzam N. [Naval; Shao-Horn, Yang

    2017-09-12

    Herein we investigate the reaction intermediates formed during CO oxidation on copper-substituted ceria nanoparticles (Cu0.1Ce0.9O2–x) by means of in situ spectroscopic techniques and identify an activity descriptor that rationalizes a trend with other metal substitutes (M0.1Ce0.9O2–x, M = Mn, Fe, Co, Ni). In situ X-ray absorption spectroscopy (XAS) performed under catalytic conditions demonstrates that O2– transfer occurs at dispersed copper centers, which are redox active during catalysis. In situ XAS reveals a dramatic reduction at the copper centers that is fully reversible under catalytic conditions, which rationalizes the high catalytic activity of Cu0.1Ce0.9O2–x. Ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) show that CO can be oxidized to CO32– in the absence of O2. We find that CO32– desorbs as CO2 only under oxygen-rich conditions when the oxygen vacancy is filled by the dissociative adsorption of O2. These data, along with kinetic analyses, lend support to a mechanism in which the breaking of copper–oxygen bonds is rate-determining under oxygen-rich conditions, while refilling the resulting oxygen vacancy is rate-determining under oxygen-lean conditions. On the basis of these observations and density functional calculations, we introduce the computed oxygen vacancy formation energy (Evac) as an activity descriptor for substituted ceria materials and demonstrate that Evac successfully rationalizes the trend in the activities of M0.1Ce0.9O2–x catalysts that spans three orders of magnitude. The applicability of Evac as a useful design descriptor is demonstrated by the catalytic performance of the ternary oxide Cu0.1La0.1Ce0.8O2–x, which has an apparent activation energy rivaling those of state-of-the-art Au/TiO2 materials. Thus, we suggest that cost-effective catalysts for CO oxidation can be rationally designed by judicious choice of substituting

  2. CO oxidation on PtSn nanoparticle catalysts occurs at the interface of Pt and Sn oxide domains formed under reaction conditions

    KAUST Repository

    Michalak, William D.

    2014-04-01

    The barrier to CO oxidation on Pt catalysts is the strongly bound adsorbed CO, which inhibits O2 adsorption and hinders CO2 formation. Using reaction studies and in situ X-ray spectroscopy with colloidally prepared, monodisperse ∼2 nm Pt and PtSn nanoparticle catalysts, we show that the addition of Sn to Pt provides distinctly different reaction sites and a more efficient reaction mechanism for CO oxidation compared to pure Pt catalysts. To probe the influence of Sn, we intentionally poisoned the Pt component of the nanoparticle catalysts using a CO-rich atmosphere. With a reaction environment comprised of 100 Torr CO and 40 Torr O2 and a temperature range between 200 and 300 C, Pt and PtSn catalysts exhibited activation barriers for CO2 formation of 133 kJ/mol and 35 kJ/mol, respectively. While pure Sn is readily oxidized and is not active for CO oxidation, the addition of Sn to Pt provides an active site for O2 adsorption that is important when Pt is covered with CO. Sn oxide was identified as the active Sn species under reaction conditions by in situ ambient pressure X-ray photoelectron spectroscopy measurements. While chemical signatures of Pt and Sn indicated intermixed metallic components under reducing conditions, Pt and Sn were found to reversibly separate into isolated domains of Pt and oxidic Sn on the nanoparticle surface under reaction conditions of 100 mTorr CO and 40 mTorr O2 between temperatures of 200-275 C. Under these conditions, PtSn catalysts exhibited apparent reaction orders in O2 for CO 2 production that were 0.5 and lower with increasing partial pressures. These reaction orders contrast the first-order dependence in O 2 known for pure Pt. The differences in activation barriers, non-first-order dependence in O2, and the presence of a partially oxidized Sn indicate that the enhanced activity is due to a reaction mechanism that occurs at a Pt/Sn oxide interface present at the nanoparticle surface. © 2014 Published by Elsevier Inc.

  3. Interfacial-Bonding-Regulated CO Oxidation over Pt Atoms Immobilized on Gas-Exfoliated Hexagonal Boron Nitride

    KAUST Repository

    Liu, Xin; Zhu, Hongdan; Linguerri, Roberto; Han, Yu; Chambaud, Gilberte; Meng, Changgong

    2017-01-01

    We compared the electronic structure and CO oxidation mechanisms over Pt atoms immobilized by both B-vacancies and N-vacancies on gas-exfoliated hexagonal boron nitride. We showed that chemical bonds are formed between the B atoms associated

  4. Copper atoms embedded in hexagonal boron nitride as potential catalysts for CO oxidation: A first-principles investigation

    KAUST Repository

    Liu, Xin; Duan, Ting; Sui, Yanhui; Meng, Changgong; Han, Yu

    2014-01-01

    We addressed the electronic structure of Cu atoms embedded in hexagonal boron nitride (h-BN) and their catalytic role in CO oxidation by first-principles-based calculations. We showed that Cu atoms prefer to bind directly with the localized defects

  5. Isotope labelling study of CO oxidation-assisted epoxidation of propene. Implications for oxygen activation on Au catalysts.

    Science.gov (United States)

    Jiang, Jian; Oxford, Sean M; Fu, Baosong; Kung, Mayfair C; Kung, Harold H; Ma, Jiantai

    2010-06-07

    (18)O isotope labelling studies of the CO oxidation-assisted epoxidation of propene, catalyzed by a mixture of Au/TiO(2) and TS-1, using a methanol-H(2)O solvent showed the O in the epoxide was exclusively from O(2) and not H(2)O or methanol.

  6. Magnetic properties of Fe-oxide and (Fe, Co) oxide nanoparticles synthesized in polystyrene resin matrix

    Science.gov (United States)

    Rodak, D.; Kroll, E.; Tsoi, G. M.; Vaishnava, P. P.; Naik, R.; Wenger, L. E.; Suryanarayanan, R.; Naik, V. M.; Boolchand, P.

    2003-03-01

    Magnetic nanoparticles have potential applications ranging from drug delivery and imaging in the medical field to sensing and memory storage in technology. The preparation, structure, and physical properties of iron oxide-based nanoparticles synthesized by ion exchange in a polystyrene resin matrix have been investigated. Employing a synthesis method developed originally by Ziolo, et. al^1, nanoparticles were prepared in a sulfonated divinyl benzene polystyrene resin matrix using various aqueous solutions of (1) FeCl_2, (2) FeCl_3, (3) FeCl2 : 2FeCl3 , (4) 9FeCl2 : CoCl_2, and (5) 4FeCl2 : CoCl_2. Powder x-ray diffraction measurements were used to identify the phases present while transmission electron microscopy was used for particle size distribution determinations. SQUID magnetization measurements (field-cooled and zero-field-cooled) and Fe^57 Mössbauer effect measurements indicate the presence of ferromagnetic iron oxide phases and a superparamagnetic behavior with blocking temperatures (T_B) varying from 50 K to room temperature. Nanoparticles synthesized using a stoichiometric mixture of FeCl2 and FeCl3 exhibit the lowest TB and smallest particle size distribution. The Mössbauer effect measurements have also been used to identify the iron oxides phases present and their relative amounts in the nanoparticles ^1R.F. Ziolo, et al., Science 207, 219 (1992). *Permanent address: Kettering University, Flint, MI 48504

  7. A comparative DFT study on CO oxidation reaction over Si-doped BC2N nanosheet and nanotube

    Science.gov (United States)

    Nematollahi, Parisa; Neyts, Erik C.

    2018-05-01

    In this study, we performed density functional theory (DFT) calculations to investigate different reaction mechanisms of CO oxidation catalyzed by the Si atom embedded defective BC2N nanostructures as well as the analysis of the structural and electronic properties. The structures of all the complexes are optimized and characterized by frequency calculations at the M062X/6-31G∗ computational level. Also, The electronic structures and thermodynamic parameters of adsorbed CO and O2 molecules over Si-doped BC2N nanostructures are examined in detail. Moreover, to investigate the curvature effect on the CO oxidation reaction, all the adsorption and CO oxidation reactions on a finite-sized armchair (6,6) Si-BC2NNT are also studied. Our results indicate that there can be two possible pathways for the CO oxidation with O2 molecule: O2(g) + CO(g) → O2(ads) + CO(ads) → CO2(g) + O(ads) and O(ads) + CO(g) → CO2(g). The first reaction proceeds via the Langmuir-Hinshelwood (LH) mechanism while the second goes through the Eley-Rideal (ER) mechanism. On the other hand, by increasing the tube diameter, the energy barrier increases due to the strong adsorption energy of the O2 molecule which is related to its dissociation over the tube surface. Our calculations indicate that the two step energy barrier of the oxidation reaction over Si-BC2NNS is less than that over the Si-BC2NNT. Hence, Si-BC2NNS may serve as an efficient and highly activated substrate to CO oxidation rather than (4,4) Si-BC2NNT.

  8. Low temperature oxidation, co-oxidation and auto-ignition of olefinic and aromatic blending compounds: Experimental study of interactions during the oxidation of a surrogate fuel; Oxydation, co-oxydation et auto-inflammation a basses temperatures d'alcenes et aromatiques types: etude experimentale des interactions au sein d'un carburant-modele

    Energy Technology Data Exchange (ETDEWEB)

    Vanhove, G.

    2004-12-15

    The low-temperature (600-900 K) and high-pressure (5-25 bar) oxidation and auto-ignition of the three position isomers of hexene, of binary mixtures of 1-hexene, toluene and iso-octane, and of a surrogate fuel composed of these three compounds were studied in motor conditions using a rapid compression machine. Auto-ignition delay times were measured as long as intermediate products concentrations during the delay. The results show that the oxidation chemistry of the hexenes is very dependent on the position of the double bond inside the molecule, and that strong interactions between the oxidation mechanisms of hydrocarbons in mixtures can occur. The data obtained concerning the surrogate fuel give a good insight into the behaviour of a practical gasoline after an homogeneous charge compression. (author)

  9. A Reactive Oxide Overlayer on Rh Nanoparticles during CO Oxidation and Its Size Dependence Studied by in Situ Ambient Pressure XPS

    International Nuclear Information System (INIS)

    Grass, Michael E.; Zhang, Yawen; Butcher, Derek R.; Park, Jeong Y.; Li, Yimin; Bluhm, Hendrik; Bratlie, Kaitlin M.; Zhang, Tianfu; Somorjai, Gabor A.

    2008-01-01

    CO oxidation is one of the most studied heterogeneous reactions, being scientifically and industrially important, particularly for removal of CO from exhaust streams and preferential oxidation for hydrogen purification in fuel cell applications. The precious metals Ru, Rh, Pd, Pt, and Au are most commonly used for this reaction because of their high activity and stability. Despite the wealth of experimental and theoretical data, it remains unclear what is the active surface for CO oxidation under catalytic conditions for these metals. In this communication, we utilize in situ synchrotron ambient pressure X-ray photoelectron spectroscopy (APXPS) to monitor the oxidation state at the surface of Rh nanoparticles during CO oxidation and demonstrate that the active catalyst is a surface oxide, the formation of which is dependent on particle size. The amount of oxide formed and the reaction rate both increase with decreasing particle size.

  10. A density functional theory study of CO oxidation on CuO1-x(111).

    Science.gov (United States)

    Yang, Bing-Xing; Ye, Li-Ping; Gu, Hui-Jie; Huang, Jin-Hua; Li, Hui-Ying; Luo, Yong

    2015-08-01

    The surface structures, CO adsorption, and oxidation-reaction properties of CuO1-x(111) with different reduction degree have been investigated by using density functional theory including on-site Coulomb corrections (DFT + U). Results indicate that the reduction of Cu has a great influence on the adsorption of CO. Electron localization caused by the reduction turns Cu(2+) to Cu(+), which interacts much stronger with CO, and the adsorption strength of CO is related to the electronic interaction with the substrate as well as the structural relaxation. In particular, the electronic interaction is proved to be the decisive factor. The surfaces of CuO1-x(111) with different reduction degree all have good adsorption to CO. With the expansion of the surface reduction degree, the amount of CO that is stably adsorbed on the surface increases, while the number of surface active lattice O decreases. In general, the activity of CO oxidation first rises and then declines.

  11. Illumination wavelength and time dependent nano gold photo-deposition and CO oxidation

    Directory of Open Access Journals (Sweden)

    Siewhui Chong

    Full Text Available In this study, nano gold (Au was deposited on titanium dioxide (TiO2 of different morphologies and crystallinities by photo-deposition method under LED irradiation with various wavelengths and irradiation times. The reactivity of carbon monoxide (CO oxidation of the as-prepared catalysts was examined and correlated with the characteristics of TiO2 support and gold particles. Characterization and activity tests showed that the effective illumination wavelength of photo-deposition is strongly determined by the band-gap of TiO2. Au/Cubic-TiO2 (450 nm, 5 min yielded comparatively highest CO conversion of 71%, followed by Au/P25 (375 nm, 1 min and Au/ST21 (340 nm, 1 min. When the photon energy of the LED is lower than the band-gap of TiO2, CO conversion rate increases with the irradiation time due to the decrease in gold particle size which could possibly due to the lower speed of photo-deposition compared to that of concentration diffusion. Keywords: Gold, Catalyst, TiO2, Photodeposition, Carbon monoxide, Oxidation

  12. Nanoroses of nickel oxides: Synthesis, electron tomography study, and application in CO oxidation and energy storage

    KAUST Repository

    Fihri, Aziz; Sougrat, Rachid; Baby, Rakhi Raghavan; Rahal, Raed; Cha, Dong Kyu; Hedhili, Mohamed N.; Bouhrara, Mohamed; Alshareef, Husam N.; Polshettiwar, Vivek

    2012-01-01

    Nickel oxide and mixed-metal oxide structures were fabricated by using microwave irradiation in pure water. The nickel oxide self-assembled into unique rose-shaped nanostructures. These nickel oxide roses were studied by performing electron

  13. Crystal Structural Effect of AuCu Alloy Nanoparticles on Catalytic CO Oxidation

    International Nuclear Information System (INIS)

    Zhan, Wangcheng; Wang, Jinglin; Wang, Haifeng; Zhang, Jinshui; Liu, Xiaofei

    2017-01-01

    Controlling the physical and chemical properties of alloy nanoparticles (NPs) is an important approach to optimize NP catalysis. Unlike other tuning knobs, such as size, shape, and composition, crystal structure has received limited attention and not been well understood for its role in catalysis. This deficiency is mainly due to the difficulty in synthesis and fine-tuning of the NPs’ crystal structure. Here, Exemplifying by AuCu alloy NPs with face centered cubic (fcc) and face centered tetragonal (fct) structure, we demonstrate a remarkable difference in phase segregation and catalytic performance depending on the crystal structure. During the thermal treatment in air, the Cu component in fcc-AuCu alloy NPs segregates more easily onto the alloy surface as compared to that in fct-AuCu alloy NPs. As a result, after annealing at 250 °C in air for 1 h, the fcc- and fct-AuCu alloy NPs are phase transferred into Au/CuO and AuCu/CuO core/shell structures, respectively. More importantly, this variation in heterostructures introduces a significant difference in CO adsorption on two catalysts, leading to a largely enhanced catalytic activity of AuCu/CuO NP catalyst for CO oxidation. Furthermore, the same concept can be extended to other alloy NPs, making it possible to fine-tune NP catalysis for many different chemical reactions.

  14. Stereoselectivity in catalytic reactions: CO oxidation on Pd(100) by rotationally aligned O2 molecules

    Science.gov (United States)

    Vattuone, L.; Gerbi, A.; Savio, L.; Cappelletti, D.; Pirani, F.; Rocca, M.

    2010-05-01

    We report on stereodynamical effects in heterogeneous catalytic reactions as measured by molecular beam-surface experiments. Specifically for CO oxidation on Pd(100) we find that the rotational alignment of the incoming O2 at low (Θ = 0.04 ML) and at intermediate (ΘCO = 0.17 ML) CO pre-coverage, causes a higher reactivity of molecules in high and in low helicity states, respectively (corresponding to helicoptering and cartwheeling motion of O2). In first approximation, at low CO pre-coverage the difference in reactivity is determined by the different location of the O atoms generated in the dissociation process by the different parent molecules, while at intermediate CO pre-coverage the reactivity is influenced also by the different ability of cartwheeling and helicoptering O2 to penetrate through the CO adlayer. In accord with this the total amount of CO2 produced is always largest for helicopters which generate supersurface O atoms at least in the low CO pre-coverage limit. A deeper inspection of the data indicates, however, that the dynamics is more complex, two different pathways being present for the reaction with O generated by helicopters and one for O generated by cartwheels. Moreover, cartwheels generated oxygen influences the reactivity of subsequently arriving helicopters.

  15. Crystal Structural Effect of AuCu Alloy Nanoparticles on Catalytic CO Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Zhan, Wangcheng [East China Univ. of Science and Technology, Shanghai (China); Wang, Jinglin [East China Univ. of Science and Technology, Shanghai (China); Wang, Haifeng [East China Univ. of Science and Technology, Shanghai (China); Zhang, Jinshui [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Liu, Xiaofei [East China Univ. of Science and Technology, Shanghai (China); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Zhang, Pengfei [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Chi, Miaofang [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Guo, Yanglong [East China Univ. of Science and Technology, Shanghai (China); Guo, Yun [East China Univ. of Science and Technology, Shanghai (China); Lu, Guanzhong [East China Univ. of Science and Technology, Shanghai (China); Sun, Shouheng [Brown Univ., Providence, RI (United States); Dai, Sheng [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States); Zhu, Huiyuan [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2017-06-07

    Controlling the physical and chemical properties of alloy nanoparticles (NPs) is an important approach to optimize NP catalysis. Unlike other tuning knobs, such as size, shape, and composition, crystal structure has received limited attention and not been well understood for its role in catalysis. This deficiency is mainly due to the difficulty in synthesis and fine-tuning of the NPs’ crystal structure. Here, Exemplifying by AuCu alloy NPs with face centered cubic (fcc) and face centered tetragonal (fct) structure, we demonstrate a remarkable difference in phase segregation and catalytic performance depending on the crystal structure. During the thermal treatment in air, the Cu component in fcc-AuCu alloy NPs segregates more easily onto the alloy surface as compared to that in fct-AuCu alloy NPs. As a result, after annealing at 250 °C in air for 1 h, the fcc- and fct-AuCu alloy NPs are phase transferred into Au/CuO and AuCu/CuO core/shell structures, respectively. More importantly, this variation in heterostructures introduces a significant difference in CO adsorption on two catalysts, leading to a largely enhanced catalytic activity of AuCu/CuO NP catalyst for CO oxidation. Furthermore, the same concept can be extended to other alloy NPs, making it possible to fine-tune NP catalysis for many different chemical reactions.

  16. The effect of Pd ensemble structure on the O2 dissociation and CO oxidation mechanisms on Au—Pd(100) surface alloys

    Science.gov (United States)

    Oǧuz, Ismail-Can; Mineva, Tzonka; Guesmi, Hazar

    2018-01-01

    The reactivity of various Pd ensembles on the Au—Pd(100) alloy catalyst toward CO oxidation was investigated by using density functional theory (DFT). This study was prompted by the search for efficient catalysts operating at low temperature for the CO oxidation reaction that is of primary environmental importance. To this aim, we considered Pd modified Au(100) surfaces including Pd monomers, Pd dimers, second neighboring Pd atoms, and Pd chains in a comparative study of the minimum energy reaction pathways. The effect of dispersion interactions was included in the calculations of the O2 dissociation reaction pathway by using the DFT-D3 scheme. The addition of the dispersion interaction strongly improves the adsorption ability of O2 on the Au—Pd surface but does not affect the activation energy barriers of the Transitions States (TSs). As for O2 to dissociate, it is imperative that the TS has lower activation energy than the O2 desorption energy. DFT-D3 is found to favor, in some cases, O2 dissociation on configurations being identified from uncorrected DFT calculations as inactive. This is the case of the second neighboring Pd configuration for which uncorrected DFT predicts positive Gibbs free energy (ΔG) of the O2 adsorption, therefore an endergonic reaction. With the addition of D3 correction, ΔG becomes negative that reveals a spontaneous O2 adsorption. Among the investigated Au—Pd (100) ensembles, the Pd chain dissociates most easily O2 and highly stabilizes the dissociated O atoms; however, it has an inferior reactivity toward CO oxidation and CO2 formation. Indeed, CO strongly adsorbs on the palladium bridge sites and therefore poisoning the surface Pd chain. By contrast, the second neighboring Pd configuration that shows somewhat lower ability to dissociate O2 turns out to be more reactive in the CO2 formation step. These results evidence the complex effect of Pd ensembles on the CO oxidation reaction. Associative CO oxidation proceeds with high

  17. Synthesis of octahedral like Cu-BTC derivatives derived from MOF calcined under different atmosphere for application in CO oxidation

    Science.gov (United States)

    Yang, Yiqiong; Dong, Han; Wang, Yin; He, Chi; Wang, Yuxin; Zhang, Xiaodong

    2018-02-01

    A series of octahedral structure Cu-BTC derivatives were successfully achieved through direct calcination of copper based metal organic framework Cu-BTC under different atmosphere (CO reaction gas, oxidizing gas O2, reducing gas H2, inert gas Ar). The Cu-BTC derivatives were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), laser Raman spectroscopy (LRS), N2 adsorption-desorption isotherm, element analysis, H2-temperature program reduction (H2-TPR) and X-ray photoelectron spectroscopic (XPS). It is found that Cu-BTC derivative derived from MOF calcined under reaction gas/O2 (Cu-BTC-CO/Cu-BTC-O) only retain Cu2O and CuO species. In addition, a weak Cu-BTC structure and Cu particles were observed on Cu-BTC derivative derived from MOF calcined under H2 (Cu-BTC-H). Obviously differently, Cu-BTC derivative derived from MOF calcined under Ar (Cu-BTC-Ar) still retains good MOF structure. The catalytic performance for CO oxidation over Cu-BTC derivatives was studied. It was found that Cu-BTC-CO showed a smaller specific surface area (8.0 m2/g), but presented an excellent catalytic performance, long-term stability and cycling stability with a complete CO conversion temperature (T100) of 140 °C, which was ascribed to the higher Cu2O/CuO ratio, good low temperature reduction behavior and a high quantity of surface active oxygen species.

  18. A computational study of catalysis by gold in applications of CO oxidation

    NARCIS (Netherlands)

    Hussain, A.

    2010-01-01

    Au based catalysts have been extensively studied since Masatake Haruta in Japan discovered that small Au nanoparticles supported on transition metal oxides are exceptionally active catalysts for oxidation reactions at low temperature. However, what makes gold, being inert in the bulk form, active is

  19. Interfacial-Bonding-Regulated CO Oxidation over Pt Atoms Immobilized on Gas-Exfoliated Hexagonal Boron Nitride

    KAUST Repository

    Liu, Xin

    2017-10-12

    We compared the electronic structure and CO oxidation mechanisms over Pt atoms immobilized by both B-vacancies and N-vacancies on gas-exfoliated hexagonal boron nitride. We showed that chemical bonds are formed between the B atoms associated with dangling bonds around the vacancies and Pt atoms. These bonds not only alter the thermodynamics and kinetics for the aggregation and effectively immobilize Pt atoms, but also significantly change the composition and energetic distribution of the electronic states of the composites to circumvent CO poisoning and to favour coadsorption of CO and O2, which further regulates the reactions to proceed through a Langmuir-Hinshelwood mechanism. The CO oxidation over Pt atoms immobilized at N-vacancies involves formation of an intermediate with –C(O)-O−O- bonded to Pt, the generation of CO2 by peroxo O−O bond scission and the reduction of the remnant oxygen, and the calculated energy barriers are 0.49, 0.23 and 0.18 eV, respectively. Such small energy barriers are comparable to those over Pt atoms trapped at B-vacancies, showing the effectiveness of Pt/hexagonal boron nitride atomic composites as catalysts for CO oxidation. These findings also suggest the feasibility of regulating the reaction pathways over single atom catalysts via interfacial engineering.

  20. Synthesis of highly efficient α-Fe{sub 2}O{sub 3} catalysts for CO oxidation derived from MIL-100(Fe)

    Energy Technology Data Exchange (ETDEWEB)

    Cui, Lifeng; Zhao, Di; Yang, Yang [Environment and Low-Carbon Research Center, School of Environment and Architecture, University of Shanghai for Science and Technology, Shanghai 200093 (China); Wang, Yuxin [Institute of Applied Biotechnology, Taizhou Vocation & Technical College, Taizhou, Zhejiang 318000 (China); Zhang, Xiaodong, E-mail: fatzhxd@126.com [Environment and Low-Carbon Research Center, School of Environment and Architecture, University of Shanghai for Science and Technology, Shanghai 200093 (China)

    2017-03-15

    Mesoporous hollow α-Fe{sub 2}O{sub 3} bricks were synthesized via a hydrothermal method to create a precursor MIL-100(Fe) and a subsequent calcination process was applied to prepare the Fe{sub 2}O{sub 3} phase. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results showed the morphology of hollow α-Fe{sub 2}O{sub 3} bricks which inherited from the MIL-100(Fe) template. The catalytic activities of hollow α-Fe{sub 2}O{sub 3} bricks for CO oxidation are studied in this work. Due to better low temperature reduction behavior, mesoporous hollow α-Fe{sub 2}O{sub 3} bricks obtained at calcination temperature of 430 °C displayed high catalytic activity and excellent stability with a complete CO conversion temperature (T{sub 100}) of 255 °C. - Graphical abstract: Synthesis of highly efficient α-Fe{sub 2}O{sub 3} catalysts for CO oxidation derived from MIL-100(Fe). - Highlights: • α-Fe{sub 2}O{sub 3} is prepared by the thermolysis of a MIL-100(Fe) template. • The morphology of hollow α-Fe{sub 2}O{sub 3} bricks is inherited from MIL-100(Fe) template. • α-Fe{sub 2}O{sub 3} obtained at calcined temperature of 430 °C displays high activity • Enhanced activity is attributed to crystal plane and reduction behavior.

  1. Bi-template assisted synthesis of mesoporous manganese oxide nanostructures: Tuning properties for efficient CO oxidation.

    Science.gov (United States)

    Roy, Mouni; Basak, Somjyoti; Naskar, Milan Kanti

    2016-02-21

    A simple soft bi-templating process was used for the synthesis of mesoporous manganese oxide nanostructures using KMnO4 as a precursor and polyethylene glycol and cetyltrimethylammonium bromide as templates in the presence of benzaldehyde as an organic additive in alkaline media, followed by calcination at 400 °C. X-ray diffraction and Raman spectroscopic analysis of the calcined products confirmed the existence of stoichiometric (MnO2 and Mn5O8) and non-stoichiometric mixed phases (MnO2 + Mn5O8) of Mn oxides obtained by tuning the concentration of the additive and the synthesis time. The surface properties of the prepared Mn oxides were determined by X-ray photoelectron spectroscopy. The mesoporosity of the samples was confirmed by N2 adsorption-desorption. Different synthetic conditions resulted in the formation of different morphologies of the Mn oxides (α-MnO2, Mn5O8, and α-MnO2 + Mn5O8), such as nanoparticles, nanorods, and nanowires. The synthesized mesoporous Mn oxide nanostructures were used for the catalytic oxidation of the harmful air pollutant carbon monoxide. The Mn5O8 nanoparticles with the highest Brunauer-Emmett-Teller surface area and the non-stoichiometric manganese oxide (α-MnO2 + Mn5O8) nanorods with a higher Mn(3+) concentration had the best catalytic efficiency.

  2. Effect of Preparation Methods on Al2O3 Supported CuO-CeO2-ZrO2 Catalysts for CO Oxidation

    Directory of Open Access Journals (Sweden)

    Gaurav Rattan

    2012-12-01

    Full Text Available To examine the effect of preparation methods, four catalyst samples having same composition (CuCe5.17Zr3.83Ox/g-Al2O3 (15wt% were prepared by four different methods for CO oxidation. The catalysts were prepared by co-impregnation, citric acid sol-gel, urea nitrate combustion and urea gelation co-precipitation methods, and characterized by BET, XRD, TGA/DSC and SEM. The The air oxidation of CO was carried out in a tubular fixed bed reactor under the following operating conditions: catalyst weight - 100 mg, temperature - ambient to 250 oC, pressure - atmospheric, 2.5% CO in air, total feed rate - 60 ml/min.  It was observed that the catalytic activity greatly influenced by the preparation methods. The highest activity of the catalyst prepared by the sol gel method appeared to be associated with its largest BET surface area. All the four catalysts were active for CO oxidation and did not show deactivation of catalytic activity for 50 hours of continuous runs. The ranking order of the preparation methods of the catalyst is as follows: sol-gel > co-impregnation > urea gelation > urea nitrate combustion. Copyright © 2012 by BCREC UNDIP. All rights reservedReceived: 14th June 2012, Revised: 8th September 2012, Accepted: 19th September 2012[How to Cite: G. Rattan, R. Prasad, R.C.Katyal. (2012. Effect of Preparation Methods on Al2O3 Supported CuO-CeO2-ZrO2 Catalysts for CO Oxidation. Bulletin of Chemical Reaction Engineering & Catalysis, 7(2: 112-123. doi:10.9767/bcrec.7.2.3646.112-123] [How to Link / DOI: http://dx.doi.org/10.9767/bcrec.7.2.3646.112-123 ] | View in 

  3. Kinetics of CO Oxidation over Unloaded and Pd-Loaded α-Fe2O3 Spherical Submicron Powder Catalysts: Photoacoustic Investigations at Low Pressure

    Directory of Open Access Journals (Sweden)

    Joong-Seok Roh

    2018-02-01

    Full Text Available In this study, α-Fe2O3 spherical particles with an average diameter of approximately 200 nm were synthesized by a solvothermal method for use as both a catalyst and medium for a Pd catalyst. The kinetics of CO oxidation over powders of α-Fe2O3 spherical particles and 14 wt % Pd/α-Fe2O3 spherical particles were measured in a static reactor by using a CO2 laser-based photoacoustic technique. The total pressure was fixed at 40 Torr for the CO/O2/N2 mixture for temperatures in the range of 225–350 °C. The variation in the CO2 photoacoustic signal with the CO2 concentration during CO oxidation was recorded as a function of time, and the CO2 photoacoustic data at the early reaction stage was used to estimate the rates of CO2 formation. Based on plots of ln(rate vs. 1/T, apparent activation energies were calculated as 13.4 kcal/mol for the α-Fe2O3 submicron powder and 13.2 kcal/mol for the 14 wt % Pd/α-Fe2O3 submicron powder. Reaction orders with respect to CO and O2 were determined from the rates measured at various partial pressures of CO and O2 at 350 °C. The zero-order of the reaction with respect to Po2 was observed for CO oxidation over α-Fe2O3 submicron powder, while 0.48 order to Po2 was observed for CO oxidation over Pd/α-Fe2O3 submicron powder. The partial orders with respect to PCO were determined as 0.58 and 0.54 for the α-Fe2O3, and the Pd/α-Fe2O3 submicron powders, respectively. The kinetic results obtained from both catalysts were compared with those for the α-Fe2O3 fine powder catalysts and were used to understand the reaction mechanism.

  4. CO oxidation on PtSn nanoparticle catalysts occurs at the interface of Pt and Sn oxide domains formed under reaction conditions

    KAUST Repository

    Michalak, William D.; Krier, James M.; Alayoglu, Selim; Shin, Jae-Yoon; An, Kwangjin; Komvopoulos, Kyriakos; Liu, Zhi; Somorjai, Gabor A.

    2014-01-01

    The barrier to CO oxidation on Pt catalysts is the strongly bound adsorbed CO, which inhibits O2 adsorption and hinders CO2 formation. Using reaction studies and in situ X-ray spectroscopy with colloidally prepared, monodisperse ∼2 nm Pt and PtSn

  5. Identification of a Catalytically Highly Active Surface Phase for CO Oxidation over PtRh Nanoparticles under Operando Reaction Conditions

    Science.gov (United States)

    Hejral, U.; Franz, D.; Volkov, S.; Francoual, S.; Strempfer, J.; Stierle, A.

    2018-03-01

    Pt-Rh alloy nanoparticles on oxide supports are widely employed in heterogeneous catalysis with applications ranging from automotive exhaust control to energy conversion. To improve catalyst performance, an atomic-scale correlation of the nanoparticle surface structure with its catalytic activity under industrially relevant operando conditions is essential. Here, we present x-ray diffraction data sensitive to the nanoparticle surface structure combined with in situ mass spectrometry during near ambient pressure CO oxidation. We identify the formation of ultrathin surface oxides by detecting x-ray diffraction signals from particular nanoparticle facets and correlate their evolution with the sample's enhanced catalytic activity. Our approach opens the door for an in-depth characterization of well-defined, oxide-supported nanoparticle based catalysts under operando conditions with unprecedented atomic-scale resolution.

  6. Au-HKUST-1 Composite Nanocapsules: Synthesis with a Coordination Replication Strategy and Catalysis on CO Oxidation.

    Science.gov (United States)

    Liu, Yongxin; Zhang, Jiali; Song, Lingxiao; Xu, Wenyuan; Guo, Zanru; Yang, Xiaomin; Wu, Xiaoxin; Chen, Xi

    2016-09-07

    A novel coordination replication of Cu2O redox-template strategy is reported to efficiently fabricate Au-HKUST-1 composite nanocapsule, with a HKUST-1 sandwich shell and an embedded Au nanoparticles layer. The novel synthesis procedure involves forming Au nanoparticles on the surface of Cu2O, transforming partial Cu2O into HKUST-1 shell via coordination replication, and removing the residual Cu2O by acid. The as-prepared Au-HKUST-1 composite nanocapsules displayed high catalytic activity on CO oxidation.

  7. Biomolecule-assisted synthesis of In(OH)₃ nanocubes and In₂O₃ nanoparticles: photocatalytic degradation of organic contaminants and CO oxidation.

    Science.gov (United States)

    Nayak, Arpan Kumar; Lee, Seungwon; Sohn, Youngku; Pradhan, Debabrata

    2015-12-04

    The synthesis of nanostructured materials without any hazardous organic chemicals and expensive capping reagents is one of the challenges in nanotechnology. Here we report on the L-arginine (a biomolecule)-assisted synthesis of single crystalline cubic In(OH)3 nanocubes of a size in the range of 30-60 nm along the diagonal using hydrothermal methods. Upon calcining at 750 °C for 1 h in air, In(OH)3 nanocubes are transformed into In2O3 nanoparticles (NPs) with voids. The morphology transformation and formation of voids with the increase of the calcination temperature is studied in detail. The possible mechanism of the voids' formation is discussed on the basis of the Kirkendall effect. The photocatalytic properties of In(OH)3 nanocubes and In2O3 NPs are studied for the degradation of rhodamin B and alizarin red S. Furthermore, the CO oxidation activity of In(OH)3 nanocubes and In2O3 NPs is examined. The photocatalytic and CO oxidation activity are measured to be higher for In2O3 NPs than for In(OH)3 nanocubes. This is attributed to the lower energy gap and higher specific surface area of the former. The present green synthesis has potential for the synthesis of other inorganic nanomaterials.

  8. A facile synthesis for cauliflower like CeO2 catalysts from Ce-BTC precursor and their catalytic performance for CO oxidation

    Science.gov (United States)

    Zhang, Xiaodong; Hou, Fulin; Yang, Yang; Wang, Yuxin; Liu, Ning; Chen, Dan; Yang, Yiqiong

    2017-11-01

    The paper presents a novel and facile method for preparing cauliflowerlike CeO2 through direct decomposition of cerium based metal-organic framework (MOF) Ce-BTC (BTC = 1,3,5-benzenetricarboxylic acid) straw in air. Several analytical tools such as Scanning electron microscopy (SEM), X-ray diffraction (XRD), Thermogravimetric (TG), N2 adsorption-desorption, Temperature programmed reduction (TPR), Raman, X-ray photoelectron spectroscopic (XPS) and Photoluminescence (PL) have been used to characterize Ce-BTC and CeO2. The Ce-BTC calcined at 500 °C (CeO2-500) maintains the morphology of its template ;Ce-BTC; and forms a special cauliflower-like structure. XRD patterns showed that the catalyst has a perfect CeO2 crystal structure and has a smaller particle size. The prepared CeO2 cauliflowers exhibit excellent catalytic activities, long-term stability, and cycling stability for CO oxidation. The improved catalytic activities could be attributed to porous nanorods of CeO2 cauliflowers, which provide more active sites and oxygen vacancy for CO oxidation.

  9. Synthesis of highly efficient Mn{sub 2}O{sub 3} catalysts for CO oxidation derived from Mn-MIL-100

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Xiaodong, E-mail: fatzhxd@126.com [Environment and Low-Carbon Research Center, School of Environment and Architecture, University of Shanghai for Science and Technology, Shanghai 200093 (China); Li, Hongxin; Hou, Fulin; Yang, Yang; Dong, Han; Liu, Ning [Environment and Low-Carbon Research Center, School of Environment and Architecture, University of Shanghai for Science and Technology, Shanghai 200093 (China); Wang, Yuxin [Institute of Applied Biotechnology, Taizhou Vocation & Technical College, Taizhou, Zhejiang 318000 (China); Cui, Lifeng, E-mail: lifeng.cui@gmail.com [Environment and Low-Carbon Research Center, School of Environment and Architecture, University of Shanghai for Science and Technology, Shanghai 200093 (China)

    2017-07-31

    Highlights: • The morphology of porous Mn{sub 2}O{sub 3} cubes was inherited from Mn-MIL-100 template. • Mn{sub 2}O{sub 3} obtained at calcined temperature of 700 °C displayed high activity. • Enhanced activity is attributed to surface active oxygen, and reduction behavior. - Abstract: In this work, metal-organic frameworks (MOFs) Mn-MIL-100 were first prepared, which were next used as templates to obtain the irregular porous Mn{sub 2}O{sub 3} cubes through calcination with air at different temperature. The catalysts were characterized by N{sub 2} adsorption-desorption, X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), H{sub 2}-temperature program reduction (H{sub 2}-TPR) and X-ray photoelectron spectroscopic (XPS). The catalytic activity for CO oxidation over Mn{sub 2}O{sub 3} catalysts was investigated. It was found that calcination temperature had a strong effect on the structure and catalytic activity of Mn{sub 2}O{sub 3} catalyst. Mn{sub 2}O{sub 3} catalyst obtained by calcined at 700 °C (Mn{sub 2}O{sub 3}-700) showed a smaller specific surface area, but displayed a high catalytic activity and excellent stability with a complete CO conversion temperature (T{sub 98}) of 240 °C, which was attributed to the unique structure, a high quantity of surface active oxygen species, smaller particle size, oxygen vacancies and good low temperature reduction behavior. The effect of water vapor on catalytic activity was also examined. The introduction of water vapor to the feedstock induced a positive effect on CO oxidation over Mn{sub 2}O{sub 3}-700 catalyst. Furthermore, no obvious drop is observed in activity over catalysts even in the presence of water vapor during 48 h.

  10. Effect of phase interaction on catalytic CO oxidation over the SnO{sub 2}/Al{sub 2}O{sub 3} model catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Chai, Shujing [Collaborative Innovation Center of Chemical Science & Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science & Technology, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300354 (China); The Institute of Seawater Desalination and Miltipurpose Utilization, State Oceanic Administration, Tianjin 300192 (China); Bai, Xueqin; Li, Jing; Liu, Cheng; Ding, Tong; Tian, Ye; Liu, Chang [Collaborative Innovation Center of Chemical Science & Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science & Technology, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300354 (China); Xian, Hui [Tianjin Polytechnic University, School of Computer Science & Software Engineering, Tianjin 300387 (China); Mi, Wenbo [Tianjin Key Laboratory of Low Dimensional Materials Physics and Preparation Technology, Faculty of Science, Tianjin University, Tianjin 300354 (China); Li, Xingang, E-mail: xingang_li@tju.edu.cn [Collaborative Innovation Center of Chemical Science & Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science & Technology, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300354 (China)

    2017-04-30

    Highlights: • Activity for CO oxidation is greatly enhanced by interaction between SnO{sub 2} and Al{sub 2}O{sub 3}. • Interaction between SnO{sub 2} and Al{sub 2}O{sub 3} phases can generate oxygen vacancies. • Oxygen vacancies play an import role for catalytic CO oxidation. • Sn{sup 4+} cations are the effective sites for catalytic CO oxidation. • Langmuir-Hinshelwood model is preferred for catalytic CO oxidation. - Abstract: We investigated the catalytic CO oxidation over the SnO{sub 2}/Al{sub 2}O{sub 3} model catalysts. Our results show that interaction between the Al{sub 2}O{sub 3} and SnO{sub 2} phases results in the significantly improved catalytic activity because of the formation of the oxygen vacancies. The oxygen storage capacity of the SnO{sub 2}/Al{sub 2}O{sub 3} catalyst prepared by the physically mixed method is nearly two times higher than that of the SnO{sub 2}, which probably results from the change of electron concentration on the interface of the SnO{sub 2} and Al{sub 2}O{sub 3} phases. Introducing water vapor to the feeding gas would a little decrease the activity of the catalysts, but the reaction rate could completely recover after removal of water vapor. The kinetics results suggest that the surface Sn{sup 4+} cations are effective CO adsorptive sites, and the surface adsorbed oxygen plays an important role upon CO oxidation. The reaction pathways upon the SnO{sub 2}-based catalysts for CO oxidation follow the Langmuir-Hinshelwood model.

  11. Pt/MOx/SiO2, Pt/MOx/TiO2, and Pt/MOx/Al2O3 Catalysts for CO Oxidation

    Directory of Open Access Journals (Sweden)

    Hongmei Qin

    2015-04-01

    Full Text Available Conventional supported Pt catalysts have often been prepared by loading Pt onto commercial supports, such as SiO2, TiO2, Al2O3, and carbon. These catalysts usually have simple metal-support (i.e., Pt-SiO2 interfaces. To tune the catalytic performance of supported Pt catalysts, it is desirable to modify the metal-support interfaces by incorporating an oxide additive into the catalyst formula. Here we prepared three series of metal oxide-modified Pt catalysts (i.e., Pt/MOx/SiO2, Pt/MOx/TiO2, and Pt/MOx/Al2O3, where M = Al, Fe, Co, Cu, Zn, Ba, La for CO oxidation. Among them, Pt/CoOx/SiO2, Pt/CoOx/TiO2, and Pt/CoOx/Al2O3 showed the highest catalytic activities. Relevant samples were characterized by N2 adsorption-desorption, X-ray diffraction (XRD, transmission electron microscopy (TEM, H2 temperature-programmed reduction (H2-TPR, X-ray photoelectron spectroscopy (XPS, CO temperature-programmed desorption (CO-TPD, O2 temperature-programmed desorption (O2-TPD, and CO2 temperature-programmed desorption (CO2-TPD.

  12. Hydrogen poisoning of the CO oxidation reaction on Pt and Pd under ultrahigh vacuum conditions

    International Nuclear Information System (INIS)

    Strozier, J.A.

    1977-01-01

    The poisoning by hydrogen of the catalyzed oxidation of CO on Pt and Pd under ultrahigh vacuum conditions was investigated. ac pulsing techniques are used in which the pressure of the reactant CO in the reaction chamber is modulated periodically by means of a fast piezoelectric ultrahigh vacuum valve, and the ac component of the product CO 2 is recorded mass spectroscopically by phase-sensitive techniques. The ac CO 2 production rate is measured as a function of hydrogen pressure (1 - 10 x 10 -9 toor) at constant CO and O 2 pressures (approximately equal to 5 x 10 -8 torr), and constant temperature (approximately equal to 700 K). Exact theoretical calculations of CO 2 production rates were carried out employing several models, i.e., oxygen burn-off by hydrogen, incorporating both the Eley-Rideal and Langmuir-Hinshelwood mechanisms. From a comparison with the experimental results, the probable reaction is of the Langmuir-Hinshelwood type and the relevant rate constant is also determined. These results are compared with other results in the literature on hydrogen oxidation on the surface of Pt

  13. Application of Ni-Oxide@TiO2 Core-Shell Structures to Photocatalytic Mixed Dye Degradation, CO Oxidation, and Supercapacitors

    Directory of Open Access Journals (Sweden)

    Seungwon Lee

    2016-12-01

    Full Text Available Performing diverse application tests on synthesized metal oxides is critical for identifying suitable application areas based on the material performances. In the present study, Ni-oxide@TiO2 core-shell materials were synthesized and applied to photocatalytic mixed dye (methyl orange + rhodamine + methylene blue degradation under ultraviolet (UV and visible lights, CO oxidation, and supercapacitors. Their physicochemical properties were examined by field-emission scanning electron microscopy, X-ray diffraction analysis, Fourier-transform infrared spectroscopy, and UV-visible absorption spectroscopy. It was shown that their performances were highly dependent on the morphology, thermal treatment procedure, and TiO2 overlayer coating.

  14. Spatio-temporal dynamics of oscillatory heterogeneous catalysis: CO oxidation on platinum

    Science.gov (United States)

    Yamamoto, S. Y.; Surko, C. M.; Maple, M. B.; Pina, R. K.

    1995-06-01

    Reaction-rate oscillations in the oxidation of carbon monoxide on the surface of platinum catalysts are studied in a continuous flow reactor at atmospheric pressure using infrared imaging. Small-amplitude temperature oscillations (0.2-8 K) result in approximately isothermal conditions, where changes in rate constants, for typical activation energies and temperatures, are small. The catalysts are in the form of platinum thin films on quartz substrates and provide highly repeatable oscillatory behavior. The platinum films are fabricated in the form of annular rings which provide a quasi-one-dimensional geometry in order to simplify comparison to theoretical models. Time-series measurements by means of thermocouples are used to characterize the oscillations. The infrared images show that most oscillations are spatially synchronized to within the 0.25 s time resolution of the experiment. The images also show that ``fine structure'' oscillations (i.e., small-amplitude, high frequency oscillations superimposed on larger-amplitude waveforms) are associated with spatially desynchronized patterns.

  15. Facile synthesis of highly efficient amorphous Mn-MIL-100 catalysts: The formation mechanism and the structure changes during the application for CO oxidation.

    Science.gov (United States)

    Zhang, Xiaodong; Li, Hongxin; Lv, Xutian; Xu, Jingcheng; Wang, Yuxin; He, Chi; Liu, Ning; Yang, Yiqiong; Wang, Yin

    2018-04-13

    A comprehensive study was carried out on amorphous metal-organic frameworks Mn-MIL-100 as efficient catalysts towards CO oxidation. This study focuses on explaining the crystalline-amorphous-crystalline transformations during thermolysis process of Mn-MIL-100 and studying the structure changes during the reaction process for CO oxidation. A possible formation mechanism of amorphous Mn-MIL-100 was proposed. Amorphous Mn-MIL-100 obtained by calcination at 250°C (a-Mn-250) showed a smaller specific surface area (4 m2/g), but displayed a high catalytic activity. Furthermore, the structure of amorphous Mn-MIL-100 was labile during the reaction process. When used a-Mn-250 were treated with reaction atmosphere at high temperature (named used a-Mn-250-S), the amorphous catalysts transformed to Mn2O3. Meanwhile, BET surface area (164 m2/g) and the catalytic performance both sharply increased. In addition, used a-Mn-250-S catalyst transformed from Mn2O3 to Mn3O4, resulting in the slightly decrease of catalytic activity under the presence of 1 vol% water vapor in the stream. A schematic of the structure changes during the reaction process was proposed. The achievement of our synthesis relies on the increase of BET surface area using CO as retreatment atmosphere, and the enhanced catalytic activity was attributed to the unique structure, a high quantity of surface active oxygen species, oxygen vacancies and good low temperature reduction behavior. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Pt atoms stabilized on hexagonal boron nitride as efficient single-atom catalysts for CO oxidation: A first-principles investigation

    KAUST Repository

    Liu, Xin; Duan, Ting; Meng, Changgong; Han, Yu

    2015-01-01

    Taking CO oxidation as a probe, we investigated the electronic structure and reactivity of Pt atoms stabilized by vacancy defects on hexagonal boron nitride (h-BN) by first-principles-based calculations. As a joint effect of the high reactivity

  17. CO Oxidation on the Au15Cu15 Cluster and the Role of Vacancies in the MgO(100) Support

    DEFF Research Database (Denmark)

    Ma, Li; Melander, Marko; Weckman, Timo

    2016-01-01

    analysis reveals that CO oxidation is very sensitive to the CO partial pressure, as the relatively strong CO binding leads readily to CO poisoning of the cluster surface sites and hinders CO2 formation. For low CO partial pressures, the catalytic reaction takes place already at 150 K for the cluster...

  18. The PEMFC-integrated CO oxidation — a novel method of simplifying the fuel cell plant

    Science.gov (United States)

    Rohland, Bernd; Plzak, Vojtech

    Natural gas and methanol are the most economical fuels for residential fuel cell power generators as well as for mobile PEM-fuel cells. However, they have to be reformed with steam into hydrogen, which is to be cleaned from CO by shift-reaction and by partial oxidation to a level of no more than 30 ppm CO. This level is set by the Pt/Ru-C-anode of the PEMFC. A higher partial oxidation reaction rate for CO than those of Pt/Ru-C can be achieved in an oxidic Au-catalyst system. In the Fe 2O 3-Au system, a reaction rate of 2·10 -3 mol CO/s g Au at 1000 ppm CO and 5% "air bleed" at 80°C is achieved. This high rate allows to construct a catalyst-sheet for each cell within a PEMFC-stack. Practical and theoretical current/voltage characteristics of PEMFCs with catalyst-sheet are presented at 1000 ppm CO in hydrogen with 5% "air bleed". This gives the possibility of simplifying the gas processor of the plant.

  19. Gold Nanoparticles Supported on Fibrous Silica Nanospheres (KCC-1) as Efficient Heterogeneous Catalysts for CO Oxidation

    KAUST Repository

    Qureshi, Ziyauddin S.; Sarawade, Pradip B.; Hussain, Irshad; Zhu, Haibo; Al-Johani, Hind; Anjum, Dalaver H.; Hedhili, Mohamed N.; Maity, Niladri; D'Elia, Valerio; Basset, Jean-Marie

    2016-01-01

    Gold nanoparticles (Au NPs) of different sizes were supported on fibrous silica nanospheres (KCC-1) by various methods. The size and the location of the Au NPs on the support were found to depend on the preparation method. The KCC-1-supported Au NPs were thoroughly characterized by using HR-TEM, XRD, X-ray photoelectron spectroscopy, UV, and Brunauer-Emmett-Teller surface area measurements and were applied in catalysis for the oxidation of CO. The catalytic performance is discussed in relation to the morphological properties of KCC-1. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Gold Nanoparticles Supported on Fibrous Silica Nanospheres (KCC-1) as Efficient Heterogeneous Catalysts for CO Oxidation

    KAUST Repository

    Qureshi, Ziyauddin S.

    2016-04-13

    Gold nanoparticles (Au NPs) of different sizes were supported on fibrous silica nanospheres (KCC-1) by various methods. The size and the location of the Au NPs on the support were found to depend on the preparation method. The KCC-1-supported Au NPs were thoroughly characterized by using HR-TEM, XRD, X-ray photoelectron spectroscopy, UV, and Brunauer-Emmett-Teller surface area measurements and were applied in catalysis for the oxidation of CO. The catalytic performance is discussed in relation to the morphological properties of KCC-1. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Kinetic Study of Oxygen Adsorption over Nanosized Au/γ-Al2O3 Supported Catalysts under Selective CO Oxidation Conditions

    Directory of Open Access Journals (Sweden)

    George Karaiskakis

    2012-04-01

    Full Text Available O2 adsorption is a key process for further understanding the mechanism of selective CO oxidation (SCO on gold catalysts. Rate constants related to the elementary steps of O2 adsorption, desorption and surface bonding, as well as the respective activation energies, over a nanosized Au/γ-Al2O3 catalyst, were determined by Reversed-Flow Inverse Gas Chromatography (RF-IGC. The present study, carried-out in a wide temperature range (50–300 °C, both in excess as well as in the absence of H2, resulted in mechanistic insights and kinetic as well as energetic comparisons, on the sorption processes of SCO reactants. In the absence of H2, the rate of O2 binding, over Au/γ-Al2O3, drastically changes with rising temperature, indicating possible O2 dissociation at elevated temperatures. H2 facilitates stronger O2 bonding at higher temperatures, while low temperature binding remains practically unaffected. The lower energy barriers observed, under H2 rich conditions, can be correlated to O2 dissociation after hydrogenation. Although, H2 enhances both selective CO reactant’s desorption, O2 desorption is more favored than that of CO, in agreement with the well-known mild bonding of SCO reactant’s at lower temperatures. The experimentally observed drastic change in the strength of CO and O2 binding is consistent both with well-known high activity of SCO at ambient temperatures, as well as with the loss of selectivity at higher temperatures.

  2. Kinetic Study of Oxygen Adsorption over Nanosized Au/γ-Al2O3 Supported Catalysts under Selective CO Oxidation Conditions

    Directory of Open Access Journals (Sweden)

    George Karaiskakis

    2012-04-01

    Full Text Available O2 adsorption is a key process for further understanding the mechanism of selective CO oxidation (SCO on gold catalysts. Rate constants related to the elementary steps of O2 adsorption, desorption and surface bonding, as well as the respective activation energies, over a nanosized Au/γ-Al2O3 catalyst, were determined by Reversed-Flow Inverse Gas Chromatography (RF-IGC. The present study, carried-out in a wide temperature range (50–300 °C, both in excess as well as in the absence of H2, resulted in mechanistic insights and kinetic as well as energetic comparisons, on the sorption processes of SCO reactants. In the absence of H2, the rate of O2 binding, over Au/γ-Al2O3, drastically changes with rising temperature, indicating possible O2 dissociation at elevated temperatures. H2 facilitates stronger O2 bonding at higher temperatures, while low temperature binding remains practically unaffected. The lower energy barriers observed, under H2 rich conditions, can be correlated to O2 dissociation after hydrogenation. Although, H2 enhances both selective CO reactant’s desorption, O2 desorption is more favored than that of CO, in agreement with the well-known mild bonding of SCO reactant’s at lower temperatures. The experimentally observed drastic change in the strength of CO and O2 binding is consistent both with well-known high activity of SCO at ambient temperatures, as well as with the loss of selectivity at higher temperatures.

  3. Visualization of Gas Distribution in a Model AP-XPS Reactor by PLIF: CO Oxidation over a Pd(100 Catalyst

    Directory of Open Access Journals (Sweden)

    Jianfeng Zhou

    2017-01-01

    Full Text Available In situ knowledge of the gas phase around a catalyst is essential to make an accurate correlation between the catalytic activity and surface structure in operando studies. Although ambient pressure X-ray photoelectron spectroscopy (AP-XPS can provide information on the gas phase as well as the surface structure of a working catalyst, the gas phase detected has not been spatially resolved to date, thus possibly making it ambiguous to interpret the AP-XPS spectra. In this work, planar laser-induced fluorescence (PLIF is used to visualize the CO2 distribution in a model AP-XPS reactor, during CO oxidation over a Pd(100 catalyst. The results show that the gas composition in the vicinity of the sample measured by PLIF is significantly different from that measured by a conventional mass spectrometer connected to a nozzle positioned just above the sample. In addition, the gas distribution above the catalytic sample has a strong dependence on the gas flow and total chamber pressure. The technique presented has the potential to increase our knowledge of the gas phase in AP-XPS, as well as to optimize the design and operating conditions of in situ AP-XPS reactors for catalysis studies.

  4. Thermally stable single atom Pt/m-Al2O3 for selective hydrogenation and CO oxidation

    KAUST Repository

    Zhang, Zailei

    2017-07-27

    Single-atom metal catalysts offer a promising way to utilize precious noble metal elements more effectively, provided that they are catalytically active and sufficiently stable. Herein, we report a synthetic strategy for Pt single-atom catalysts with outstanding stability in several reactions under demanding conditions. The Pt atoms are firmly anchored in the internal surface of mesoporous Al2O3, likely stabilized by coordinatively unsaturated pentahedral Al3+ centres. The catalyst keeps its structural integrity and excellent performance for the selective hydrogenation of 1,3-butadiene after exposure to a reductive atmosphere at 200 °C for 24 h. Compared to commercial Pt nanoparticle catalyst on Al2O3 and control samples, this system exhibits significantly enhanced stability and performance for n-hexane hydro-reforming at 550 °C for 48 h, although agglomeration of Pt single-atoms into clusters is observed after reaction. In CO oxidation, the Pt single-atom identity was fully maintained after 60 cycles between 100 and 400 °C over a one-month period.

  5. Physicochemical properties of manganese dioxide synthesized using C2–C5 alcohols as reducing agents and their catalytic activities for CO oxidation

    KAUST Repository

    Lee, Young-Ho

    2015-09-26

    MnO2 catalysts were synthesized in an aqueous solution of KMnO4 and C2–C5 alcohols using a simple redox method at room temperature. The crystalline structure of all samples was δ-MnO2 after being calcined at 300 °C. However, other physicochemical properties of the samples varied depending on the symmetry of the alcohols used. For the catalytic oxidation of CO, MnO2 catalysts prepared with 1° alcohols performed better than the samples prepared in 2° alcohols. Catalytic activities were correlated to the quantity of labile oxygen species of the catalysts. In CO-TPD analysis, the relative area of desorbed radical dotCO2, which is the product of the reaction between adsorbed CO and lattice oxygen species, becomes larger for MnO2 prepared with 1° alcohols than with 2° alcohols. These results were primarily resulted from the innate hydrogen dissociation behavior of alcohol in solution. The pKa was found to be an important factor in determining the physicochemical properties and catalytic activity toward CO oxidation of MnO2.

  6. Physicochemical properties of manganese dioxide synthesized using C2–C5 alcohols as reducing agents and their catalytic activities for CO oxidation

    KAUST Repository

    Lee, Young-Ho; Park, Jung-Hyun; Shin, Chae-Ho

    2015-01-01

    MnO2 catalysts were synthesized in an aqueous solution of KMnO4 and C2–C5 alcohols using a simple redox method at room temperature. The crystalline structure of all samples was δ-MnO2 after being calcined at 300 °C. However, other physicochemical properties of the samples varied depending on the symmetry of the alcohols used. For the catalytic oxidation of CO, MnO2 catalysts prepared with 1° alcohols performed better than the samples prepared in 2° alcohols. Catalytic activities were correlated to the quantity of labile oxygen species of the catalysts. In CO-TPD analysis, the relative area of desorbed radical dotCO2, which is the product of the reaction between adsorbed CO and lattice oxygen species, becomes larger for MnO2 prepared with 1° alcohols than with 2° alcohols. These results were primarily resulted from the innate hydrogen dissociation behavior of alcohol in solution. The pKa was found to be an important factor in determining the physicochemical properties and catalytic activity toward CO oxidation of MnO2.

  7. Complete genome sequence of the aerobic CO-oxidizing thermophile Thermomicrobium roseum.

    Directory of Open Access Journals (Sweden)

    Dongying Wu

    Full Text Available In order to enrich the phylogenetic diversity represented in the available sequenced bacterial genomes and as part of an "Assembling the Tree of Life" project, we determined the genome sequence of Thermomicrobium roseum DSM 5159. T. roseum DSM 5159 is a red-pigmented, rod-shaped, Gram-negative extreme thermophile isolated from a hot spring that possesses both an atypical cell wall composition and an unusual cell membrane that is composed entirely of long-chain 1,2-diols. Its genome is composed of two circular DNA elements, one of 2,006,217 bp (referred to as the chromosome and one of 919,596 bp (referred to as the megaplasmid. Strikingly, though few standard housekeeping genes are found on the megaplasmid, it does encode a complete system for chemotaxis including both chemosensory components and an entire flagellar apparatus. This is the first known example of a complete flagellar system being encoded on a plasmid and suggests a straightforward means for lateral transfer of flagellum-based motility. Phylogenomic analyses support the recent rRNA-based analyses that led to T. roseum being removed from the phylum Thermomicrobia and assigned to the phylum Chloroflexi. Because T. roseum is a deep-branching member of this phylum, analysis of its genome provides insights into the evolution of the Chloroflexi. In addition, even though this species is not photosynthetic, analysis of the genome provides some insight into the origins of photosynthesis in the Chloroflexi. Metabolic pathway reconstructions and experimental studies revealed new aspects of the biology of this species. For example, we present evidence that T. roseum oxidizes CO aerobically, making it the first thermophile known to do so. In addition, we propose that glycosylation of its carotenoids plays a crucial role in the adaptation of the cell membrane to this bacterium's thermophilic lifestyle. Analyses of published metagenomic sequences from two hot springs similar to the one from which

  8. Synthesis of MnFe2O4@Mn-Co oxide core-shell nanoparticles and their excellent performance for heavy metal removal.

    Science.gov (United States)

    Ma, Zichuan; Zhao, Dongyuan; Chang, Yongfang; Xing, Shengtao; Wu, Yinsu; Gao, Yuanzhe

    2013-10-21

    Magnetic nanomaterials that can be easily separated and recycled due to their magnetic properties have received considerable attention in the field of water treatment. However, these nanomaterials usually tend to aggregate and alter their properties. Herein, we report an economical and environmentally friendly method for the synthesis of magnetic nanoparticles with core-shell structure. MnFe2O4 nanoparticles have been successfully coated with amorphous Mn-Co oxide shells. The synthesized MnFe2O4@Mn-Co oxide nanoparticles have highly negatively charged surface in aqueous solution over a wide pH range, thus preventing their aggregation and enhancing their performance for heavy metal cation removal. The adsorption isotherms are well fitted to a Langmuir adsorption model, and the maximal adsorption capacities of Pb(II), Cu(II) and Cd(II) on MnFe2O4@Mn-Co oxide are 481.2, 386.2 and 345.5 mg g(-1), respectively. All the metal ions can be completely removed from the mixed metal ion solutions in a short time. Desorption studies confirm that the adsorbent can be effectively regenerated and reused.

  9. Spectroscopic identification of the active site for CO oxidation on Rh/Al{sub 2}O{sub 3} by concentration modulation in situ DRIFTS

    Energy Technology Data Exchange (ETDEWEB)

    Cavers, M.; Davidson, J.M.; Harkness, I.R.; Rees, L.V.C.; McDougall, G.S.

    1999-12-10

    Diffuse reflectance infrared spectroscopy experiments are described in which the concentrations of the reactant gases passing over a solid catalyst are modulated. This simple modification to the normal in situ experiment enables direct correlation of specific surface species with the production of gaseous products. Spectra of solely the active surface intermediates with no contribution from so called spectator species are generated. For CO oxidation over a Rh/alumina catalyst at 576 K, the active CO species is identified as linearly adsorbed CO on oxidized Rh sites ({nu}{sub CO} = 2,100 cm{sup {minus}1}) on a catalyst surface apparently otherwise dominated by CO adsorbed as unreactive geminal dicarbonyl.

  10. Realistic multisite lattice-gas modeling and KMC simulation of catalytic surface reactions: Kinetics and multiscale spatial behavior for CO-oxidation on metal (1 0 0) surfaces

    Science.gov (United States)

    Liu, Da-Jiang; Evans, James W.

    2013-12-01

    A realistic molecular-level description of catalytic reactions on single-crystal metal surfaces can be provided by stochastic multisite lattice-gas (msLG) models. This approach has general applicability, although in this report, we will focus on the example of CO-oxidation on the unreconstructed fcc metal (1 0 0) or M(1 0 0) surfaces of common catalyst metals M = Pd, Rh, Pt and Ir (i.e., avoiding regimes where Pt and Ir reconstruct). These models can capture the thermodynamics and kinetics of adsorbed layers for the individual reactants species, such as CO/M(1 0 0) and O/M(1 0 0), as well as the interaction and reaction between different reactant species in mixed adlayers, such as (CO + O)/M(1 0 0). The msLG models allow population of any of hollow, bridge, and top sites. This enables a more flexible and realistic description of adsorption and adlayer ordering, as well as of reaction configurations and configuration-dependent barriers. Adspecies adsorption and interaction energies, as well as barriers for various processes, constitute key model input. The choice of these energies is guided by experimental observations, as well as by extensive Density Functional Theory analysis. Model behavior is assessed via Kinetic Monte Carlo (KMC) simulation. We also address the simulation challenges and theoretical ramifications associated with very rapid diffusion and local equilibration of reactant adspecies such as CO. These msLG models are applied to describe adsorption, ordering, and temperature programmed desorption (TPD) for individual CO/M(1 0 0) and O/M(1 0 0) reactant adlayers. In addition, they are also applied to predict mixed (CO + O)/M(1 0 0) adlayer structure on the nanoscale, the complete bifurcation diagram for reactive steady-states under continuous flow conditions, temperature programmed reaction (TPR) spectra, and titration reactions for the CO-oxidation reaction. Extensive and reasonably successful comparison of model predictions is made with experimental

  11. Aluminum Wire Meshes Coated with Co-Mn-Al and Co Oxides as Catalysts for Deep Ethanol Oxidation.

    Czech Academy of Sciences Publication Activity Database

    Jirátová, Květa; Kovanda, F.; Balabánová, Jana; Kšírová, P.

    2018-01-01

    Roč. 304, SI (2018), s. 165-171 ISSN 0920-5861. [Czech-Italian-Spanish Symposium in Catalysis /7./. Třešť, 13.06.2017-17.06.2017] R&D Projects: GA ČR GA17-08389S Institutional support: RVO:67985858 Keywords : GA17-08389S * Co-Mn-Al mixed oxides * aluminum mesh Subject RIV: CI - Industrial Chemistry, Chemical Engineering OBOR OECD: Chemical process engineering Impact factor: 4.636, year: 2016

  12. Mathematical modeling of synthesis gas fueled electrochemistry and transport including H2/CO co-oxidation and surface diffusion in solid oxide fuel cell

    Science.gov (United States)

    Bao, Cheng; Jiang, Zeyi; Zhang, Xinxin

    2015-10-01

    Fuel flexibility is a significant advantage of solid oxide fuel cell (SOFC). A comprehensive macroscopic framework is proposed for synthesis gas (syngas) fueled electrochemistry and transport in SOFC anode with two main novelties, i.e. analytical H2/CO electrochemical co-oxidation, and correction of gas species concentration at triple phase boundary considering competitive absorption and surface diffusion. Staring from analytical approximation of the decoupled charge and mass transfer, we present analytical solutions of two defined variables, i.e. hydrogen current fraction and enhancement factor. Giving explicit answer (rather than case-by-case numerical calculation) on how many percent of the current output contributed by H2 or CO and on how great the water gas shift reaction plays role on, this approach establishes at the first time an adaptive superposition mechanism of H2-fuel and CO-fuel electrochemistry for syngas fuel. Based on the diffusion equivalent circuit model, assuming series-connected resistances of surface diffusion and bulk diffusion, the model predicts well at high fuel utilization by keeping fixed porosity/tortuosity ratio. The model has been validated by experimental polarization behaviors in a wide range of operation on a button cell for H2-H2O-CO-CO2-N2 fuel systems. The framework could be helpful to narrow the gap between macro-scale and meso-scale SOFC modeling.

  13. Use of periodic variations of reactant concentrations in time resolved ftir studies of CO oxidation on Pd/ZrO{sub 2} catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Ortelli, E; Wokaun, A [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    Sine wave modulation of feed concentrations was used to induce dynamic variations in the concentrations of products, intermediates and reactants, which were monitored in a diffuse reflectance FTIR (DRIFT) cell. The phase shift {Delta}{phi} between the external perturbation of the feed and the signals of products, intermediates and reactants was examined in dependence on the modulation frequency {omega}. Reaction constants of a simplified model mechanism were estimated for a Pd{sub 25}Zr{sub 75} based catalyst for CO oxidation. (author) 1 fig., 2 refs.

  14. Confined Catalysis in the g-C3N4/Pt(111) Interface: Feasible Molecule Intercalation, Tunable Molecule-Metal Interaction, and Enhanced Reaction Activity of CO Oxidation.

    Science.gov (United States)

    Wang, Shujiao; Feng, Yingxin; Yu, Ming'an; Wan, Qiang; Lin, Sen

    2017-09-27

    The deposition of a two-dimensional (2D) atomic nanosheet on a metal surface has been considered as a new route for tuning the molecule-metal interaction and surface reactivity in terms of the confinement effect. In this work, we use first-principles calculations to systematically explore a novel nanospace constructed by placing a 2D graphitic carbon nitride (g-C 3 N 4 ) nanosheet over a Pt(111) surface. The confined catalytic activity in this nanospace is investigated using CO oxidation as a model reaction. With the inherent triangular pores in the g-C 3 N 4 overlayer being taken advantage of, molecules such as CO and O 2 can diffuse to adsorb on the Pt(111) surface underneath the g-C 3 N 4 overlayer. Moreover, the mechanism of intercalation is also elucidated, and the results reveal that the energy barrier depends mainly on the properties of the molecule and the channel. Importantly, the molecule-catalyst interaction can be tuned by the g-C 3 N 4 overlayer, considerably reducing the adsorption energy of CO on Pt(111) and leading to enhanced reactivity in CO oxidation. This work will provide important insight for constructing a promising nanoreactor in which the following is observed: The molecule intercalation is facile; the molecule-metal interaction is efficiently tuned; the metal-catalyzed reaction is promoted.

  15. Shape and catalytic mechanism of RuO{sub 2} particles at CO oxidation reaction conditions. First-principles based multi-scale modeling

    Energy Technology Data Exchange (ETDEWEB)

    Reuter, Karsten [TU Muenchen (Germany). Lehrstuhl fuer Theoretische Chemie

    2016-11-01

    For model catalyst studies on low-index single-crystal surfaces close agreement between detailed measurements and quantitative microkinetic modeling can increasingly be achieved. However, for 'real' catalyst particles, such structure-morphology-activity relationships are only scarcely established. This is prototypically reflected by the situation for RuO{sub 2}, as a most active catalyst for CO oxidation. Here, existing first-principles kinetic modeling is restricted to just one facet, namely the RuO{sub 2}(110) surface, which is not able to fully account for activity data obtained from polycrystalline RuO{sub 2} powder catalysts. The overarching objective of this project was correspondingly to close this gap and demonstrate that similarly close agreement as for individual single-crystal model catalysts can also be achieved for catalyst particles. Specifically, we addressed experiments where an intact RuO{sub 2} bulk structure is conserved, and establish the atomic-scale structure and reactivity of other RuO{sub 2} low-index facets under the gas-phase conditions characteristic for catalytic CO oxidation.

  16. Formation of polyhedral ceria nanoparticles with enhanced catalytic CO oxidation activity in thermal plasma via a hydrogen mediated shape control mechanism

    International Nuclear Information System (INIS)

    Zheng Jie; Zhang Yaohua; Song Xubo; Li Xingguo

    2011-01-01

    Ceria nanoparticles with well defined facets are prepared in argon–hydrogen thermal plasma followed by controlled oxidation. With increasing hydrogen fraction in the plasma, a clear sphere-to-polyhedron shape transition is observed. The heat released during the hydrogenation of cerium, which significantly enhances the species mobility on the surface, favors the growth of well defined facets. The polyhedron ceria nanoparticles, though lower in specific surface area, exhibit superior catalytic performance for CO oxidation over the round particles, which is attributed to the higher density of the reactive {200} and {220} facets on the surface. The hydrogen mediated shape control mechanism provides new insights into the shape control of nanoparticles during thermal plasma processing.

  17. The effect of defects on the catalytic activity of single Au atom supported carbon nanotubes and reaction mechanism for CO oxidation.

    Science.gov (United States)

    Ali, Sajjad; Fu Liu, Tian; Lian, Zan; Li, Bo; Sheng Su, Dang

    2017-08-23

    The mechanism of CO oxidation by O 2 on a single Au atom supported on pristine, mono atom vacancy (m), di atom vacancy (di) and the Stone Wales defect (SW) on single walled carbon nanotube (SWCNT) surface is systematically investigated theoretically using density functional theory. We determine that single Au atoms can be trapped effectively by the defects on SWCNTs. The defects on SWCNTs can enhance both the binding strength and catalytic activity of the supported single Au atom. Fundamental aspects such as adsorption energy and charge transfer are elucidated to analyze the adsorption properties of CO and O 2 and co-adsorption of CO and O 2 molecules. It is found that CO binds stronger than O 2 on Au supported SWCNT. We clearly demonstrate that the defected SWCNT surface promotes electron transfer from the supported single Au atom to O 2 molecules. On the other hand, this effect is weaker for pristine SWCNTs. It is observed that the high density of spin-polarized states are localized in the region of the Fermi level due to the strong interactions between Au (5d orbital) and the adjacent carbon (2p orbital) atoms, which influence the catalytic performance. In addition, we elucidate both the Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms of CO oxidation by O 2 . For the LH pathway, the barriers of the rate-limiting step are calculated to be 0.02 eV and 0.05 eV for Au/m-SWCNT and Au/di-SWCNT, respectively. To regenerate the active sites, an ER-like reaction occurs to form a second CO 2 molecule. The ER pathway is observed on Au/m-SWCNT, Au/SW-SWCNT and Au/SWCNT in which the Au/m-SWCNT has a smaller barrier. The comparison with a previous study (Lu et al., J. Phys. Chem. C, 2009, 113, 20156-20160.) indicates that the curvature effect of SWCNTs is important for the catalytic property of the supported single Au. Overall, Au/m-SWCNT is identified as the most active catalyst for CO oxidation compared to pristine SWCNT, SW-SWCNT and di-SWCNT. Our findings give a

  18. The influences of microwave irradiation and polyol precursor pH on Cu/AC catalyst and its CO oxidation performance

    Science.gov (United States)

    Chuang, Kui-Hao; Shih, Kaimin; Wey, Ming-Yen

    2012-10-01

    This study evaluated the effects of microwave irradiation parameters and the pH of the polyol precursor on the morphological features and catalytic performances of Cu/activated carbon (AC) catalysts. Experimental results of carbon monoxide (CO) oxidation indicated that the highest catalytic activity is achieved when the Cu/AC catalyst is prepared with microwave irradiation at 700 W for 60 s. Scanning electron microscopy revealed the presence of beneficial small copper aciculae on the Cu/AC catalyst under such a microwave irradiation scheme. Further investigation of operational parameters found that the performance of Cu/AC catalysts is enhanced by adopting a pH = 12 polyol precursor solution. With the observation that small cube copper ( 16 nm) aggregates form when a pH = 12 polyol precursor solution is used, this study also demonstrated the importance of controlling the morphology of metal nanoparticles on Cu/AC catalysts when using the microwave-assisted polyol method.

  19. The influences of microwave irradiation and polyol precursor pH on Cu/AC catalyst and its CO oxidation performance

    International Nuclear Information System (INIS)

    Chuang, Kui-Hao; Shih, Kaimin; Wey, Ming-Yen

    2012-01-01

    This study evaluated the effects of microwave irradiation parameters and the pH of the polyol precursor on the morphological features and catalytic performances of Cu/activated carbon (AC) catalysts. Experimental results of carbon monoxide (CO) oxidation indicated that the highest catalytic activity is achieved when the Cu/AC catalyst is prepared with microwave irradiation at 700 W for 60 s. Scanning electron microscopy revealed the presence of beneficial small copper aciculae on the Cu/AC catalyst under such a microwave irradiation scheme. Further investigation of operational parameters found that the performance of Cu/AC catalysts is enhanced by adopting a pH = 12 polyol precursor solution. With the observation that small cube copper (∼16 nm) aggregates form when a pH = 12 polyol precursor solution is used, this study also demonstrated the importance of controlling the morphology of metal nanoparticles on Cu/AC catalysts when using the microwave-assisted polyol method.

  20. Influence of natural convection and diluent inerting on H2 and CO oxidation in the reactor cavity

    International Nuclear Information System (INIS)

    Wong, C.C.

    1988-01-01

    The question of complete in-cavity oxidation of combustible gases produced by core-concrete interactions following vessel breach has been investigated. It is overly optimistic to assume a complete oxidation because a variety of phenomena, such as steam inerting and oxygen transport by natural convection, may influence the degree of in-cavity oxidation that takes place. HECTR analyses of an ice-condenser containment during an S2HF drain-closed accident show that the in-cavity oxidation process is limited by the rate at which oxygen is transported into the reactor cavity region. Accumulation and subsequent combustion of hydrogen and carbon monoxide in the upper and lower compartments generate a peak pressure of 384 kPa (56 psig) at 7.4 h, that an earlier IDCOR analysis did not predict. (orig.)

  1. Sucrose-assisted synthesis of three-dimensionally ordered macroporous CeO{sub 2} and its use as a support for promotional catalytic performance of CO oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Zhi, E-mail: zhiliu@lnnu.edu.cn; Tan, Xiuli; Lv, Cong

    2013-10-15

    In this work, several three-dimensionally ordered macroporous (3DOM) CeO{sub 2} having hierarchical pore structure were successfully prepared via a dual ‘hard-soft’ templating strategy using Ce(NO{sub 3}){sub 3}·6H{sub 2}O containing sucrose as the ceria precursor. The resulting CeO{sub 2} samples were characterized by N{sub 2} adsorption–desorption analysis, scanning electron microscopy, and transmission electron microscopy, which showed that the hierarchical 3DOM CeO{sub 2} possessed interconnected networks of the ordered macropore structures with large mesopores, and both the BET surface area and pore volume increased significantly compared with the conventional 3DOM CeO{sub 2}. The content of sucrose had a great effect on the textural parameters of the 3DOM CeO{sub 2}. The improved textural parameters should be attributed to the emergence of mesopores in the interconnected three-dimensional skeleton, which were formed by oxidative removal of carbon produced from carbonization of sucrose. The hierarchical 3DOM CeO{sub 2} exhibited a superior performance to the conventional 3DOM or bulk CeO{sub 2} when used as supports for Ir catalysts in CO oxidation.

  2. Density functional theoretical study on the C-F and C-O oxidative addition reaction at an AI center

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Yong Seong [Dept. of Science Education, Kyungnam University, Masan (Korea, Republic of); Cho, Hyun; Hwang, Sungu [Dept. of Nanomechatronics Engineering, Pusan National University, Miryang (Korea, Republic of)

    2017-02-15

    In this study, B3LYP/LACVP** level calculations were chosen because the level of theory was applied successfully to calculations of the thermodynamic and kinetic features of the oxidative addition reactions of alkyl and aryl halides to pincer-type complexes. This study examined the effects of the substituents on the phenyl rings of the Al(I) center. Isopropyl side chains in the phenyl rings attached to N atoms of the pincer ligand were replaced with a methyl (Me) (2) or tertiary butyl ( t Bu) group. The oxidative addition of C[BOND]F and C[BOND]O bonds to an Al (I) center was investigated computationally by DFT calculations. The geometries, thermodynamic, and kinetic features were in good agreement with the experimental data, as in previous studies on the transition metal complexes. The computational results showed that the DFT calculations could provide qualitative insight into the reactivity and thermodynamics of the oxidative addition reactions of C[BOND]F bonds.

  3. Determination of the apparent transfer coefficient for CO oxidation on Pt(poly), Pt(111), Pt(665) and Pt(332) using a potential modulation technique.

    Science.gov (United States)

    Wang, Han-Chun; Ernst, Siegfried; Baltruschat, Helmut

    2010-03-07

    The apparent transfer coefficient, which gives the magnitude of the potential dependence of the electrochemical reaction rates, is the key quantity for the elucidation of electrochemical reaction mechanisms. We introduce the application of an ac method to determine the apparent transfer coefficient alpha' for the oxidation of pre-adsorbed CO at polycrystalline and single-crystalline Pt electrodes in sulfuric acid. The method allows to record alpha' quasi continuously as a function of potential (and time) in cyclic voltammetry or at a fixed potential, with the reaction rate varying with time. At all surfaces (Pt(poly), Pt(111), Pt(665), and Pt(332)) we clearly observed a transition of the apparent transfer coefficient from values around 1.5 at low potentials to values around 0.5 at higher potentials. Changes of the apparent transfer coefficients for the CO oxidation with potential were observed previously, but only from around 0.7 to values as low as 0.2. In contrast, our experimental findings completely agree with the simulation by Koper et al., J. Chem. Phys., 1998, 109, 6051-6062. They can be understood in the framework of a Langmuir-Hinshelwood mechanism. The transition occurs when the sum of the rate constants for the forward reaction (first step: potential dependent OH adsorption, second step: potential dependent oxidation of CO(ad) with OH(ad)) exceeds the rate constant for the back-reaction of the first step. We expect that the ac method for the determination of the apparent transfer coefficient, which we used here, will be of great help also in many other cases, especially under steady conditions, where the major limitations of the method are avoided.

  4. Understanding Catalytic Activity Trends for NO Decomposition and CO Oxidation using Density Functional Theory and Microkinetic Modeling

    DEFF Research Database (Denmark)

    Falsig, Hanne

    -metal surfaces by combining a database of adsorption energies on stepped metal surfaces with known Brønsted–Evans–Polanyi (BEP) relations for the activation barriers of dissociation of diatomic molecules over stepped transition- and noble-metal surfaces. The potential energy diagram directly points to why Pd......The main aim of this thesis is to understand the catalytic activity of transition metals and noble metals for the direct decomposition of NO and the oxidation of CO. The formation of NOx from combustion of fossil and renewable fuels continues to be a dominant environmental issue. We take one step...... towards rationalizing trends in catalytic activity of transition metal catalysts for NO decomposition by combining microkinetic modelling with density functional theory calculations. We establish the full potential energy diagram for the direct NO decomposition reaction over stepped transition...

  5. Effect of сopper сoating on fibers made of aluminum alloy, titanium, and FeCrAl alloy on surface morphology and activity in CO oxidation

    Science.gov (United States)

    Lukiyanchuk, I. V.; Rudnev, V. S.; Serov, M. M.; Krit, B. L.; Lukiyanchuk, G. D.; Nedozorov, P. M.

    2018-04-01

    The catalytic activity of both copper fibers and copper-coated fibers of a diameter of 50-100 μm made of aluminum alloy, technical grade titanium, and FeCrAl alloy in CO oxidation has been estimated. Metal fibers have been fabricated by the method of pendant drop melt extraction (PDME). The fibers copper plating was carried out by chemical and electrochemical methods. The composition and structure of samples and coatings before and after catalytic tests have been characterized by the methods of scanning electron microscopy, energy-dispersive analysis, and X-ray fluorescence analysis. It has been shown that the catalytic activity of copper-coated fibers made of FeCrAl alloy in the reaction of CO oxidation is not inferior to that of copper fibers.

  6. Influence of foreign cations (Zr4+, La3+, Pr3+ and Sm3+) on CuO-CeO2: microwave induced solution combustion synthesis, characterization and CO oxidation activity

    International Nuclear Information System (INIS)

    Reddy, Lankela H.; Devaiah, D.; Jampaiah, D.; Venkata Swamy, P.; Reddy, Benjaram M.

    2012-01-01

    Carbon monoxide treatment by catalytic oxidation, such as water-gas-shift reaction (WGSR), preferential oxidation of CO in H 2 rich streams (PROX) and its simple oxidation have received a great attention by the scientific community. The noble metal-based nanocomposites have proven to be the highly effective candidates towards the CO oxidation. However, some of the disadvantages associated with the noble metals leads to an extensive search for alternative materials. In recent years, copper-cerium based mixed oxides have received much attention because they are inexpensive, environmentally benign and can be prepared easily. Therefore, the present study was aimed at developing a new class of copper promoted metal doped CeO 2 catalysts using microwave-assisted combustion method

  7. Oxidation reaction of 4-allyl-4-hydroperoxy-2-methoxycyclohexa-2,5-dienone in the presence of potassium permanganate without a co-oxidant

    Directory of Open Access Journals (Sweden)

    Mehmet Serdar Gültekin

    2016-12-01

    Full Text Available 4-Allyl-4-hydroperoxy-2-methoxycyclohexa-2,5-dienone (5 was synthesized by photooxygenation of commercially available Eugenol in the presence of tetraphenylporphyrin (TPP as a singlet oxygen sensitizer. The brief and one-pot syntheses of some natural product skeletons were conducted using the corresponding allylic hydroperoxide at different temperatures (0 oC and room temperature with potassium permanganate (KMnO 4 in mild condition at N 2(g atm.

  8. Kinetic Studies on the Oxidation of Some para and meta-Substituted Cinnamic Acids by Pyridinium Bromochromate in the Presence of Oxalic Acid (A Co-oxidation Study

    Directory of Open Access Journals (Sweden)

    G. Vanangamudi

    2009-01-01

    Full Text Available The kinetics of oxidation of cinnamic acids by pyridinium bromochromate (PBC in the presence of oxalic acid has been studied in acetic acid-water (60:40% medium. The reaction shows unit order dependence each with respect to oxidant as well as oxalic acid [OX], the order with respect to [H+] and [CA] are fractional. The reaction is acid catalyzed and a low dielectric constant favours the reaction. Increase the ionic strength has no effect on the reaction rate. In the case of substituted cinnamic acids the order with respect to substrate vary depending upon the nature of the substituent present in the ring. In general, the electron withdrawing substituents retard the rate while the electron releasing substituents enhance the rate of reaction. From the kinetic data obtained the activation parameters have been computed and a suitable mechanism has been proposed.

  9. Production of nitrous oxide from anaerobic digester centrate and its use as a co-oxidant of biogas to enhance energy recovery.

    Science.gov (United States)

    Scherson, Yaniv D; Woo, Sung-Geun; Criddle, Craig S

    2014-05-20

    Coupled Aerobic-anoxic Nitrous Decomposition Operation (CANDO) is a new process for wastewater treatment that removes nitrogen from wastewater and recovers energy from the nitrogen in three steps: (1) NH4(+) oxidation to NO2(-); (2) NO2(-) reduction to N2O gas; and (3) N2O conversion to N2 with energy production. In this work, we optimize Steps 1 and 2 for anaerobic digester centrate, and we evaluate Step 3 for a full-scale biogas-fed internal combustion engine. Using a continuous stirred reactor coupled to a bench-scale sequencing batch reactor, we observed sustained partial oxidation of NH4(+) to NO2(-) and sustained (3 months) partial reduction of NO2(-) to N2O (75-80% conversion, mass basis), with >95% nitrogen removal (Step 2). Alternating pulses of acetate and NO2(-) selected for Comamonas (38%), Ciceribacter (16%), and Clostridium (11%). Some species stored polyhydroxybutyrate (PHB) and coupled oxidation of PHB to reduction of NO2(-) to N2O. Some species also stored phosphorus as polyphosphate granules. Injections of N2O into a biogas-fed engine at flow rates simulating a full-scale system increased power output by 5.7-7.3%. The results underscore the need for more detailed assessment of bioreactor community ecology and justify pilot- and full-scale testing.

  10. Generation and reactivity of putative support systems, Ce-Al neutral binary oxide nanoclusters: CO oxidation and C-H bond activation

    Science.gov (United States)

    Wang, Zhe-Chen; Yin, Shi; Bernstein, Elliot R.

    2013-11-01

    Both ceria (CeO2) and alumina (Al2O3) are very important catalyst support materials. Neutral binary oxide nanoclusters (NBONCs), CexAlyOz, are generated and detected in the gas phase and their reactivity with carbon monoxide (CO) and butane (C4H10) is studied. The very active species CeAlO4• can react with CO and butane via O atom transfer (OAT) and H atom transfer (HAT), respectively. Other CexAlyOz NBONCs do not show reactivities toward CO and C4H10. The structures, as well as the reactivities, of CexAlyOz NBONCs are studied theoretically employing density functional theory (DFT) calculations. The ground state CeAlO4• NBONC possesses a kite-shaped structure with an OtCeObObAlOt configuration (Ot, terminal oxygen; Ob, bridging oxygen). An unpaired electron is localized on the Ot atom of the AlOt moiety rather than the CeOt moiety: this Ot centered radical moiety plays a very important role for the reactivity of the CeAlO4• NBONC. The reactivities of Ce2O4, CeAlO4•, and Al2O4 toward CO are compared, emphasizing the importance of a spin-localized terminal oxygen for these reactions. Intramolecular charge distributions do not appear to play a role in the reactivities of these neutral clusters, but could be important for charged isoelectronic BONCs. DFT studies show that the reaction of CeAlO4• with C4H10 to form the CeAlO4H•C4H9• encounter complex is barrierless. While HAT processes have been previously characterized for cationic and anionic oxide clusters, the reported study is the first observation of a HAT process supported by a ground state neutral oxide cluster. Mechanisms for catalytic oxidation of CO over surfaces of AlxOy/MmOn or MmOn/AlxOy materials are proposed consistent with the presented experimental and theoretical results.

  11. Synthesis and microstructure of La_1_−_xCa_xCoO_3 nanoparticles and their catalytic activity for CO oxidation

    International Nuclear Information System (INIS)

    Luu, Tien Hung; Nguyen, Xuan Dung; Phan, Thi Minh Huyen; Schulze, Steffen; Hietschold, Michael

    2015-01-01

    Perovskite nanoparticles of La_1_−_xCa_xCoO_3 (x = 0, 0.2, 0.3, 0.5) were synthesized by the combustion method using polyvinyl alcohol (PVA) and corresponding metal nitrates. Microstructure of samples was characterized by high resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) combined with x-ray diffraction (XRD). The nanoparticles were characterized by thermogravimetric and differential thermal analysis (TG-DTA) and BET (Brunauer–Emmet–Teller). A high surface area (15–21 m"2 g"−"1) at low temperature (600 °C) of samples was obtained. The optimal preparative conditions were PVA/metals 2:1 by mole, pH = 3 and 80 °C for gel formation. Perovskites exhibit a good catalytic activity in total oxidation of CO at the low temperature (<250 °C) of reaction. (paper)

  12. Yolk-shell gold nanoparticles as model materials for support-effect studies in heterogeneous catalysis: Au, @C and Au, @ZrO2 for CO oxidation as an example.

    Science.gov (United States)

    Galeano, Carolina; Güttel, Robert; Paul, Michael; Arnal, Pablo; Lu, An-Hui; Schüth, Ferdi

    2011-07-18

    The use of nanostructured yolk-shell materials offers a way to discriminate support and particle-size effects for mechanistic studies in heterogeneous catalysis. Herein, gold yolk-shell materials have been synthesized and used as model catalysts for the investigation of support effects in CO oxidation. Carbon has been selected as catalytically inert support to study the intrinsic activity of the gold nanoparticles, and for comparison, zirconia has been used as oxidic support. Au, @C materials have been synthesized through nanocasting using two different nonporous-core@mesoporous-shell exotemplates: Au@SiO(2)@ZrO(2) and Au@SiO(2)@m-SiO(2). The catalytic activity of Au, @C with a gold core of about 14 nm has been evaluated and compared with Au, @ZrO(2) of the same gold core size. The strong positive effect of metal oxide as support material on the activity of gold has been proved. Additionally, size effects were investigated using carbon as support to determine only the contribution of the nanoparticle size on the catalytic activity of gold. Therefore, Au, @C with a gold core of about 7 nm was studied showing a less pronounced positive effect on the activity than the metal oxide support effect. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Inhibition of ammonia poisoning by addition of platinum to Ru/α-Al2 O3 for preferential CO oxidation in fuel cells.

    Science.gov (United States)

    Sato, Katsutoshi; Yagi, Sho; Zaitsu, Shuhei; Kitayama, Godai; Kayada, Yuto; Teramura, Kentaro; Takita, Yusaku; Nagaoka, Katsutoshi

    2014-12-01

    In polymer electrolyte fuel cell (PEFC) systems, small amounts of ammonia (NH3 ) present in the reformate gas deactivate the supported ruthenium catalysts used for preferential oxidation (PROX) of carbon monoxide (CO). In this study, we investigated how the addition of a small amount of platinum to a Ru/α-Al2 O3 catalyst (Pt/Ru=1:9 w/w) affected the catalyst's PROX activity in both the absence and the presence of NH3 (130 ppm) under conditions mimicking the reformate conditions during steam reforming of natural gas. The activity of undoped Ru/α-Al2 O3 decreased sharply upon addition of NH3 , whereas Pt/Ru/α-Al2 O3 exhibited excellent PROX activity even in the presence of NH3 . Ruthenium K-edge X-ray absorption near-edge structure (XANES) spectra indicated that in the presence of NH3 , some of the ruthenium in the undoped catalyst was oxidized in the presence of NH3 , whereas ruthenium oxidation was not observed with Pt/Ru/α-Al2 O3 . These results suggest that ruthenium oxidation is retarded by the platinum, so that the catalyst shows high activity even in the presence of NH3 . © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Synthesis of pigments of Fe2O3·SiO2 system, with Ca, Mg, or Co oxide additions

    Directory of Open Access Journals (Sweden)

    Tsvetan Dimitrov

    2017-03-01

    Full Text Available The present research work is based on the comparative evaluation of the Ca, Mg, and Co dopant impact on the properties of new ceramic pigments from the system Fe2O3·SiO2 obtained via classical ceramic technology. This approach enabled determination of the optimal temperature for the synthesis and the most appropriate mineralizer. The obtained specimens were submitted to systematical analysis, including X-ray Diffraction (XRD spectroscopy, Electron Paramagnetic Resonance (EPR analysis and Mössbauer spectroscopy for crystalline phase determination. The color characteristics are quantified by spectrophotometric measurements. The pigments particle size has been determined by Scanning Electron Microscopy (SEM, combined by Energy Dispersion X-ray spectroscopy (EDX. The obtained results enabled to determine the correlation between the calcination temperature and the phase compositions of the obtained pigments. In addition, some interesting magnetic properties were detected for the Co-doped composition.

  15. Synthesis of pigments of Fe2O3·SiO2 system, with Ca, Mg, or Co oxide additions

    Energy Technology Data Exchange (ETDEWEB)

    Dimitrov, T.; Kozhukharov, S.; Velinov, N.

    2017-07-01

    The present research work is based on the comparative evaluation of the Ca, Mg, and Co dopant impact on the properties of new ceramic pigments from the system Fe2O3·SiO2 obtained via classical ceramic technology. This approach enabled determination of the optimal temperature for the synthesis and the most appropriate mineralizer. The obtained specimens were submitted to systematical analysis, including X-ray Diffraction (XRD) spectroscopy, Electron Paramagnetic Resonance (EPR) analysis and Mössbauer spectroscopy for crystalline phase determination. The color characteristics are quantified by spectrophotometric measurements. The pigments particle size has been determined by Scanning Electron Microscopy (SEM), combined by Energy Dispersion X-ray spectroscopy (EDX). The obtained results enabled to determine the correlation between the calcination temperature and the phase compositions of the obtained pigments. In addition, some interesting magnetic properties were detected for the Co-doped composition. (Author)

  16. High temperature oxidation resistant cermet compositions

    Science.gov (United States)

    Phillips, W. M. (Inventor)

    1976-01-01

    Cermet compositions are designed to provide high temperature resistant refractory coatings on stainless steel or molybdenum substrates. A ceramic mixture of chromium oxide and aluminum oxide form a coating of chromium oxide as an oxidation barrier around the metal particles, to provide oxidation resistance for the metal particles.

  17. 1D Ni-Co oxide and sulfide nanoarray/carbon aerogel hybrid nanostructures for asymmetric supercapacitors with high energy density and excellent cycling stability.

    Science.gov (United States)

    Hao, Pin; Tian, Jian; Sang, Yuanhua; Tuan, Chia-Chi; Cui, Guanwei; Shi, Xifeng; Wong, C P; Tang, Bo; Liu, Hong

    2016-09-15

    The fabrication of supercapacitor electrodes with high energy density and excellent cycling stability is still a great challenge. A carbon aerogel, possessing a hierarchical porous structure, high specific surface area and electrical conductivity, is an ideal backbone to support transition metal oxides and bring hope to prepare electrodes with high energy density and excellent cycling stability. Therefore, NiCo 2 S 4 nanotube array/carbon aerogel and NiCo 2 O 4 nanoneedle array/carbon aerogel hybrid supercapacitor electrode materials were synthesized by assembling Ni-Co precursor needle arrays on the surface of the channel walls of hierarchical porous carbon aerogels derived from chitosan in this study. The 1D nanostructures grow on the channel surface of the carbon aerogel vertically and tightly, contributing to the enhanced electrochemical performance with ultrahigh energy density. The energy density of NiCo 2 S 4 nanotube array/carbon aerogel and NiCo 2 O 4 nanoneedle array/carbon aerogel hybrid asymmetric supercapacitors can reach up to 55.3 Wh kg -1 and 47.5 Wh kg -1 at a power density of 400 W kg -1 , respectively. These asymmetric devices also displayed excellent cycling stability with a capacitance retention of about 96.6% and 92% over 5000 cycles.

  18. High temperature oxidation behavior of ODS steels

    Science.gov (United States)

    Kaito, T.; Narita, T.; Ukai, S.; Matsuda, Y.

    2004-08-01

    Oxide dispersion strengthened (ODS) steels are being developing for application as advanced fast reactor cladding and fusion blanket materials, in order to allow increased operation temperature. Oxidation testing of ODS steel was conducted under a controlled dry air atmosphere to evaluate the high temperature oxidation behavior. This showed that 9Cr-ODS martensitic steels and 12Cr-ODS ferritic steels have superior high temperature oxidation resistance compared to 11 mass% Cr PNC-FMS and 17 mass% Cr ferritic stainless steel. This high temperature resistance is attributed to earlier formation of the protective α-Cr 2O 3 on the outer surface of ODS steels.

  19. Oxidation of boron carbide at high temperatures

    International Nuclear Information System (INIS)

    Steinbrueck, Martin

    2005-01-01

    The oxidation kinetics of various types of boron carbides (pellets, powder) were investigated in the temperature range between 1073 and 1873 K. Oxidation rates were measured in transient and isothermal tests by means of mass spectrometric gas analysis. Oxidation of boron carbide is controlled by the formation of superficial liquid boron oxide and its loss due to the reaction with surplus steam to volatile boric acids and/or direct evaporation at temperatures above 1770 K. The overall reaction kinetics is paralinear. Linear oxidation kinetics established soon after the initiation of oxidation under the test conditions described in this report. Oxidation is strongly influenced by the thermohydraulic boundary conditions and in particular by the steam partial pressure and flow rate. On the other hand, the microstructure of the B 4 C samples has a limited influence on oxidation. Very low amounts of methane were produced in these tests

  20. Tantalum high-temperature oxidation kinetics

    International Nuclear Information System (INIS)

    Grigor'ev, Yu.M.; Sarkisyan, A.A.; Merzhanov, A.G.

    1981-01-01

    Kinetics of heat release and scale growth during tantalum oxidation within 650-1300 deg C temperature range in oxygen-containing media is investigated. Kinetic equations and temperature and pressure dependences of constants are ound Applicability of the kinetic Lorie mechanism for the description of the tantalum oxidation kinetics applicably to rapid-passing processes is shown. It is stated that the process rate (reaction ability) is determined by adsorption desorption factors on the external surface of the ''protective'' oxide for the ''linear'' oxidation stage [ru

  1. Corium Oxidation at Temperatures Above 2000 K

    International Nuclear Information System (INIS)

    Hagrman, Donald L.; Rempe, Joy L.

    2001-01-01

    A mechanistic model, based on a quasi-equilibrium analysis of oxidation reactions, is proposed for predicting high-temperature corium oxidation. The analysis suggests that oxide forming on the surface of corium containing uranium, zirconium, and iron is similar to the oxides formed on zirconium and uranium as long as there is a small percentage of unoxidized zirconium or uranium in the metallic phase. This is because of the higher affinity of zirconium and uranium for oxygen. Hence, oxidation rates and heat production rates are similar to (U,Zr) compounds until nearly all the uranium and zirconium in the corium oxidizes. Oxidation rates after this point are predicted to be similar to those implied by the oxide thickness present when the forming oxide ceases to be protective, and heat generation rates should be similar to those implied by iron oxidation, i.e., ∼4% of the zirconium oxidation heating rate.The maximum atomic ratio of unoxidized iron to unoxidized liquid zirconium plus uranium for the formation of a solid protective oxide below 2800 K is estimated for a temperature, T (in Kelvin), as follows:(unoxidized iron)/(unoxidized zirconium + turanium) = (1/28){5.7/exp[-(147 061 + 12.08T log(T) - 61.03T - 0.000555T 2 /1.986T)]} 1/2 .As long as this limit is not exceeded, either zirconium or uranium metal oxidation rates and heating describe the corium oxidation rate. If this limit is exceeded, diffusion of steam to the corium surface will limit the oxidation rate, and linear time-dependent growth of a nonprotective, mostly FeO, layer will occur below the protective (Zr,U) O 2 scale. When this happens, the oxidation should be at the constant rate given by the thickness of the protective layer. Heat generation should be similar to that of iron oxidation

  2. Corium Oxidation at Temperatures Above 2000 K

    Energy Technology Data Exchange (ETDEWEB)

    Hagrman, Donald Lee; Rempe, Joy Lynn

    2001-02-01

    A mechanistic model, based on a quasi-equilibrium analysis of oxidation reactions, is proposed for predicting high-temperature corium oxidation. The analysis suggests that oxide forming on the surface of corium containing uranium, zirconium, and iron is similar to the oxides formed on zirconium and uranium as long as there is a small percentage of unoxidized zirconium or uranium in the metallic phase. This is because of the higher affinity of zirconium and uranium for oxygen. Hence, oxidation rates and heat production rates are similar to (U,Zr) compounds until nearly all the uranium and zirconium in the corium oxidizes. Oxidation rates after this point are predicted to be similar to those implied by the oxide thickness present when the forming oxide ceases to be protective, and heat generation rates should be similar to those implied by iron oxidation, i.e., ~4% of the zirconium oxidation heating rate. The maximum atomic ratio of unoxidized iron to unoxidized liquid zirconium plus uranium for the formation of a solid protective oxide below 2800 K is estimated for a temperature, T (in Kelvin), as follows: (unoxidized iron)/(unoxidized zirconium + turanium) = (1/28){5.7/exp[-(147 061 + 12.08T log(T) - 61.03T - 0.000555T2/1.986T)]}1/2. As long as this limit is not exceeded, either zirconium or uranium metal oxidation rates and heating describe the corium oxidation rate. If this limit is exceeded, diffusion of steam to the corium surface will limit the oxidation rate, and linear time-dependent growth of a nonprotective, mostly FeO, layer will occur below the protective (Zr,U) O2 scale. When this happens, the oxidation should be at the constant rate given by the thickness of the protective layer. Heat generation should be similar to that of iron oxidation.

  3. Mesoporous Mn promoted Co3O4 oxides as an efficient and stable catalyst for low temperature oxidation of CO

    Science.gov (United States)

    Liu, Changxiang; Gong, Lei; Dai, Runying; Lu, Meijuan; Sun, Tingting; Liu, Qian; Huang, Xigen; Huang, Zhong

    2017-09-01

    Mesoporous Mn-doped Co3O4 catalysts were successfully prepared via a dry soft reactive grinding method based on solid state reaction, and their catalytic performances on CO oxidation were evaluated at a high space velocity of 49,500 mL g-1 h-1. A significant promoted effect was observed once the atomic ratios of Mn/(Co+Mn) were lower than 10%, for instance, the temperature for 50% conversion decreased to about -60 °C, showing superior catalytic performance compared to the single metal oxide. Especially, the Mn-promoted Co3O4 catalyst with a Mn/(Co+Mn) molar ratio of 10% could convert 100% CO after 3000 min of time-on-steam without any deactivation at room temperature. As prepared catalysts were characterized by XRD, N2-adsorption/desorption, TEM, H2-TPR, O2-TPD and CO-titration analysis. The significant enhancement of performance for oxidation of CO over Mn-Co-O mixed oxides was associated with the high active oxygen species concentrations formed during the pretreatment in O2 atmosphere.

  4. Initial stages of high temperature metal oxidation

    International Nuclear Information System (INIS)

    Yang, C.Y.; O'Grady, W.E.

    1981-01-01

    The application of XPS and UPS to the study of the initial stages of high temperature (> 350 0 C) electrochemical oxidation of iron and nickel is discussed. In the high temperature experiments, iron and nickel electrodes were electrochemically oxidized in contact with a solid oxide electrolyte in the uhv system. The great advantages of this technique are that the oxygen activity at the interface may be precisely controlled and the ability to run the reactions in uhv allows the simultaneous observation of the reactions by XPS

  5. High temperature oxidation kinetics of dysprosium particles

    Energy Technology Data Exchange (ETDEWEB)

    Jaques, Brian J.; Butt, Darryl P., E-mail: DarrylButt@BoiseState.edu

    2015-09-25

    Highlights: • The oxidation behavior of dysprosium particles was studied from 500 to 1000 °C. • Activation energy in initial region found as 8–25 kJ/mol, depending on atmosphere. • Activation energy in intermediate region found as 80–95 kJ/mol. • The oxide grows at the metal–oxide interface. • Generally, the formed oxide behaved as a p-type semiconductor. - Abstract: Rare earth elements have been recognized as critical materials for the advancement of many strategic and green technologies. Recently, the United States Department of Energy has invested many millions of dollars to enhance, protect, and forecast their production and management. The work presented here attempts to clarify the limited and contradictory literature on the oxidation behavior of the rare earth metal, dysprosium. Dysprosium particles were isothermally oxidized from 500 to 1000 °C in N{sub 2}–(2%, 20%, and 50%) O{sub 2} and Ar–20% O{sub 2} using simultaneous thermal analysis techniques. Two distinct oxidation regions were identified at each isothermal temperature in each oxidizing atmosphere. Initially, the oxidation kinetics are very fast until the reaction enters a slower, intermediate region of oxidation. The two regions are defined and the kinetics of each are assessed to show an apparent activation energy of 8–25 kJ/mol in the initial region and 80–95 kJ/mol in the intermediate oxidation reaction region. The effects of varying the oxygen partial pressure on the reaction rate constant are used to show that dysprosium oxide (Dy{sub 2}O{sub 3}) generally acts as a p-type semiconductor in both regions of oxidation (with an exception above 750 °C in the intermediate region)

  6. Contribution to the study of the oxidation reaction of the carbon oxide in contact with catalysts issued from the decomposition of nickel hydro-aluminates at various temperatures

    International Nuclear Information System (INIS)

    Samaane, Mikhail

    1966-01-01

    Addressing the study of the oxidation reaction of carbon oxide which produces carbon dioxide, this research thesis reports the study of this reaction in presence of catalysts (2NiO + Al 2 O 3 , NiAl 2 O 4 and NiO + NiAl 2 O 4 ) issued from the decomposition of nickel hydro-aluminates at different temperatures. The first part describes experimental techniques and the nature of materials used in this study. The second part reports the study of the catalytic activity of the 2NiO+Al 2 O 3 catalyst during the oxidation of CO. Preliminary studies are also reported: structure and texture of nickel hydro-aluminate which is the raw material used to produce catalysts, activation of this compound to develop the catalytic activity in CO oxidation, chemisorption of CO, O 2 and CO 2 on the 2NiO+Al 2 O 3 solid, interaction of adsorbed gases at the solid surface, and kinetic study of the oxidation reaction. The third part reports the study of the catalytic activity in the oxidation reaction of CO of spinel catalysts (NiAl 2 O 4 and NiO+NiAl 2 O 4 ) obtained by calcination of nickel hydro-aluminates at high temperature. The formation of the spinel phase, the chemisorption of CO, O 2 and CO 2 on NiAl 2 O 4 , and the kinetic of the oxidation reaction are herein studied

  7. Temperature effect on surface oxidation of titanium

    International Nuclear Information System (INIS)

    Vaquilla, I.; Barco, J.L. del; Ferron, J.

    1990-01-01

    The effect of temperature on the first stages of the superficial oxidation of polycrystalline titanium was studied using both Auger electron spectroscopy (AES) and emission shreshold (AEAPS). The number of compounds present on the surface was determined by application of the factor analysis technique. Reaction evolution was followed through the relative variation of Auger LMM and LMV transitions which are characteristic of titanium. Also the evolution of the chemical shift was determined by AEAPS. The amount of oxygen on the surface was quantified using transition KLL of oxygen. It was found that superficial oxidation depends on temperature. As much as three different compounds were determined according to substrate temperature and our exposure ranges. (Author). 7 refs., 5 figs

  8. Study of Hopcalite (CuMnOx) Catalysts Prepared Through A Novel Route for the Oxidation of Carbon Monoxide at Low Temperature

    OpenAIRE

    Subhashish Dey; Ganesh Chandra Dhal; Devendra Mohan; Ram Prasad

    2017-01-01

    Carbon monoxide (CO) is a poisonous gas, recognized as a silent killer. The gas is produced by incomplete combustion of carbonaceous fuel. Recent studies have shown that hopcalite group is one of the promising catalysts for CO oxidation at low temperature. In this study, hopcalite (CuMnOx) catalysts were prepared by KMnO4 co-precipitation method followed by washing, drying the precipitate at different temperatures (22, 50, 90, 110, and 120 oC) for 12 h in an oven and subsequent calcination at...

  9. Nitrous oxide emissions at low temperatures

    International Nuclear Information System (INIS)

    Martikainen, P.J.

    2002-01-01

    Microbial processes in soil are generally stimulated by temperature, but at low temperatures there are anomalies in the response of microbial activities. Soil physical-chemical characteristics allow existence of unfrozen water in soil also at temperatures below zero. Therefore, some microbial activities, including those responsible for nitrous oxide (N 2 0) production, can take place even in 'frozen' soil. Nitrous oxide emissions during winter are important even in boreal regions where they can account for more than 50% of the annual emissions. Snow pack therefore has great importance for N 2 0 emissions, as it insulates soil from the air allowing higher temperatures in soil than in air, and possible changes in snoav cover as a result of global warming would thus affect the N 2 0 emission from northern soils. Freezing-thawing cycles highly enhance N 2 0 emissions from soil, probably because microbial nutrients, released from disturbed soil aggregates and lysed microbial cells, support microbial N 2 0 production. However, the overall interactions between soil physics, chemistry, microbiology and N 2 0 production at low temperatures, including effects of freezing-thawing cycles, are still poorly known. (au)

  10. Design of a core–shell Pt–SiO2 catalyst in a reverse microemulsion system: Distinctive kinetics on CO oxidation at low temperature

    KAUST Repository

    Al Mana, Noor; Phivilay, Somphonh Peter; Laveille, Paco; Hedhili, Mohamed N.; Fornasiero, Paolo; Takanabe, Kazuhiro; Basset, Jean-Marie

    2016-01-01

    The mechanism of formation of Pt@SiO2 as a model of core–shell nanoparticles via water-in-oil reverse microemulsions was studied in detail. By controlling the time of growth of Pt precursors, Pt(OH)x, after hydrolysis in NH3 aq. before adding SiO2

  11. Study of nitric oxide catalytic oxidation on manganese oxides-loaded activated carbon at low temperature

    Energy Technology Data Exchange (ETDEWEB)

    You, Fu-Tian [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); University of Chinese Academy of Sciences, Beijing (China); Yu, Guang-Wei, E-mail: gwyu@iue.ac.cn [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Wang, Yin, E-mail: yinwang@iue.ac.cn [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Xing, Zhen-Jiao [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Liu, Xue-Jiao; Li, Jie [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); University of Chinese Academy of Sciences, Beijing (China)

    2017-08-15

    Highlights: • Loading manganese oxides on activated carbon effectively promotes NO oxidation. • NO adsorption-desorption on activated carbon is fundamental to NO oxidation. • A high Mn{sup 4+}/Mn{sup 3+} ratio contributes to NO oxidation by promoting lattice O transfer. - Abstract: Nitric oxide (NO) is an air pollutant that is difficult to remove at low concentration and low temperature. Manganese oxides (MnO{sub x})-loaded activated carbon (MLAC) was prepared by a co-precipitation method and studied as a new catalyst for NO oxidation at low temperature. Characterization of MLAC included X-ray diffraction (XRD), scanning electron microscopy (SEM), N{sub 2} adsorption/desorption and X-ray photoelectron spectroscopy (XPS). Activity tests demonstrated the influence of the amount of MnO{sub x} and the test conditions on the reaction. MLAC with 7.5 wt.% MnO{sub x} (MLAC003) exhibits the highest NO conversion (38.7%) at 1000 ppm NO, 20 vol.% O{sub 2}, room temperature and GHSV ca. 16000 h{sup −1}. The NO conversion of MLAC003 was elevated by 26% compared with that of activated carbon. The results of the MLAC003 activity test under different test conditions demonstrated that NO conversion is also influenced by inlet NO concentration, inlet O{sub 2} concentration, reaction temperature and GHSV. The NO adsorption-desorption process in micropores of activated carbon is fundamental to NO oxidation, which can be controlled by pore structure and reaction temperature. The activity elevation caused by MnO{sub x} loading is assumed to be related to Mn{sup 4+}/Mn{sup 3+} ratio. Finally, a mechanism of NO catalytic oxidation on MLAC based on NO adsorption-desorption and MnO{sub x} lattice O transfer is proposed.

  12. High temperature oxidation behavior of TiAl-based intermetallics

    International Nuclear Information System (INIS)

    Stroosnijder, M.F.; Sunderkoetter, J.D.; Haanappel, V.A.C.

    1996-01-01

    TiAl-based intermetallic compounds have attracted considerable interest as structural materials for high-temperature applications due to their low density and substantial mechanical strength at high temperatures. However, one major drawback hindering industrial application arises from the insufficient oxidation resistance at temperatures beyond 700 C. In the present contribution some general aspects of high temperature oxidation of TiAl-based intermetallics will be presented. This will be followed by a discussion of the influence of alloying elements, in particular niobium, and of the effect of nitrogen in the oxidizing environment on the high temperature oxidation behavior of such materials

  13. Gallium Oxide Nanostructures for High Temperature Sensors

    Energy Technology Data Exchange (ETDEWEB)

    Chintalapalle, Ramana V. [Univ. of Texas, El Paso, TX (United States)

    2015-04-30

    Gallium oxide (Ga2O3) thin films were produced by sputter deposition by varying the substrate temperature (Ts) in a wide range (Ts=25-800 °C). The structural characteristics and electronic properties of Ga2O3 films were evaluated using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectrometry (EDS), Rutherford backscattering spectrometry (RBS) and spectrophotometric measurements. The effect of growth temperature is significant on the chemistry, crystal structure and morphology of Ga2O3 films. XRD and SEM analyses indicate that the Ga2O3 films grown at lower temperatures were amorphous while those grown at Ts≥500 oC were nanocrystalline. RBS measurements indicate the well-maintained stoichiometry of Ga2O3 films at Ts=300-800 °C. The electronic structure determination indicated that the nanocrystalline Ga2O3films exhibit a band gap of ~5 eV. Tungsten (W) incorporated Ga2O3 films were produced by co-sputter deposition. W-concentration was varied by the applied sputtering-power. No secondary phase formation was observed in W-incorporated Ga2O3 films. W-induced effects were significant on the structure and electronic properties of Ga2O3 films. The band gap of Ga2O3 films without W-incorporation was ~5 eV. Oxygen sensor characteristics evaluated using optical and electrical methods indicate a faster response in W-doped Ga2O3 films compared to intrinsic Ga2O3 films. The results demonstrate the applicability of both intrinsic and W-doped Ga-oxide films for oxygen sensor application at temperatures ≥700 °C.

  14. Medium-temperature solid oxide fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Maffei, N.; Kuriakose, A.K. [Natural Resources Canada, Ottawa, ON (Canada). Materials Technology Lab

    2000-07-01

    The Materials Technology Laboratory (MTL) of Natural Resources Canada has been conducting research on the development of a solid oxide fuel cell (SOFC) for the past decade. Fuel cells convert chemical energy directly into electric energy in an efficient and environmentally friendly manner. SOFCs are considered to be good stationary power sources for commercial and residential applications and will likely be commercialized in the near future. The research at MTL has focused on the development of new electrolytes for use in SOFCs. In the course of this research, monolithic planar single cell SOFCs based on doubly doped ceria and lanthanum gallate have been fabricated and tested at 700 degrees C. This paper compared the performance characteristics of both these systems. The data suggested the presence of a significant electronic conductivity in the SOFC incorporating doubly doped ceria, resulting in lower than expected voltage output. The stability of the SOFC, however, did not appear to be negatively affected. The lanthanum gallate based SOFC performed well. It was concluded that reducing the operating temperature of SOFCs would improve their reliability and enhance their operating life. First generation commercial SOFCs will use a zirconium oxide-based electrolytes while second generation units might possibly use ceria-based and/or lanthanum gallate electrolytes. 24 refs., 6 figs.

  15. Dense high temperature ceramic oxide superconductors

    Science.gov (United States)

    Landingham, Richard L.

    1993-01-01

    Dense superconducting ceramic oxide articles of manufacture and methods for producing these articles are described. Generally these articles are produced by first processing these superconducting oxides by ceramic processing techniques to optimize materials properties, followed by reestablishing the superconducting state in a desired portion of the ceramic oxide composite.

  16. Evaluation of biochars by temperature programmed oxidation/mass spectrometry

    Science.gov (United States)

    Michael Jackson; Thomas Eberhardt; Akwasi Boateng; Charles Mullen; Les Groom

    2013-01-01

    Biochars produced from thermochemical conversions of biomass were evaluated by temperature programmed oxidation (TPO). This technique, used to characterize carbon deposits on petroleum cracking catalysts, provides information on the oxidative stability of carbonaceous solids, where higher temperature reactivity indicates greater structural order, an important property...

  17. New insight of high temperature oxidation on self-exfoliation capability of graphene oxide

    Science.gov (United States)

    Liu, Yuhang; Zeng, Jie; Han, Di; Wu, Kai; Yu, Bowen; Chai, Songgang; Chen, Feng; Fu, Qiang

    2018-05-01

    The preparation of graphene oxide (GO) via Hummers method is usually divided into two steps: low temperature oxidation at 35 °C (step I oxidation) and high temperature oxidation at 98 °C (step II oxidation). However, the effects of these two steps on the exfoliation capability and chemical structure of graphite oxide remain unclear. In this study, both the functional group content of graphite oxide and the entire evolution of interlayer spacing were investigated during the two steps. Step I oxidation is a slowly inhomogeneous oxidation step to remove unoxidized graphite flakes. The prepared graphite oxide can be easily self-exfoliated but contains a lot of organic sulfur. During the first 20 min of step II oxidation, the majority of organic sulfur can be efficiently removed and graphite oxide still remains a good exfoliation capability due to sharp increasing of carboxyl groups. However, with a longer oxidation time at step II oxidation, the decrease of organic sulfur content is slowed down apparently but without any carboxyl groups forming, then graphite oxide finally loses self-exfoliation capability. It is concluded that a short time of step II oxidation can produce purer and ultralarge GO sheets via self-exfoliation. The pure GO is possessed with better thermal stability and liquid crystal behavior. Besides, reduced GO films prepared from step II oxidation show better mechanical and electric properties after reducing compared with that obtained only via step I oxidation.

  18. Selective carbon monoxide oxidation over Ag-based composite oxides

    Energy Technology Data Exchange (ETDEWEB)

    Guldur, C. [Gazi University, Ankara (Turkey). Chemical Engineering Department; Balikci, F. [Gazi University, Ankara (Turkey). Institute of Science and Technology, Environmental Science Department

    2002-02-01

    We report our results of the synthesis of 1 : 1 molar ratio of the silver cobalt and silver manganese composite oxide catalysts to remove carbon monoxide from hydrogen-rich fuels by the catalytic oxidation reaction. Catalysts were synthesized by the co-precipitation method. XRD, BET, TGA, catalytic activity and catalyst deactivation studies were used to identify active catalysts. Both CO oxidation and selective CO oxidation were carried out in a microreactor using a reaction gas mixture of 1 vol% CO in air and another gas mixture was prepared by mixing 1 vol% CO, 2 vol% O{sub 2}, 84 vol% H{sub 2}, the balance being He. 15 vol% CO{sub 2} was added to the reactant gas mixture in order to determine the effect of CO{sub 2}, reaction gases were passed through the humidifier to determine the effect of the water vapor on the oxidation reaction. It was demonstrated that metal oxide base was decomposed to the metallic phase and surface areas of the catalysts were decreased when the calcination temperature increased from 200{sup o}C to 500{sup o}C. Ag/Co composite oxide catalyst calcined at 200{sup o}C gave good activity at low temperatures and 90% of CO conversion at 180{sup o}C was obtained for the selective CO oxidation reaction. The addition of the impurities (CO{sub 2} or H{sub 2}O) decreased the activity of catalyst for selective CO oxidation in order to get highly rich hydrogen fuels. (author)

  19. Pressure effects on high temperature steam oxidation of Zircaloy-4

    International Nuclear Information System (INIS)

    Park, Kwangheon; Kim, Kwangpyo; Ryu, Taegeun

    2000-01-01

    The pressure effects on Zircaloy-4 (Zry-4) cladding in high temperature steam have been analyzed. A double layer autoclave was made for the high pressure, high temperature oxidation tests. The experimental test temperature range was 700 - 900 deg C, and pressures were 0.1 - 15 MPa. Steam partial pressure turns out to be an important one rather than total pressure. Steam pressure enhances the oxidation rate of Zry-4 exponentially. The enhancement depends on the temperature, and the maximum exists between 750 - 800 deg C. Pre-existing oxide layer decreases the enhancement about 40 - 60%. The acceleration of oxidation rate by high pressure team seems to be originated from the formation of cracks by abrupt transformation of tetragonal phase in oxide, where the un-stability of tetragonal phase comes from the reduction of surface energy by steam. (author)

  20. Low Temperature Oxidation of Methane: The Influence of Nitrogen Oxides

    DEFF Research Database (Denmark)

    Bendtsen, Anders Broe; Glarborg, Peter; Dam-Johansen, Kim

    2000-01-01

    by the competition between three reaction paths from CH3 to CH2O. A direct high temperature path (A), a two-step NO2 enhanced low temperature path (B) and a slow three step NO enhanced path (C), which may produce NO2 to activate path B. The negative temperature coefficient behaviour was explained by a competition...

  1. Oxidation of zircaloy-2 in high temperature steam

    International Nuclear Information System (INIS)

    Ikeda, Seiichi; Ito, Goro; Ohashi, Shigeo

    1975-01-01

    Oxidation tests were conducted for zircaloy-2 in steam at temperature ranging from 900 to 1300 0 C to clarify its oxidation kinetics as a nuclear fuel cladding materials in case of a loss-of-coolant accident. The influence of maximum temperature and heating rate of the specimen on its oxidation rate in steam was investigated. The changes in mechanical properties of the specimens after oxidation tests are also studied. The results obtained were summarized as follows: (1) The weight of the specimen after oxidation in steam increased two times as the time required to reach the maximum temperature increased from 1 to 10 mins. (2) The kinetics of oxidation of zircaloy-2 in steam were not affected by the difference in the surface condition before test such as chemical polishing or pre-oxidation in steam. (3) The dominant growth of oxide film on the surface of zircaloy-2 was observed at the initial stage of oxidation in steam. However, the thickness of oxygen-rich solid solution layer under the film increased gradually with the progress of oxidation and the ratio of oxygen in oxide to that in solid solution has a constant value of 8:2. (4) The breakaway took place only in the specimen subjected to 900 0 C repeated heating. This penomenon was caused by the local growth of the oxide below a crack of the oxide film resulting from the reheating of the specimen. (5) The results of bending tests showed that the deflection until fracture of the specimen was smaller for the one heated at a higher temperature even if the weight increase was of the same order of magnitude for both specimens. (6) It was concluded that the ductility of zircaloy-2 decreased remarkably at a heating temperature in excess of 1100 0 C for more than 5 min. (auth.)

  2. Low Temperature Processed Complementary Metal Oxide Semiconductor (CMOS) Device by Oxidation Effect from Capping Layer

    KAUST Repository

    Wang, Zhenwei

    2015-04-20

    In this report, both p- and n-type tin oxide thin-film transistors (TFTs) were simultaneously achieved using single-step deposition of the tin oxide channel layer. The tuning of charge carrier polarity in the tin oxide channel is achieved by selectively depositing a copper oxide capping layer on top of tin oxide, which serves as an oxygen source, providing additional oxygen to form an n-type tin dioxide phase. The oxidation process can be realized by annealing at temperature as low as 190°C in air, which is significantly lower than the temperature generally required to form tin dioxide. Based on this approach, CMOS inverters based entirely on tin oxide TFTs were fabricated. Our method provides a solution to lower the process temperature for tin dioxide phase, which facilitates the application of this transparent oxide semiconductor in emerging electronic devices field.

  3. Low Temperature Processed Complementary Metal Oxide Semiconductor (CMOS) Device by Oxidation Effect from Capping Layer

    KAUST Repository

    Wang, Zhenwei; Al-Jawhari, Hala A.; Nayak, Pradipta K.; Caraveo-Frescas, J. A.; Wei, Nini; Hedhili, Mohamed N.; Alshareef, Husam N.

    2015-01-01

    , which is significantly lower than the temperature generally required to form tin dioxide. Based on this approach, CMOS inverters based entirely on tin oxide TFTs were fabricated. Our method provides a solution to lower the process temperature for tin

  4. High Temperature Strength of Oxide Dispersion Strengthened Aluminium

    DEFF Research Database (Denmark)

    Clauer, A.H.; Hansen, Niels

    1984-01-01

    constant (except for the material with the lowest oxide content). The high temperature values of the modulus-corrected yield stresses are approximately two-thirds of the low temperature value. During high temperature creep, there is a definite indication of a threshold stress. This threshold stress......The tensile flow stress of coarse-grained dispersion strengthened Al-Al2O3 materials were measured as a function of temperature (77–873 K) and volume fraction (0.19-0.92 vol.%) of aluminium oxide. For the same material, the creep strength was determined as a function of temperature in the range 573......–873 K. The modulus-corrected yield stress (0.01 offset) is found to be temperature independent at low temperature (195–472 K). Between 473 and 573 K, the yield stress starts to decrease with increasing temperature. At high temperatures (573–873 K), the modulus-corrected yield stress is approximately...

  5. In-situ positron emission of CO oxidation

    OpenAIRE

    Vonkeman, K.A.; Jonkers, G.; Wal, van der, S.W.A.; Santen, van, R.A.

    1993-01-01

    Using a Neuro ECAT positron tomog., the Positron Emission computed Tomog. (PET) was utilized to image the catalytic oxidn. of CO by using CO and CO2, labeled with short lived positron emitting nuclides. Studies were performed over highly dispersed CeO2/g-Al2O3 supported Pt and Rh catalysts. With a math. model of the reaction kinetics, based on the elementary steps of the catalytic reaction and partially on literature surface science data, the effect of CeO2 promotion and the presence of NO we...

  6. In-situ positron emission of CO oxidation

    NARCIS (Netherlands)

    Vonkeman, K.A.; Jonkers, G.; Wal, van der S.W.A.; Santen, van R.A.

    1993-01-01

    Using a Neuro ECAT positron tomog., the Positron Emission computed Tomog. (PET) was utilized to image the catalytic oxidn. of CO by using CO and CO2, labeled with short lived positron emitting nuclides. Studies were performed over highly dispersed CeO2/g-Al2O3 supported Pt and Rh catalysts. With a

  7. Lipoxygenase and carotenoids: A co-oxidation story

    African Journals Online (AJOL)

    user

    2013-05-15

    May 15, 2013 ... occurs only in bacteria, fungi and plants where they have established functions that include their role as antenna in the light-harvesting .... malian LOX and some marine invertebrate LOXs produce ... Arachidonic acid metabolism by LOX in human plate-lets ... During secondary technological processes a.

  8. Elementary steps of the catalytic oxidation of CO in a gas phase in the presence of rhenium cations with carbonyl and oxygen ligands: a comparison with heterogeneous catalysis

    International Nuclear Information System (INIS)

    Goncharov, V.B.; Fialko, E.F.; Shejnin, D.Eh.; Kikhtenko, A.V.

    1997-01-01

    Reactivity in a gaseous phase o rhenium (Re + ) and rhenium monocarbonyl (ReCO + ) in the reaction of CO oxidation in oxygen-containing reagents (NO, O 2 , H 2 O) is studied through the method of the ionic cyclotron resonance. It is shown that presence of carbonyl ligand essentially influences the ion reactivity. The effective channel of the metal monocarbonyl ions oxidation through molecular oxygen is found. Accounting for this stage makes of possible to explain the low-temperature activity of a number of oxide catalyzer Mo, W in the reaction of CO oxidation by molecular oxygen

  9. Characterization of low-temperature microwave loss of thin aluminum oxide formed by plasma oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Chunqing, E-mail: cdeng@uwaterloo.ca; Otto, M.; Lupascu, A., E-mail: alupascu@uwaterloo.ca [Institute for Quantum Computing, Department of Physics and Astronomy, and Waterloo Institute for Nanotechnology, University of Waterloo, Waterloo, Ontario N2L 3G1 (Canada)

    2014-01-27

    We report on the characterization of microwave loss of thin aluminum oxide films at low temperatures using superconducting lumped resonators. The oxide films are fabricated using plasma oxidation of aluminum and have a thickness of 5 nm. We measure the dielectric loss versus microwave power for resonators with frequencies in the GHz range at temperatures from 54 to 303 mK. The power and temperature dependence of the loss are consistent with the tunneling two-level system theory. These results are relevant to understanding decoherence in superconducting quantum devices. The obtained oxide films are thin and robust, making them suitable for capacitors in compact microwave resonators.

  10. Analysis of thermodynamic properties for high-temperature superconducting oxides

    International Nuclear Information System (INIS)

    Kushwah, S.S.; Shanker, J.

    1993-01-01

    Analysis of thermodynamic properties such as specific heat, Debye temperature, Einstein temperature, thermal expansion coefficient, bulk modulus, and Grueneisen parameter is performed for rare-earth-based, Tl-based, and Bi-based superconducting copper oxides. Values of thermodynamic parameters are calculated and reported. The relationship between the Debye temperature and the superconducting transition temperature is used to estimate the values of T c using the interaction parameters from Ginzburg. (orig.)

  11. High temperature cyclic oxidation and hot corrosion behaviours of ...

    Indian Academy of Sciences (India)

    Administrator

    eutectic reaction below 600°C. When the temperature ... blades, consequently corrosion rate rapidly increases due ... the corrosion run. ... Figure 1. Surface macrographs of superalloys subjected to hot corrosion and oxidation .... show the oxide scales of three different chemical compo- .... Li J and Wahi R P 1995 Acta Metall.

  12. High Temperature Oxidation of Superalloys and Intermetallic Compounds

    Science.gov (United States)

    2010-02-28

    Oxid. Met. Vol.14, pp. 217-234. 1980. 20. T.A. Rannanarayanan, M. Raghavan and R. Petrovic-Luton. Metallic Yttrium Additions to High Temperatura ... Temperatura Alloys: Influence of AI2O3 Scale Properties. Oxid. Met. Vol.22, pp. 83-100. 1984. 21. High-temperature characterization of reactively

  13. Propane Oxidation at High Pressure and Intermediate Temperatures

    DEFF Research Database (Denmark)

    Hashemi, Hamid; Christensen, Jakob Munkholt; Glarborg, Peter

    Propane oxidation at intermediate temperatures (500—900 K) and high pressure (100 bar) has been characterized by conducting experiments in a laminar flow reactor over a wide range of stoichiometries. The onset of fuel oxidation was found to be 600—725 K, depending on mixture stoichiometry...

  14. High temperature oxidation of slurry coated interconnect alloys

    DEFF Research Database (Denmark)

    Persson, Åsa Helen

    with this interaction mechanism mainly give a geometrical protection against oxidation by blocking oxygen access at the surface of the oxide scale. The protecting effect is gradually reduced as the oxide scale grows thicker than the diameter of the coating particles. Interaction mechanism B entails a chemical reaction...... scale. The incorporated coating particles create a geometrical protection against oxidation that should not loose their effect after the oxide scale has grown thicker than the diameter of the coating particles. The two single layer coatings consisting of (La0.85Sr0.15)MnO3 + 10% excess Mn, LSM, and (La0......In this project, high temperature oxidation experiments of slurry coated ferritic alloys in atmospheres similar to the atmosphere found at the cathode in an SOFC were conducted. From the observations possible interaction mechanisms between the slurry coatings and the growing oxide scale...

  15. Materials and coatings to resist high temperature oxidation and corrosion

    International Nuclear Information System (INIS)

    1977-01-01

    Object of the given papers are the oxidation and corrosion behaviour of several materials (such as stainless steels, iron-, or nickel-, or cobalt-base alloys, Si-based ceramics) used at high temperatures and various investigations on high-temperature protective coatings. (IHoe) [de

  16. Nitrous oxide flux under changing temperature and CO2

    Science.gov (United States)

    We are investigating nitrous oxide flux seasonal trends and response to temperature and CO2 increases in a boreal peatland. Peatlands located in boreal regions make up a third of global wetland area and are expected to have the highest temperature increases in response to climat...

  17. Enhanced low-temperature oxidation of zirconium alloys under irradiation

    International Nuclear Information System (INIS)

    Cox, B.; Fidleris, V.

    1989-01-01

    The linear growth of relatively thick (>300 nm) interference-colored oxide films on zirconium alloy specimens exposed in the Advanced Test Reactor (ATR) coolant at ≤55 o C was unexpected. Initial ideas were that this was a photoconduction effect. Experiments to study photoconduction in thin anodic zirconium oxide (ZrO 2 ) films in the laboratory were initiated to provide background data. It was found that, in the laboratory, provided a high electric field was maintained across the oxide during ultraviolet (UV) irradiation, enhanced growth of oxide occurred in the irradiated area. Similarly enhanced growth could be obtained on thin thermally formed oxide films that were immersed in an electrolyte with a high electric field superimposed. This enhanced growth was found to be caused by the development of porosity in the barrier oxide layer by an enhanced local dissolution and reprecipitation process during UV irradiation. Similar porosity was observed in the oxide films on the ATR specimens. Since it is not thought that a high electric field could have been present in this instance, localized dissolution of fast-neutron primary recoil tracks may be the operative mechanism. In all instances, the specimens attempt to maintain the normal barrier-layer oxide thickness, which causes the additional oxide growth. Similar mechanisms may have operated during the formation of thick loosely adherent, porous oxides in homogeneous reactor solutions under irradiation, and may be the cause of enhanced oxidation of zirconium alloys in high-temperature water-cooled reactors in some water chemistries. (author)

  18. CATALYSTS BASED ON UKRAINIAN NATURAL SORBENTS FOR LOW-TEMPERATURE CARBON MONOXIDE OXIDATION MEANT FOR INDIVIDUAL RESPIRATORY PROTECTIVE DEVICES

    Directory of Open Access Journals (Sweden)

    T. L. Rakyts’ka

    2015-11-01

    Full Text Available In spite of a great number of patented formulas of catalysts for neutralization of carbon monoxide (CO which is the most widespread atmospheric pollutant, only batch-produced hopcalite and alumina supported palladium (Pd/Al2O3 are used in practice. The named catalysts have significant defects: hopcalite is poisonable in the presence of water vapor and Pd/Al2O3 is characterized by the great content of palladium. We have found the possibility of using inexpensive Ukrainian natural sorbents differing by their mineralogical and chemical compositions, i.e. zeolites, bentonites, basalt tuffs, and disperse silicas, as supports for development and subsequent application of palladium(II and copper(II based catalysts for carbon monoxide oxidation. Acid-thermally modified Ukrainian sorbents have been found to be proper for obtaining supported copper-palladium complexes the most catalytically active in the reaction. Application of Ukrainian natural tripolis permitted to avoid the step of acid-thermal modification complicating the technique of catalyst production. As was found, the origin and phase composition of tripolis affect the activity of catalysts supported on them in the reaction of low-temperature Co oxidation. The most active catalyst permitting sanitary purification of air from CO to a level permissible for atmosphere of populated areas have been obtained in the case of insignificantly (thermally or hydrothermally modified tripoli from Konoplianskoe deposit.

  19. MHD oxidant intermediate temperature ceramic heater study

    Science.gov (United States)

    Carlson, A. W.; Chait, I. L.; Saari, D. P.; Marksberry, C. L.

    1981-09-01

    The use of three types of directly fired ceramic heaters for preheating oxygen enriched air to an intermediate temperature of 1144K was investigated. The three types of ceramic heaters are: (1) a fixed bed, periodic flow ceramic brick regenerative heater; (2) a ceramic pebble regenerative heater. The heater design, performance and operating characteristics under conditions in which the particulate matter is not solidified are evaluated. A comparison and overall evaluation of the three types of ceramic heaters and temperature range determination at which the particulate matter in the MHD exhaust gas is estimated to be a dry powder are presented.

  20. The high temperature oxidation behaviour of austenitic stainless steels

    International Nuclear Information System (INIS)

    Hales, R.

    1977-04-01

    High temperature annealing in a dynamic vacuum has been utilised to induce the growth of duplex oxide over the whole surface of stainless steel specimens. It is found that duplex oxide grows at a rate which does not obey a simple power law. The oxidation kinetics and oxide morphology have also been studied for a series of ternary austenitic alloys which cover a range of composition between 5 and 20% chromium. A model has been developed to describe the formation of duplex oxide and the subsequent formation of a 'healing layer' which virtually causes the oxidation process to stop. This phase tends to form at grain boundaries and a relationship has been derived for the reaction kinetics which relates the reaction rate with grain size of the substrate. (author)

  1. Computational Chemistry of Cyclopentane Low Temperature Oxidation

    KAUST Repository

    El Rachidi, Mariam

    2015-03-30

    Cycloalkanes are significant constituents of conventional fossil fuels, but little is known concerning their combustion chemistry and kinetics, particularly at low temperatures. This study investigates the pressure dependent kinetics of several reactions occurring during low-temperature cyclopentane combustion using theoretical chemical kinetics. The reaction pathways of the cyclopentyl + O2 adduct is traced to alkylhydroperoxide, cyclic ether, β-scission and HO2 elimination products. The calculations are carried out at the UCCSD(T)-F12b/cc-pVTZ-F12//M06-2X/6-311++G(d,p) level of theory. The barrierless entrance channel is treated using variable-reaction-coordinate transition state theory (VRC-TST) at the CASPT2(7e,6o) level of theory, including basis set, geometry relaxation and ZPE corrections. 1-D time-dependent multiwell master equation analysis is used to determine pressure-and temperature-dependent rate parameters of all investigated reactions. Tunneling corrections are included using Eckart barriers. Comparison with cyclohexane is used to elucidate the effect of ring size on the low temperature reactivity of naphthenes. The rate coefficients reported herein are suitable for use in cyclopentane and methylcyclopentane combustion models, even below ~900 K, where ignition is particularly sensitive to these pressure-dependent values.

  2. Ammonia oxidation at high pressure and intermediate temperatures

    DEFF Research Database (Denmark)

    Song, Yu; Hashemi, Hamid; Christensen, Jakob Munkholt

    2016-01-01

    Ammonia oxidation experiments were conducted at high pressure (30 bar and 100 bar) under oxidizing and stoichiometric conditions, respectively, and temperatures ranging from 450 to 925 K. The oxidation of ammonia was slow under stoichiometric conditions in the temperature range investigated. Under...... oxidizing conditions the onset temperature for reaction was 850–875 K at 30 bar, while at 100 bar it was about 800 K, with complete consumption of NH3 at 875 K. The products of reaction were N2 and N2O, while NO and NO2 concentrations were below the detection limit even under oxidizing conditions. The data...... was satisfactory. The main oxidation path for NH3 at high pressure under oxidizing conditions is NH3⟶+OH NH2⟶+HO2,NO2 H2NO⟶+O2 HNO⟶+O2 NO ⟶+NH2 N2. The modeling predictions are most sensitive to the reactions NH2 + NO = NNH + OH and NH2 + HO2 = H2NO + OH, which promote the ammonia consumption by forming OH...

  3. Computational Chemistry of Cyclopentane Low Temperature Oxidation

    KAUST Repository

    El Rachidi, Mariam; Zá dor, Judit; Sarathy, Mani

    2015-01-01

    reactions occurring during low-temperature cyclopentane combustion using theoretical chemical kinetics. The reaction pathways of the cyclopentyl + O2 adduct is traced to alkylhydroperoxide, cyclic ether, β-scission and HO2 elimination products. The calculations are carried out at the UCCSD(T)-F12b/cc-pVTZ-F12//M06-2X/6-311++G(d,p) level of theory. The barrierless entrance channel is treated using variable-reaction-coordinate transition state theory (VRC-TST) at the CASPT2(7e,6o) level of theory, including basis set, geometry relaxation and ZPE corrections. 1-D time-dependent multiwell master equation analysis is used to determine pressure-and temperature-dependent rate parameters of all investigated reactions. Tunneling corrections are included using Eckart barriers. Comparison with cyclohexane is used to elucidate the effect of ring size on the low temperature reactivity of naphthenes. The rate coefficients reported herein are suitable for use in cyclopentane and methylcyclopentane combustion models, even below ~900 K, where ignition is particularly sensitive to these pressure-dependent values.

  4. Molybdenum Disilicide Oxidation Kinetics in High Temperature Steam

    Energy Technology Data Exchange (ETDEWEB)

    Wood, Elizabeth Sooby [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Parker, Stephen Scott [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Nelson, Andrew Thomas [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-09-07

    The Fuel Cycle Research and Development program’s Advanced Fuels Campaign is currently supporting a range of experimental efforts aimed at the development and qualification of ‘accident tolerant’ nuclear fuel forms. One route to enhance the accident tolerance of nuclear fuel is to replace the zirconium alloy cladding, which is prone to rapid oxidation in steam at elevated temperatures, with a more oxidation-resistant cladding. Several cladding replacement solutions have been envisaged. The cladding can be completely replaced with a more oxidation resistant alloy, a layered approach can be used to optimize the strength, creep resistance, and oxidation tolerance of various materials, or the existing zirconium alloy cladding can be coated with a more oxidation-resistant material. Molybdenum is one candidate cladding material favored due to its high temperature creep resistance. However, it performs poorly under autoclave testing and suffers degradation under high temperature steam oxidation exposure. Development of composite cladding architectures consisting of a molybdenum core shielded by a molybdenum disilicide (MoSi2) coating is hypothesized to improve the performance of a Mo-based cladding system. MoSi2 was identified based on its high temperature oxidation resistance in O2 atmospheres (e.g. air and “wet air”). However, its behavior in H2O is less known. This report presents thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and x-ray diffraction (XRD) results for MoSi2 exposed to 670-1498 K water vapor. Synthetic air (80-20%, Ar-O2) exposures were also performed, and those results are presented here for a comparative analysis. It was determined that MoSi2 displays drastically different oxidation behavior in water vapor than in dry air. In the 670-1498 K temperature range, four distinct behaviors are observed. Parabolic oxidation is exhibited in only 670

  5. High temperature transient deformation of mixed oxide fuels

    International Nuclear Information System (INIS)

    Slagle, O.D.

    1986-01-01

    The purpose of this paper is to present recent experimental results on fuel creep under transient conditions at high temperatures. The effect of temperature, stress, heating rate, density and grain size were considered. An empirical formulation is derived for the relationship between strain, stress, temperature and heating rate. This relationship provides a means for incorporating stress relief into the analysis of fuel-cladding interaction during an overpower transient. The effect of sample density and initial grain size is considered by varying the sample parameters. Previously derived steady-state creep relationships for the high temperature creep of mixed oxide fuel were combined with the time dependency of creep found for UO 2 to calculate a transient creep relationship for mixed oxide fuel. These calculated results were found to be in good agreement with the measured high temperature transient creep results

  6. Amorphous gallium oxide grown by low-temperature PECVD

    KAUST Repository

    Kobayashi, Eiji

    2018-03-02

    Owing to the wide application of metal oxides in energy conversion devices, the fabrication of these oxides using conventional, damage-free, and upscalable techniques is of critical importance in the optoelectronics community. Here, the authors demonstrate the growth of hydrogenated amorphous gallium oxide (a-GaO:H) thin-films by plasma-enhanced chemical vapor deposition (PECVD) at temperatures below 200 °C. In this way, conformal films are deposited at high deposition rates, achieving high broadband transparency, wide band gap (3.5-4 eV), and low refractive index (1.6 at 500 nm). The authors link this low refractive index to the presence of nanoscale voids enclosing H, as indicated by electron energy-loss spectroscopy. This work opens the path for further metal-oxide developments by low-temperature, scalable and damage-free PECVD processes.

  7. Effect of oxidation and annealing temperature on optical and ...

    Indian Academy of Sciences (India)

    Administrator

    Tin oxide thin films were deposited on glass substrate with 100 nm thickness of Sn, which was coated by magnetron sputtering followed by thermal oxidation at different temperatures. ... Annealing of the samples at 500–650 °C caused the transmittance and optical ..... (αhν)1/2 and (αhν)1/3 to determine the Eg. (b) They used.

  8. Reirradiation of mixed-oxide fuel pins at increased temperatures

    International Nuclear Information System (INIS)

    Lawrence, L.A.; Weber, E.T.

    1976-05-01

    Mixed-oxide fuel pins from EBR-II irradiations were reirradiated in the General Electric Test Reactor (GETR) at higher temperatures than experienced in EBR-II to study effects of the increased operating temperatures on thermal/mechanical and chemical behavior. The response of a mixed-oxide fuel pin to a power increase after having operated at a lower power for a significant portion of its life-time is an area of performance evaluation where little information currently exists. Results show that the cladding diameter changes resulting from the reirradiation are strongly dependent upon both prior burnup level and the magnitude of the temperature increase. Results provide the initial rough outlines of boundaries within which mixed-oxide fuel pins can or cannot tolerate power increases after substantial prior burnup at lower powers

  9. High temperature oxidation test of oxide dispersion strengthened (ODS) steel claddings

    International Nuclear Information System (INIS)

    Narita, Takeshi; Ukai, Shigeharu; Kaito, Takeji; Ohtsuka, Satoshi; Matsuda, Yasushi

    2006-07-01

    In a feasibility study of ODS steel cladding, its high temperature oxidation resistance was evaluated. Although addition of Cr is effective for preventing high temperature oxidation, excessively higher amount of Cr leads to embrittlement due to the Cr-rich α' precipitate formation. In the ODS steel developed by the Japan Atomic Energy Agency (JAEA), the Cr content is controlled in 9Cr-ODS martensite and 12Cr-ODS ferrite. In this study, high temperature oxidation test was conducted for ODS steels, and their results were compared with that of conventional austenitic stainless steel and ferritic-martensitic stainless steel. Following results were obtained in this study. (1) 9Cr-ODS martensitic and 12Cr-ODS ferritic steel have superior high temperature oxidation resistance compared to 11mass%Cr PNC-FMS and even 17mass% SUS430 and equivalent to austenitic PNC316. (2) The superior oxidation resistance of ODS steel was attributed to earlier formation of the protective alpha-Cr 2 O 3 layer at the matrix and inner oxide scale interface. The grain size of ODS steel is finer than that of PNC-FMS, so the superior oxidation resistance of ODS steel can be attributed to the enhanced Cr-supplying rate throughout the accelerated grain boundary diffusion. Finely dispersed Y 2 O 3 oxide particles in the ODS steel matrix may also stabilized the adherence between the protective alpha-Cr 2 O 3 layer and the matrix. (author)

  10. Room temperature aerobic oxidation of amines by a nanocrystalline ruthenium oxide pyrochlore nafion composite catalyst.

    Science.gov (United States)

    Venkatesan, Shanmuganathan; Kumar, Annamalai Senthil; Lee, Jyh-Fu; Chan, Ting-Shan; Zen, Jyh-Myng

    2012-05-14

    The aerobic oxidation of primary amines to their respective nitriles has been carried out at room temperature using a highly reusable nanocrystalline ruthenium oxide pyrochlore Nafion composite catalyst (see figure). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. High temperature oxidation in boiler environment of chromized steel

    Science.gov (United States)

    Alia, F. F.; Kurniawan, T.; Asmara, Y. P.; Ani, M. H. B.; Nandiyanto, A. B. D.

    2017-10-01

    The demand for increasing efficiency has led to the development and construction of higher operating temperature power plant. This condition may lead to more severe thickness losses in boiler tubes due to excessive corrosion process. Hence, the research to improve the corrosion resistance of the current operated material is needed so that it can be applied for higher temperature application. In this research, the effect of chromizing process on the oxidation behaviour of T91 steel was investigated under steam condition. In order to deposit chromium, mixture of chromium (Cr) powder as master alloy, halide salt (NH4Cl) powder as activator and alumina (Al2O3) powder as inert filler were inserted into alumina retort together with the steel sample and heated inside furnace at 1050°C for ten hours under argon gas environment. Furthermore, for the oxidation process, steels were exposed at 700°C at different oxidation time (6h-24h) under steam condition. From FESEM/EDX analysis, it was found that oxidation rate of pack cemented steel was lower than the un-packed steel. These results show that Cr from chromizing process was able to become reservoir for the formation of Cr2O3 in high temperature steam oxidation, and its existence can be used for a longer oxidation time.

  12. Low temperature ozone oxidation of solid waste surrogates

    Science.gov (United States)

    Nabity, James A.; Lee, Jeffrey M.

    2015-09-01

    Solid waste management presents a significant challenge to human spaceflight and especially, long-term missions beyond Earth orbit. A six-month mission will generate over 300 kg of solid wastes per crewmember that must be dealt with to eliminate the need for storage and prevent it from becoming a biological hazard to the crew. There are several methods for the treatment of wastes that include oxidation via ozone, incineration, microbial oxidation or pyrolysis and physical methods such as microwave drying and compaction. In recent years, a low temperature oxidation process using ozonated water has been developed for the chemical conversion of organic wastes to CO2 and H2O. Experiments were conducted to evaluate the rate and effectiveness with which ozone oxidized several different waste materials. Increasing the surface area by chopping or shredding the solids into small pieces more than doubled the rate of oxidation. A greater flow of ozone and agitation of the ozonated water system also increased processing rates. Of the materials investigated, plastics have proven the most difficult to oxidize. The processing of plastics above the glass transition temperatures caused the plastics to clump together which reduced the exposed surface area, while processing at lower temperatures reduced surface reaction kinetics.

  13. Model for low temperature oxidation during long term interim storage

    Energy Technology Data Exchange (ETDEWEB)

    Desgranges, Clara; Bertrand, Nathalie; Gauvain, Danielle; Terlain, Anne [Service de la Corrosion et du Comportement des Materiaux dans leur Environnement, CEA/Saclay - 91191 Gif-sur-Yvette Cedex (France); Poquillon, Dominique; Monceau, Daniel [CIRIMAT UMR 5085, ENSIACET-INPT, 31077 Toulouse Cedex 4 (France)

    2004-07-01

    For high-level nuclear waste containers in long-term interim storage, dry oxidation will be the first and the main degradation mode during about one century. The metal lost by dry oxidation over such a long period must be evaluated with a good reliability. To achieve this goal, modelling of the oxide scale growth is necessary and this is the aim of the dry oxidation studies performed in the frame of the COCON program. An advanced model based on the description of elementary mechanisms involved in scale growth at low temperatures, like partial interfacial control of the oxidation kinetics and/or grain boundary diffusion, is developed in order to increase the reliability of the long term extrapolations deduced from basic models developed from short time experiments. Since only few experimental data on dry oxidation are available in the temperature range of interest, experiments have also been performed to evaluate the relevant input parameters for models like grain size of oxide scale, considering iron as simplified material. (authors)

  14. Model for low temperature oxidation during long term interim storage

    International Nuclear Information System (INIS)

    Desgranges, Clara; Bertrand, Nathalie; Gauvain, Danielle; Terlain, Anne; Poquillon, Dominique; Monceau, Daniel

    2004-01-01

    For high-level nuclear waste containers in long-term interim storage, dry oxidation will be the first and the main degradation mode during about one century. The metal lost by dry oxidation over such a long period must be evaluated with a good reliability. To achieve this goal, modelling of the oxide scale growth is necessary and this is the aim of the dry oxidation studies performed in the frame of the COCON program. An advanced model based on the description of elementary mechanisms involved in scale growth at low temperatures, like partial interfacial control of the oxidation kinetics and/or grain boundary diffusion, is developed in order to increase the reliability of the long term extrapolations deduced from basic models developed from short time experiments. Since only few experimental data on dry oxidation are available in the temperature range of interest, experiments have also been performed to evaluate the relevant input parameters for models like grain size of oxide scale, considering iron as simplified material. (authors)

  15. Oxidation behaviour of titanium in high temperature steam

    Energy Technology Data Exchange (ETDEWEB)

    Moroishi, T; Shida, Y [Sumitomo Metal Industries Ltd., Amagasaki, Hyogo (Japan). Central Research Labs.

    1978-03-01

    The oxidation of pure titanium was studied in superheated steam at 400 -- 550/sup 0/C. The effects of prior cold working and several heat treatment conditions on the oxidation were examined and also the effects of the addition of small amounts of iron and oxygen were investigated. The oxidation mechanism of pure titanium is discussed in relation to the scale structure and the oxidation kinetics. Hydrogen absorption rate was also measured. As a result, the following conclusions were drawn: (1) The oxidation of pure titanium in steam was faster than in air and breakaway oxidation was observed above 500/sup 0/C after the specimen had gained a certain weight. Prior cold working and heat treatment conditions scarcely affected the oxidation rate, whereas the specimen containing small amounts of iron and oxygen showed a little more rapid oxidation. (2) At 500 and 550/sup 0/C a dark grey inner scale and a yellow-brown outer scale were formed. The outer scale was apt to exfoliate after the occurrence of breakaway oxidation. At 400 and 450/sup 0/C only a dark grey scale was observed. All of these oxides were identified as the rutile type, TiO/sub 2/. Furthermore, the presence of a thin and uniform oxygen rich layer beneath the external scale was confirmed at all test temperatures. (3) The measured weight gain approximately followed the cubic rate law; this would be expected for the following reason; one component of the weight gain is due to the dissolved oxygen, the amount of which remains constant after the early stages of oxidation. The second component is due to the parabolic growth of the external TiO/sub 2/ scale. When these contributions are added a pseudo-cubic weight gain curve results. (4) It was shown that 50 percent of the hydrogen generated during the oxidation was absorbed into the metal.

  16. Oxidation behaviour of titanium in high temperature steam

    International Nuclear Information System (INIS)

    Moroishi, Taishi; Shida, Yoshiaki

    1978-01-01

    The oxidation of pure titanium was studied in superheated steam at 400 -- 550 0 C. The effects of prior cold working and several heat treatment conditions on the oxidation were examined and also the effects of the addition of small amounts of iron and oxygen were investigated. The oxidation mechanism of pure titanium is discussed in relation to the scale structure and the oxidation kinetics. Hydrogen absorption rate was also measured. As a result, the following conclusions were drawn: (1) The oxidation of pure titanium in steam was faster than in air and breakaway oxidation was observed above 500 0 C after the specimen had gained a certain weight. Prior cold working and heat treatment conditions scarcely affected the oxidation rate, whereas the specimen containing small amounts of iron and oxygen showed a little more rapid oxidation. (2) At 500 and 550 0 C a dark grey inner scale and a yellow-brown outer scale were formed. The outer scale was apt to exfoliate after the occurrence of breakaway oxidation. At 400 and 450 0 C only a dark grey scale was observed. All of these oxides were identified as the rutile type, TiO 2 . Furthermore, the presence of a thin and uniform oxygen rich layer beneath the external scale was confirmed at all test temperatures. (3) The measured weight gain approximately followed the cubic rate law; this would be expected for the following reason; one component of the weight gain is due to the dissolved oxygen, the amount of which remains constant after the early stages of oxidation. The second component is due to the parabolic growth of the external TiO 2 scale. When these contributions are added a pseudo-cubic weight gain curve results. (4) It was shown that 50 percent of the hydrogen generated during the oxidation was absorbed into the metal. (auth.)

  17. New insights in the low-temperature oxidation of acetylene

    DEFF Research Database (Denmark)

    Wang, Bing-Yin; Liu, Yue-Xi; Weng, Jun-Jie

    2017-01-01

    This work presents new experimental data of C2H2 low-temperature oxidation for equivalence ratios Φ= 0.5–3.0 in a newly designed jet-stirred reactor over a temperature range of 600–1100K at atmospheric pressure with residence time corresponding from 1.94 to 1.06s. Mole fraction profiles of 17...... intermediates including aromatic compounds such as toluene, styrene and ethylbenzene were quantified. A detailed kinetic mechanism involving 295 species and 1830 reactions was established to predict the oxidation of C2H2 and formation of PAH. In developing the mechanism, particular attention was paid...

  18. New Oxide Materials for an Ultra High Temperature Environment

    Energy Technology Data Exchange (ETDEWEB)

    Perepezko, John H. [Univ. of Wisconsin, Madison, WI (United States). Dept. of Materials Science and Engineering

    2017-11-13

    In this project, a new oxide material, Hf6Ta2O17 has been successfully synthesized by the controlled oxidization of Hf-Ta alloys. This oxide exhibits good oxidation resistance, high temperature phase stability up to more than 2000°C, low thermal conductivity and thus could serve as a component or a coating material in an ultrahigh temperature environment. We have examined the microstructure evolution and phase formation sequence during the oxidation exposure of Hf-Ta alloys at 1500°C and identified that the oxidation of a Hf-26.7atomic %Ta alloy leads to the formation of a single phase adherent Hf6Ta2O17 with a complex atomic structure i.e. superstructure. The overall reactive diffusion pathway is consistent with the calculated Hf-Ta-O ternary phase diagram. Besides the synthesis of Hf6Ta2O17 superstructure by oxidizing Hf-Ta alloys, we have also developed a synthesis method based upon the reactive sintering of the correct ratios of mixed powders of HfO2 and Ta2O5 and verified the low thermal conductivity of Hf6Ta2O17 superstructure on these samples. We have completed a preliminary analysis of the oxidation kinetics for Hf6Ta2O17, which shows an initial parabolic oxidation kinetics.

  19. Strategies for Lowering Solid Oxide Fuel Cells Operating Temperature

    Directory of Open Access Journals (Sweden)

    Albert Tarancón

    2009-11-01

    Full Text Available Lowering the operating temperature of solid oxide fuel cells (SOFCs to the intermediate range (500–700 ºC has become one of the main SOFC research goals. High operating temperatures put numerous requirements on materials selection and on secondary units, limiting the commercial development of SOFCs. The present review first focuses on the main effects of reducing the operating temperature in terms of materials stability, thermo-mechanical mismatch, thermal management and efficiency. After a brief survey of the state-of-the-art materials for SOFCs, attention is focused on emerging oxide-ionic conductors with high conductivity in the intermediate range of temperatures with an introductory section on materials technology for reducing the electrolyte thickness. Finally, recent advances in cathode materials based on layered mixed ionic-electronic conductors are highlighted because the decreasing temperature converts the cathode into the major source of electrical losses for the whole SOFC system. It is concluded that the introduction of alternative materials that would enable solid oxide fuel cells to operate in the intermediate range of temperatures would have a major impact on the commercialization of fuel cell technology.

  20. Electrical behavior of amide functionalized graphene oxide and graphene oxide films annealed at different temperatures

    International Nuclear Information System (INIS)

    Rani, Sumita; Kumar, Mukesh; Kumar, Dinesh; Sharma, Sumit

    2015-01-01

    Films of graphene oxide (GO) and amide functionalized graphene oxides (AGOs) were deposited on SiO 2 /Si(100) by spin coating and were thermally annealed at different temperatures. Sheet resistance of GO and AGOs films was measured using four probe resistivity method. GO an insulator at room temperature, exhibits decrease in sheet resistance with increase in annealing temperature. However, AGOs' low sheet resistance (250.43 Ω) at room temperature further decreases to 39.26 Ω after annealing at 800 °C. It was observed that the sheet resistance of GO was more than AGOs up to 700 °C, but effect was reversed after annealing at higher temperature. At higher annealing temperatures the oxygen functionality reduces in GO and sheet resistance decreases. Sheet resistance was found to be annealing time dependent. Longer duration of annealing at a particular temperature results in decrease of sheet resistance. - Highlights: • Amide functionalized graphene oxides (AGOs) were synthesized at room temperature (RT). • AGO films have low sheet resistance at RT as compared to graphene oxide (GO). • Fast decrease in the sheet resistance of GO with annealing as compared to AGOs • AGOs were found to be highly dispersible in polar solvents

  1. Low temperature spent fuel oxidation under tuff repository conditions

    International Nuclear Information System (INIS)

    Einziger, R.E.; Woodley, R.E.

    1985-01-01

    The Nevada Nuclear Waste Storage Investigations Project is studying the suitability of tuffaceous rocks at Yucca Mountain, Nye County, Nevada, for high level waste disposal. The oxidation state of LWR spent fuel in a tuff repository may be a significant factor in determining its ability to inhibit radionuclide migration. Long term exposure at low temperatures to the moist air expected in a tuff repository is expected to increase the oxidation state of the fuel. A program is underway to determine the spent fuel oxidation mechanisms which might be active in a tuff repository. Initial work involves a series of TGA experiments to determine the effectiveness of the technique and to obtain preliminary oxidation data. Tests were run at 200 0 C and 225 0 C for as long as 720 hours. Grain boundary diffusion appears to open up a greater surface area for oxidation prior to onset of bulk diffusion. Temperature strongly influences the oxidation rates. The effect of moisture is small but readily measurable. 25 refs., 7 figs., 4 tabs

  2. Influence of heat treatment temperature on bonding and oxidation ...

    Indian Academy of Sciences (India)

    The effects of heat treatment temperature on the morphology, composition, chemical bonds, oxidation resistance and compressive strength of diamond particles coated with TiO2 films were characterized through scanning electron microscopy, Fourier transform infrared, Raman spectroscopy, X-ray diffraction analysis, X-ray ...

  3. Influence of heat treatment temperature on bonding and oxidation ...

    Indian Academy of Sciences (India)

    Administrator

    Diamond; TiO2 film; heat treatment temperature; anti-oxidation; mechanical properties. 1. Introduction. Due to its ..... figure 4a, which was due to the change of chemical envi- ronment of ... graphite, diamond, diamond-like carbon and carbon.10.

  4. Amorphous gallium oxide grown by low-temperature PECVD

    KAUST Repository

    Kobayashi, Eiji; Boccard, Mathieu; Jeangros, Quentin; Rodkey, Nathan; Vresilovic, Daniel; Hessler-Wyser, Aï cha; Dö beli, Max; Franta, Daniel; De Wolf, Stefaan; Morales-Masis, Monica; Ballif, Christophe

    2018-01-01

    demonstrate the growth of hydrogenated amorphous gallium oxide (a-GaO:H) thin-films by plasma-enhanced chemical vapor deposition (PECVD) at temperatures below 200 °C. In this way, conformal films are deposited at high deposition rates, achieving high broadband

  5. High temperature oxidation of β-NbTi alloys

    International Nuclear Information System (INIS)

    Parida, S.C.; Gupta, N.K.; Rama Rao, G.A.; Sen, B.K.; Krishnan, K.

    2008-01-01

    The isothermal oxidation kinetics of pure Ti metal and two different β-NbTi alloys with compositions of 85 and 75 at.% Ti were studied using thermogravimetric technique in the temperature range of 1073-1323 K at an interval of 50 K. The value of the power exponent n of the rate equation was found to be close to one suggesting that each reaction follows first order kinetic rate law. X-ray diffraction analysis of oxidation products at each temperature revealed the simultaneous formation of TiO 2 and TiNb 2 O 7 . The rate constants and the activation energies of oxidation reactions for each alloy compositions were evaluated. (author)

  6. High-temperature oxidation of ion-implanted tantalum

    International Nuclear Information System (INIS)

    Kaufmann, E.N.; Musket, R.G.; Truhan, J.J.; Grabowski, K.S.; Singer, I.L.; Gossett, C.R.

    1982-01-01

    The oxidation of ion-implanted Ta in two different high temperature regimes has been studied. Oxidations were carried out at 500 0 C in Ar/O 2 mixtures, where oxide growth is known to follow a parabolic rate law in initial stages, and at 1000 0 C in pure O 2 , where a linear-rate behavior obtains. Implanted species include Al, Ce, Cr, Li, Si and Zr at fluences of the order of 10 17 /cm 2 . Oxidized samples were studied using Rutherford backscattering, nuclear reaction analysis, Auger spectroscopy, secondary-ion mass spectroscopy, x-ray diffraction and optical microscopy. Significant differences among the specimens were noted after the milder 500 0 C treatment, specifically, in the amount of oxide formed, the degree of oxygen dissolution in the metal beneath the oxide, and in the redistribution behavior of the implanted solutes. Under the severe 1000 0 C treatment, indications of different solute distributions and of different optical features were found, whereas overall oxidation rate appeared to be unaffected by the presence of the solute. 7 figures

  7. Oxide layer stability in lead-bismuth at high temperature

    Science.gov (United States)

    Martín, F. J.; Soler, L.; Hernández, F.; Gómez-Briceño, D.

    2004-11-01

    Materials protection by 'in situ' oxidation has been studied in stagnant lead-bismuth, with different oxygen levels (H 2/H 2O ratios of 0.3 and 0.03), at temperatures from 535 °C to 600 °C and times from 100 to 3000 h. The materials tested were the martensitic steels F82Hmod, EM10 and T91 and the austenitic stainless steels, AISI 316L and AISI 304L. The results obtained point to the existence of an apparent threshold temperature above which corrosion occurs and the formation of a protective and stable oxide layer is not possible. This threshold temperature depends on material composition, oxygen concentration in the liquid lead-bismuth and time. The threshold temperature is higher for the austenitic steels, especially for the AISI 304L, and it increases with the oxygen concentration in the lead-bismuth. The oxide layer formed disappear with time and, after 3000 h all the materials, except AISI 304L, suffer corrosion, more severe for the martensitic steels and at the highest temperature tested.

  8. Ruthenium(V) oxides from low-temperature hydrothermal synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Hiley, Craig I.; Walton, Richard I. [Department of Chemistry, University of Warwick, Coventry (United Kingdom); Lees, Martin R. [Department of Physics, University of Warwick, Coventry (United Kingdom); Fisher, Janet M.; Thompsett, David [Johnson Matthey Technology Centre, Reading (United Kingdom); Agrestini, Stefano [Max-Planck Institut, CPfS, Dresden (Germany); Smith, Ronald I. [ISIS Neutron and Muon Source, Rutherford Appleton Laboratory, Harwell Oxford, Didcot (United Kingdom)

    2014-04-22

    Low-temperature (200 C) hydrothermal synthesis of the ruthenium oxides Ca{sub 1.5}Ru{sub 2}O{sub 7}, SrRu{sub 2}O{sub 6}, and Ba{sub 2}Ru{sub 3}O{sub 9}(OH) is reported. Ca{sub 1.5}Ru{sub 2}O{sub 7} is a defective pyrochlore containing Ru{sup V/VI}; SrRu{sub 2}O{sub 6} is a layered Ru{sup V} oxide with a PbSb{sub 2}O{sub 6} structure, whilst Ba{sub 2}Ru{sub 3}O{sub 9}(OH) has a previously unreported structure type with orthorhombic symmetry solved from synchrotron X-ray and neutron powder diffraction. SrRu{sub 2}O{sub 6} exhibits unusually high-temperature magnetic order, with antiferromagnetism persisting to at least 500 K, and refinement using room temperature neutron powder diffraction data provides the magnetic structure. All three ruthenates are metastable and readily collapse to mixtures of other oxides upon heating in air at temperatures around 300-500 C, suggesting they would be difficult, if not impossible, to isolate under conventional high-temperature solid-state synthesis conditions. (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. Anodes for Solid Oxide Fuel Cells Operating at Low Temperatures

    DEFF Research Database (Denmark)

    Abdul Jabbar, Mohammed Hussain

    An important issue that has limited the potential of Solid Oxide Fuel Cells (SOFCs) for portable applications is its high operating temperatures (800-1000 ºC). Lowering the operating temperature of SOFCs to 400-600 ºC enable a wider material selection, reduced degradation and increased lifetime....... On the other hand, low-temperature operation poses serious challenges to the electrode performance. Effective catalysts, redox stable electrodes with improved microstructures are the prime requisite for the development of efficient SOFC anodes. The performance of Nb-doped SrT iO3 (STN) ceramic anodes...... at 400ºC. The potential of using WO3 ceramic as an alternative anode materials has been explored. The relatively high electrode polarization resistance obtained, 11 Ohm cm2 at 600 ºC, proved the inadequate catalytic activity of this system for hydrogen oxidation. At the end of this thesis...

  10. High Temperature Oxidation Behavior of Zirconium Alloy with Nano structured Oxide Layer in Air Environment

    International Nuclear Information System (INIS)

    Park, Y. J.; Kim, J. W.; Park, J. W.; Cho, S. O.

    2016-01-01

    If the temperature of the cladding materials increases above 1000 .deg. C, which can be caused by a loss of coolant accident (LOCA), Zr becomes an auto-oxidation catalyst and hence produces a huge amount of hydrogen gas from water. Therefore, many investigations are being carried out to prevent (or reduce) the hydrogen production from Zr-based cladding materials in the nuclear reactors. Our team has developed an anodization technique by which nanostructured oxide can be formed on various flat metallic elements such as Al, Ti, and Zr-based alloy. Anodization is a simple electrochemical technique and requires only a power supply and an electrolyte. In this study, Zr-based alloys with nanostructured oxide layers were oxidized by using Thermogravimetry analysis (TGA) and compared with the pristine one. It reveals that the nanostructured oxide layer can prevent oxidation of substrate metal in air. Oxidation behavior of the pristine Zr-Nb-Sn alloy and the Zr-Nb-Sn alloy with nanostructured oxide layer evaluated by measuring weight gain (TGA). In comparison with the pristine Zr-Nb-Sn alloy, weight gain of the Zr-Nb-Sn alloy with nanostructured oxide layer is lower than 10% even for 12 hours oxidation in air.

  11. Effect of temperature on the oxidation of soybean biodiesel

    Directory of Open Access Journals (Sweden)

    Pereira, G. G.

    2015-06-01

    Full Text Available This paper proposes to examine the effect of temperature on the oxidation behavior of biodiesel. Soybean biodiesel was oxidized at different temperatures (room temperature, 60, and 110 °C, and the increase in primary and secondary oxidation products was determined based on the peroxide and anisidine values, respectively, during the induction period (IP. The results indicated that the evolution of hydroperoxides followed zero-order reaction kinetics during the IP at all temperatures, and their rate of formation was exponentially affected by temperature. It was also deduced that temperature influenced the ratio between primary and secondary oxidation products formation, which decreased as the temperature increased. Additionally, it was possible to predict the oxidation behavior of the soybean biodiesel at room temperature by an exponential model fitted to the IP values at different temperatures (70, 80, 90, 100, and 110 °C using the Rancimat apparatus.El propósito de este trabajo es evaluar el efecto de la temperatura en el comportamiento oxidativo del biodiesel. Biodiesel derivado de aceite de soja fue oxidado a diferentes temperaturas (temperatura ambiente, 60 y 110 °C y se evaluaron el contenido de compuestos primarios y secundarios de oxidación mediante el índice de peróxidos y de anisidina, respectivamente, a lo largo del periodo de inducción. Los resultados indicaron que el contenido de hidroperóxidos evolucionó siguiendo una cinética de orden cero a lo largo del periodo de inducción a todas las temperaturas y que su velocidad de formación cambió exponencialmente con la temperatura. También se dedujo que la temperatura influyó en la relación entre la formación de los productos de oxidación primarios y secundarios, disminuyendo a medida que aumentaba la temperatura. Además, fue posible predecir el comportamiento oxidativo del biodiesel de soja a temperatura ambiente ajustando a un modelo exponencial los valores de periodo

  12. Oxidation of 304 stainless steel in high-temperature steam

    Science.gov (United States)

    Ishida, Toshihisa; Harayama, Yasuo; Yaguchi, Sinnosuke

    1986-08-01

    An experiment on oxidation of 304 stainless steel was performed in steam between 900°C and 1350°C, using the spare cladding of the reactor of the nuclear-powered ship Mutsu. The temperature range was appropriate for a postulated loss of coolant accident (LOCA) analysis of a LWR. The oxidation kinetics were found to obey the parabolic law during the first period of 8 min. After the first period, the parabolic reaction rate constant decreased in the case of heating temperatures between 1100°C and 1250°C. At 1250°C, especially, a marked decrease was observed in the oxide scale-forming kinetics when the surface treated initially by mechanical polishing and given a residual stress. This enhanced oxidation resistance was attributed to the presence of a chromium-enriched layer which was detected by use of an X-ray microanalyzer. The oxidation kinetics equation obtained for the first 8 min is applicable to the model calculation of a hypothetical LOCA in a LWR, employing 304 stainless steel cladding.

  13. Low temperature solid oxide electrolytes (LT-SOE): A review

    Science.gov (United States)

    Singh, B.; Ghosh, S.; Aich, S.; Roy, B.

    2017-01-01

    Low temperature solid oxide fuel cell (LT-SOFC) can be a source of power for vehicles, online grid, and at the same time reduce system cost, offer high reliability, and fast start-up. A huge amount of research work, as evident from the literature has been conducted for the enhancement of the ionic conductivity of LT electrolytes in the last few years. The basic conduction mechanisms, advantages and disadvantages of different LT oxide ion conducting electrolytes {BIMEVOX systems, bilayer systems including doped cerium oxide/stabilised bismuth oxide and YSZ/DCO}, mixed ion conducting electrolytes {doped cerium oxides/alkali metal carbonate composites}, and proton conducting electrolytes {doped and undoped BaCeO3, BaZrO3, etc.} are discussed here based on the recent research articles. Effect of various material aspects (composition, doping, layer thickness, etc.), fabrication methods (to achieve different microstructures and particle size), design related strategies (interlayer, sintering aid etc.), characterization temperature & environment on the conductivity of the electrolytes and performance of the fuel cells made from these electrolytes are shown in tabular form and discussed. The conductivity of the electrolytes and performance of the corresponding fuel cells are compared. Other applications of the electrolytes are mentioned. A few considerations regarding the future prospects are pointed.

  14. Tunable room-temperature ferromagnet using an iron-oxide and graphene oxide nanocomposite

    KAUST Repository

    Lin, Aigu L.; Rodrigues, J. N B; Su, Chenliang; Milletari, M.; Loh, Kian Ping; Wu, Tao; Chen, Wei; Neto, A. H Castro; Adam, Shaffique; Wee, Andrew T S

    2015-01-01

    Magnetic materials have found wide application ranging from electronics and memories to medicine. Essential to these advances is the control of the magnetic order. To date, most room-temperature applications have a fixed magnetic moment whose orientation is manipulated for functionality. Here we demonstrate an iron-oxide and graphene oxide nanocomposite based device that acts as a tunable ferromagnet at room temperature. Not only can we tune its transition temperature in a wide range of temperatures around room temperature, but the magnetization can also be tuned from zero to 0.011 A m2/kg through an initialization process with two readily accessible knobs (magnetic field and electric current), after which the system retains its magnetic properties semi-permanently until the next initialization process. We construct a theoretical model to illustrate that this tunability originates from an indirect exchange interaction mediated by spin-imbalanced electrons inside the nanocomposite. © 2015 Scientific Reports.

  15. Tunable room-temperature ferromagnet using an iron-oxide and graphene oxide nanocomposite

    KAUST Repository

    Lin, Aigu L.

    2015-06-23

    Magnetic materials have found wide application ranging from electronics and memories to medicine. Essential to these advances is the control of the magnetic order. To date, most room-temperature applications have a fixed magnetic moment whose orientation is manipulated for functionality. Here we demonstrate an iron-oxide and graphene oxide nanocomposite based device that acts as a tunable ferromagnet at room temperature. Not only can we tune its transition temperature in a wide range of temperatures around room temperature, but the magnetization can also be tuned from zero to 0.011 A m2/kg through an initialization process with two readily accessible knobs (magnetic field and electric current), after which the system retains its magnetic properties semi-permanently until the next initialization process. We construct a theoretical model to illustrate that this tunability originates from an indirect exchange interaction mediated by spin-imbalanced electrons inside the nanocomposite. © 2015 Scientific Reports.

  16. Materials for high temperature solid oxide fuel cells

    International Nuclear Information System (INIS)

    Singhal, S.C.

    1987-01-01

    High temperature solid oxide fuel cells show great promise for economical production of electricity. These cells are based upon the ability of stabilized zirconia to operate as an oxygen ion conductor at elevated temperatures. The design of the tubular solid oxide fuel cell being pursued at Westinghouse is illustrated. The cell uses a calcia-stabilized zironcia porous support tube, which acts both as a structural member onto which the other cell components are fabricated in the form of thin layers, and as a functional member to allow the passage, via its porosity, of air (or oxygen) to the air electrode. This paper summarizes the materials and fabrication processes for the various cell components

  17. Melting temperature of uranium - plutonium mixed oxide fuel

    Energy Technology Data Exchange (ETDEWEB)

    Ishii, Tetsuya; Hirosawa, Takashi [Power Reactor and Nuclear Fuel Development Corp., Oarai, Ibaraki (Japan). Oarai Engineering Center

    1997-08-01

    Fuel melting temperature is one of the major thermodynamical properties that is used for determining the design criteria on fuel temperature during irradiation in FBR. In general, it is necessary to evaluate the correlation of fuel melting temperature to confirm that the fuel temperature must be kept below the fuel melting temperature during irradiation at any conditions. The correlations of the melting temperature of uranium-plutonium mixed oxide (MOX) fuel, typical FBR fuel, used to be estimated and formulized based on the measured values reported in 1960`s and has been applied to the design. At present, some experiments have been accumulated with improved experimental techniques. And it reveals that the recent measured melting temperatures does not agree well to the data reported in 1960`s and that some of the 1960`s data should be modified by taking into account of the recent measurements. In this study, the experience of melting temperature up to now are summarized and evaluated in order to make the fuel pin design more reliable. The effect of plutonium content, oxygen to metal ratio and burnup on MOX fuel melting was examined based on the recent data under the UO{sub 2} - PuO{sub 2} - PuO{sub 1.61} ideal solution model, and then formulized. (J.P.N.)

  18. Melting temperature of uranium - plutonium mixed oxide fuel

    International Nuclear Information System (INIS)

    Ishii, Tetsuya; Hirosawa, Takashi

    1997-08-01

    Fuel melting temperature is one of the major thermodynamical properties that is used for determining the design criteria on fuel temperature during irradiation in FBR. In general, it is necessary to evaluate the correlation of fuel melting temperature to confirm that the fuel temperature must be kept below the fuel melting temperature during irradiation at any conditions. The correlations of the melting temperature of uranium-plutonium mixed oxide (MOX) fuel, typical FBR fuel, used to be estimated and formulized based on the measured values reported in 1960's and has been applied to the design. At present, some experiments have been accumulated with improved experimental techniques. And it reveals that the recent measured melting temperatures does not agree well to the data reported in 1960's and that some of the 1960's data should be modified by taking into account of the recent measurements. In this study, the experience of melting temperature up to now are summarized and evaluated in order to make the fuel pin design more reliable. The effect of plutonium content, oxygen to metal ratio and burnup on MOX fuel melting was examined based on the recent data under the UO 2 - PuO 2 - PuO 1.61 ideal solution model, and then formulized. (J.P.N.)

  19. Thermal deoxygenation of graphite oxide at low temperature

    International Nuclear Information System (INIS)

    Kampars, V; Legzdina, M

    2015-01-01

    Synthesis of graphene via the deoxygenation of the graphite oxide (GO) is a method for the large-scale production of this nanomaterial possessing exceptional mechanical, electrical and translucent properties. Graphite oxide sheet contains at least four different oxygen atoms connected to the Csp 3 and Csp 2 atoms of the sheet in the form of hydroxyl, epoxy, carboxyl or carbonyl groups. Some of these functional groups are located at the surface but others situated at the edges of the platelets. To obtain the graphene nanoplatelets or the few-layer graphene the oxygen functionalities must be removed. Exfoliation and deoxygenation can be accomplished by the use of chemical reductants or heat. Thermal deoxygenation as greener and simpler approach is more preferable over chemical reduction approach. Usually a considerable mass loss of GO observed upon heating at temperatures starting at 200 °C and is attributed to the deoxygenation process. In order to avoid the defects of the obtained graphene sheets it is very important to find the methods for lowering the deoxygenation temperature of GO. Herein, we have investigated the way treatment of the Hummer's synthesis product with acetone and methyl tert-butyl ether under ultrasonication in order to lower the thermal stability of the graphite oxide and its deoxygenation temperature. The obtained results indicate that treatment of the graphite oxide with solvents mentioned above substantially reduces the reduction and exfoliation temperature (130 °C) under ambient atmosphere. The investigation of the composition of evolved gases by hyphenated Pyr/GC/MS method at different experimental conditions under helium atmosphere shows that without the expected H 2 O, CO and CO 2 also sulphur dioxide and acetone has been released

  20. Temperature-dependent electrical property transition of graphene oxide paper

    International Nuclear Information System (INIS)

    Huang Xingyi; Jiang Pingkai; Zhi Chunyi; Golberg, Dmitri; Bando, Yoshio; Tanaka, Toshikatsu

    2012-01-01

    Reduction of graphene oxide is primarily important because different reduction methods may result in graphene with totally different properties. For systematically exploring the reduction of graphene oxide, studies of the temperature-dependent electrical properties of graphene oxide (GO) are urgently required. In this work, for the first time, broadband dielectric spectroscopy was used to carry out an in situ investigation on the transition of the electrical properties of GO paper from −40 to 150 °C. The results clearly reveal a very interesting four-stage transition of electrical properties of GO paper with increasing temperature: insulator below 10 °C (stage 1), semiconductor at between 10 and 90 °C (stage 2), insulator at between 90 and 100 °C (stage 3), and semiconductor again at above 100 °C (stage 4). Subsequently, the transition mechanism was discussed in combination with detailed dielectric properties, microstructure and thermogravimetric analyses. It is suggested that the temperature-dependent transition of electronic properties of GO is closely associated with the ion mobility, water molecules removal and the reduction of GO in the GO paper. Most importantly, the present work clearly demonstrates the reduction of GO paper starts at above 100 °C. (paper)

  1. Flare pits wastes remediation by low temperature oxidation

    International Nuclear Information System (INIS)

    Catalan, L. J. L.; Jamaluddin, A. K. M.; Mehta, R.; Moore, R. G.; Okazawa, N.; Ursenbach, M.

    1997-01-01

    The remediation of contaminated soil in oilfield sites, flare pits in particular, is subject to strict environmental regulations. Most current remediation techniques such as biological or thermal treatment are not particularly effective in highly contaminated sites, or effective only at costs that are considered prohibitive. This contribution describes a cost-effective method for the treatment of contaminated soil in-situ. The proposed treatment involves low temperature oxidation which converts the hydrocarbons in the contaminated soil to inert coke. In laboratory studies contaminated soil was oxidized with air at temperatures between 150 degrees C and 170 degrees C for three weeks. After the three week treatment extractable hydrocarbon levels were reduced to less than 0.1 per cent. Bioassays also demonstrated that toxicity associated with hydrocarbons was eliminated. Salts and metals remaining in the soil after treatment were removed by leaching with water. Low temperature oxidation requires no special equipment; it can occur under conditions and with equipment that are readily available in an oilfield setting. 5 refs., 8 tabs., 7 figs

  2. Platinum redispersion on metal oxides in low temperature fuel cells.

    Science.gov (United States)

    Tripković, Vladimir; Cerri, Isotta; Nagami, Tetsuo; Bligaard, Thomas; Rossmeisl, Jan

    2013-03-07

    We have analyzed the aptitude of several metal oxide supports (TiO(2), SnO(2), NbO(2), ZrO(2), SiO(2), Ta(2)O(5) and Nb(2)O(5)) to redisperse platinum under electrochemical conditions pertinent to the Proton Exchange Membrane Fuel Cell (PEMFC) cathode. The redispersion on oxide supports in air has been studied in detail; however, due to different operating conditions it is not straightforward to link the chemical and the electrochemical environment. The largest differences reflect in (1) the oxidation state of the surface (the oxygen species coverage), (2) temperature and (3) the possibility of platinum dissolution at high potentials and the interference of redispersion with normal working potential of the PEMFC cathode. We have calculated the PtO(x) (x = 0, 1, 2) adsorption energies on different metal oxides' surface terminations as well as inside the metal oxides' bulk, and we have concluded that NbO(2) might be a good support for platinum redispersion at PEMFC cathodes.

  3. Cathodes for Solid Oxide Fuel Cells Operating at Low Temperatures

    DEFF Research Database (Denmark)

    Samson, Alfred Junio

    . High performance cathodes were obtained from strontium-doped lanthanum cobaltite (LSC) infiltrated - Ce0.9Gd0.1O1.95 (CGO) ionic conducting backbone. Systematic tuning of the CGO and LSC firing temperatures and LSC loading resulted in a cathode with low polarization resistance, Rp = 0.044 cm2 at 600......This dissertation focuses on the development of nanostructured cathodes for solid oxide fuel cells (SOFCs) and their performance at low operating temperatures. Cathodes were mainly fabricated by the infiltration method, whereby electrocatalysts are introduced onto porous, ionic conducting backbones...... with increasing LSC firing temperature, highlighting the importance of materials compability over higher ionic conductivity. The potential of Ca3Co4O9+delta as an electrocatalyst for SOFCs has also been explored and encouraging results were found i.e., Rp = 0.64 cm2 for a Ca3Co4O9+delta/CGO 50 vol % composite...

  4. Facile synthesis of iron oxides/reduced graphene oxide composites: application for electromagnetic wave absorption at high temperature

    OpenAIRE

    Lili Zhang; Xinxin Yu; Hongrui Hu; Yang Li; Mingzai Wu; Zhongzhu Wang; Guang Li; Zhaoqi Sun; Changle Chen

    2015-01-01

    Iron oxides/reduced graphene oxide composites were synthesized by facile thermochemical reactions of graphite oxide and FeSO4?7H2O. By adjusting reaction temperature, ?-Fe2O3/reduced graphene oxide and Fe3O4/reduced graphene oxide composites can be obtained conveniently. Graphene oxide and reduced graphene oxide sheets were demonstrated to regulate the phase transition from ?-Fe2O3 to Fe3O4 via ?-Fe2O3, which was reported for the first time. The hydroxyl groups attached on the graphene oxide ...

  5. Contribution to the study of the oxidation reaction of the carbon oxide in contact with catalysts issued from the decomposition of nickel hydro-aluminates at various temperatures; Contribution a l'etude de la reaction d'oxydation de l'oxyde de carbone au contact des catalyseurs issus de la decomposition a diverses temperatures des hydroaluminates de nickel

    Energy Technology Data Exchange (ETDEWEB)

    Samaane, Mikhail

    1966-09-26

    Addressing the study of the oxidation reaction of carbon oxide which produces carbon dioxide, this research thesis reports the study of this reaction in presence of catalysts (2NiO + Al{sub 2}O{sub 3}, NiAl{sub 2}O{sub 4} and NiO + NiAl{sub 2}O{sub 4}) issued from the decomposition of nickel hydro-aluminates at different temperatures. The first part describes experimental techniques and the nature of materials used in this study. The second part reports the study of the catalytic activity of the 2NiO+Al{sub 2}O{sub 3} catalyst during the oxidation of CO. Preliminary studies are also reported: structure and texture of nickel hydro-aluminate which is the raw material used to produce catalysts, activation of this compound to develop the catalytic activity in CO oxidation, chemisorption of CO, O{sub 2} and CO{sub 2} on the 2NiO+Al{sub 2}O{sub 3} solid, interaction of adsorbed gases at the solid surface, and kinetic study of the oxidation reaction. The third part reports the study of the catalytic activity in the oxidation reaction of CO of spinel catalysts (NiAl{sub 2}O{sub 4} and NiO+NiAl{sub 2}O{sub 4}) obtained by calcination of nickel hydro-aluminates at high temperature. The formation of the spinel phase, the chemisorption of CO, O{sub 2} and CO{sub 2} on NiAl{sub 2}O{sub 4}, and the kinetic of the oxidation reaction are herein studied.

  6. Asymptotic Slavery in the Copper Oxide High Temperature Superconductors

    Science.gov (United States)

    Phillips, Philip

    2004-05-01

    Vast progress in theoretical solid state physics has been made by constructing models which mimic the low-energy properties of solids. Essential to the success of this program is the separability of the high and low energy degrees of freedom. While it is hoped that a high energy reduction can be made to solve the problem of high temperature superconductivity in the copper oxide materials, I will show that no consistent theory is possible if the high energy scale is removed. At the heart of the problem is the mixing of all energy scales (that is, UV-IR mixing) in the copper-oxide materials. Optical experiments demonstrate that the number of low-energy degrees of freedom is derived from a high energy scale. The implications of the inseparability of the high and low energy degrees of freedom on the phase diagram of the cuprates is discussed.

  7. Microstructural characteristics of high-temperature oxidation in nickel-base superalloy

    International Nuclear Information System (INIS)

    Khalid, F.A.

    1997-01-01

    Superalloys are used for aerospace and nuclear applications where they can withstand high-temperature and severe oxidizing conditions. High-temperature oxidation behavior of a nickel-base superalloy is examined using optical and scanning electron microscopical techniques. The morphology of the oxide layers developed is examined, and EDX microanalysis reveals diffusion of the elements across the oxide-metal interface. Evidence of internal oxidation is presented, and the role of structural defects is considered. The morphology of the oxide-metal interface formed in the specimens exposed in steam and air is examined to elucidate the mechanism of high-temperature oxidation

  8. Proceedings of damage and oxidation protection in high temperature composites

    International Nuclear Information System (INIS)

    Haritos, G.K.; Ochoa, O.O.

    1991-01-01

    This book contains proceedings of Damage and Oxidation Protection in High Temperature Composites. Topics covered include: current issues in the development of new materials and structural concepts for the aerospace structures of the future; transportation vehicles of the future; materials and structural concepts; fundamental understanding and quantitative descriptions of the physical processes and mechanisms controlling the behavior of emerging materials and structures; and the critical need for advances in our understanding of how the interaction of service loads and environment influences the lifecycle of emerging structures and materials

  9. Composite cathode based on yttria stabilized bismuth oxide for low-temperature solid oxide fuel cells

    International Nuclear Information System (INIS)

    Xia Changrong; Zhang Yuelan; Liu Meilin

    2003-01-01

    Composites consisting of silver and yttria stabilized bismuth oxide (YSB) have been investigated as cathodes for low-temperature honeycomb solid oxide fuel cells with stabilized zirconia as electrolytes. At 600 deg. C, the interfacial polarization resistances of a porous YSB-Ag cathode is about 0.3 Ω cm 2 , more than one order of magnitude smaller than those of other reported cathodes on stabilized zirconia. For example, the interfacial resistances of a traditional YSZ-lanthanum maganites composite cathode is about 11.4 Ω cm 2 at 600 deg. C. Impedance analysis indicated that the performance of an YSB-Ag composite cathode fired at 850 deg. C for 2 h is severely limited by gas transport due to insufficient porosity. The high performance of the YSB-Ag cathodes is very encouraging for developing honeycomb fuel cells to be operated at temperatures below 600 deg. C

  10. Green synthesis of Ni-Nb oxide catalysts for low-temperature oxidative dehydrogenation of ethane

    KAUST Repository

    Zhu, Haibo

    2015-03-05

    The straightforward solid-state grinding of a mixture of Ni nitrate and Nb oxalate crystals led to, after mild calcination (T<400°C), nanostructured Ni-Nb oxide composites. These new materials efficiently catalyzed the oxidative dehydrogenation (ODH) of ethane to ethylene at a relatively low temperature (T<300°C). These catalysts appear to be much more stable than the corresponding composites prepared by other chemical methods; more than 90% of their original intrinsic activity was retained after 50h with time on-stream. Furthermore, the stability was much less affected by the Nb content than in composites prepared by classical "wet" syntheses. These materials, obtained in a solvent-free way, are thus promising green and sustainable alternatives to the current Ni-Nb candidates for the low-temperature ODH of ethane.

  11. Electronic structure of the high-temperature oxide superconductors

    International Nuclear Information System (INIS)

    Pickett, W.E.

    1989-01-01

    Since the discovery of superconductivity above 30 K by Bednorz and Mueller in the La copper oxide system, the critical temperature has been raised to 90 K in YBa 2 Cu 3 O 7 and to 110 and 125 K in Bi-based and Tl-based copper oxides, respectively. In the two years since this Nobel-prize-winning discovery, a large number of electronic structure calculations have been carried out as a first step in understanding the electronic properties of these materials. In this paper these calculations (mostly of the density-functional type) are gathered and reviewed, and their results are compared with the relevant experimental data. The picture that emerges is one in which the important electronic states are dominated by the copper d and oxygen p orbitals, with strong hybridization between them. Photon, electron, and positron spectroscopies provide important information about the electronic states, and comparison with electronic structure calculations indicates that, while many features can be interpreted in terms of existing calculations, self-energy corrections (''correlations'') are important for a more detailed understanding. The antiferromagnetism that occurs in some regions of the phase diagram poses a particularly challenging problem for any detailed theory. The study of structural stability, lattice dynamics, and electron-phonon coupling in the copper oxides is also discussed. Finally, a brief review is given of the attempts so far to identify interaction constants appropriate for a model Hamiltonian treatment of many-body interactions in these materials

  12. Properties of zinc oxide at low and moderate temperatures

    International Nuclear Information System (INIS)

    Lashkarev, G.V.; Karpina, V.A.; Lazorenko, V.I.; Evtushenko, A.I.; Shteplyuk, I.I.; Khranovskij, V.D.

    2011-01-01

    The properties of zinc oxide as an analogue of gallium nitride are considered in a wide temperature range and the field of its potential applications. The economic and ecologic benefits as well as radiation resistivity of ZnO in comparison with Group III nitrides are indicated. Methods of growth of films and nanostructures of high crystal perfection are proposed. In particular, a magnetron method for layer growth of films is implemented which permits to realize their high structural perfection and considerable thickness inappropriate to some other methods. It is shown that monochromatic UV light may be obtained on excitation of films by short-wave radiation and electrons. This makes it possible to use them in the sources of short-wave radiation. The effectiveness of field emission for ZnO nanostructures and films is demonstrated which opens the prospect for their use in vacuum microelectronics devices. In particular, a phototransistor based on ZnO films doped with nitrogen was fabricated the photosensitivity of which was two orders of magnitude higher than that of conventional detectors. The physical basis of creating blue, green LEDs based on zinc oxide film and its solid solutions with CdO are outlined. The importance of active research in physics, and production procedures of zinc oxide-based devices is underlined.

  13. Ni–Ta–O mixed oxide catalysts for the low temperature oxidative dehydrogenation of ethane to ethylene

    KAUST Repository

    Zhu, Haibo; Rosenfeld, Devon C.; Anjum, Dalaver H.; Sangaru, Shiv; Saih, Youssef; Ould-Chikh, Samy; Basset, Jean-Marie

    2015-01-01

    The "wet" sol-gel and "dry" solid-state methods were used to prepare Ni-Ta-O mixed oxide catalysts. The resulting Ni-Ta oxides exhibit high activity and selectivity for the low temperature oxidative dehydrogenation of ethane to ethylene. The Ta

  14. Thermal sensor based zinc oxide diode for low temperature applications

    Energy Technology Data Exchange (ETDEWEB)

    Ocaya, R.O. [Department of Physics, University of the Free State (South Africa); Al-Ghamdi, Ahmed [Department of Physics, Faculty of Science, King Abdulaziz University, Jeddah, 21589 (Saudi Arabia); El-Tantawy, F. [Department of Physics, Faculty of Science, Suez Canal University, Ismailia (Egypt); Center of Nanotechnology, King Abdulaziz University, Jeddah (Saudi Arabia); Farooq, W.A. [Department of Physics and Astronomy, College of Science, King Saud University, Riyadh (Saudi Arabia); Yakuphanoglu, F., E-mail: fyhan@hotmail.com [Department of Physics, Faculty of Science, King Abdulaziz University, Jeddah, 21589 (Saudi Arabia); Department of Physics, Faculty of Science, Firat University, Elazig, 23169 (Turkey)

    2016-07-25

    The device parameters of Al/p-Si/Zn{sub 1-x}Al{sub x}O-NiO/Al Schottky diode for x = 0.005 were investigated over the 50 K–400 K temperature range using direct current–voltage (I–V) and impedance spectroscopy. The films were prepared using the sol–gel method followed by spin-coating on p-Si substrate. The ideality factor, barrier height, resistance and capacitance of the diode were found to depend on temperature. The calculated barrier height has a mean. Capacitance–voltage (C–V) measurements show that the capacitance decreases with increasing frequency, suggesting a continuous distribution of interface states over the surveyed 100 kHz to 1 MHz frequency range. The interface state densities, N{sub ss}, of the diode were calculated and found to peak as functions of bias and temperature in two temperature regions of 50 K–300 K and 300 K–400 K. A peak value of approximately 10{sup 12}/eV cm{sup 2} was observed around 0.7 V bias for 350 K and at 3 × 10{sup 12}/eVcm{sup 2} around 2.2 V bias for 300 K. The relaxation time was found to average 4.7 μs over all the temperatures, but showing its lowest value of 1.58 μs at 300 K. It is seen that the interface states of the diode is controlled by the temperature. This suggests that Al/p-Si/Zn1-xAlxO-NiO/Al diode can be used as a thermal sensors for low temperature applications. - Highlights: • Al/pSi/Zn1-xAlxO-NiO/Al Schottky diode was fabricated by sol gel method. • The interface state density of the diode is controlled by the temperature. • Zinc oxide based diode can be used as a thermal sensor for low temperature applications.

  15. Temperature-independent sensors based on perovskite-type oxides

    International Nuclear Information System (INIS)

    Zaza, F.; Frangini, S.; Masci, A.; Leoncini, J.; Pasquali, M.; Luisetto, I.; Tuti, S.

    2013-01-01

    The need of energy security and environment sustainability drives toward the development of energy technology in order to enhance the performance of internal combustion engines. Gas sensors play a key role for controlling the fuel oxygen ratio and monitoring the pollution emissions. The perovskite-type oxides can be synthesized for an extremely wide variety of combinations of chemical elements, allowing to design materials with suitable properties for sensing application. Lanthanum strontium ferrites, such as La 0.7 Sr 0.3 FeO 3 , are suitable oxygen sensing materials with temperature-independence conductivity, but they have low chemical stability under reducing conditions. The addition of aluminum into the perovskite structure improves the material properties in order to develop suitable oxygen sensing probes for lean burn engine control systems. Perovskite-type oxides with formula (La 0.7 Sr 0.3 )(Al x Fe 1−x )O 3 was synthesized by the citrate-nitrate combustion synthesis method. XRD analyses, show that it was synthesized a phase-pure powder belonging to the perovskite structure. Aluminum affects both the unit cell parameters, by shrinking the unit cell, and the powder morphology, by promoting the synthesis of particles with small crystallite size and large specific surface area. The partial substitution of iron with aluminum improves the chemical stability under reducing gas conditions and modulates the oxygen sensitivity by affecting the relative amount of Fe 4+ and Fe 3+ , as confirmed from TPR profiles. In the same time, the addition of aluminum does not affects the temperature-independent properties of lanthanum strontium ferrites. Indeed, the electrical measurements show that (La 0.7 Sr 0.3 )(Al x Fe 1−x )O 3 perovskites have temperature-independence conductivity from 900 K

  16. Temperature-independent sensors based on perovskite-type oxides

    Energy Technology Data Exchange (ETDEWEB)

    Zaza, F.; Frangini, S.; Masci, A. [ENEA-Casaccia R.C., Via Anguillarese 301, 00123 S.Maria di Galeria, Rome (Italy); Leoncini, J.; Pasquali, M. [University La Sapienza, Piazza Via del Castro Laurenziano 7, 00161 Rome (Italy); Luisetto, I.; Tuti, S. [University RomaTre, Rome 00146 (Italy)

    2014-06-19

    The need of energy security and environment sustainability drives toward the development of energy technology in order to enhance the performance of internal combustion engines. Gas sensors play a key role for controlling the fuel oxygen ratio and monitoring the pollution emissions. The perovskite-type oxides can be synthesized for an extremely wide variety of combinations of chemical elements, allowing to design materials with suitable properties for sensing application. Lanthanum strontium ferrites, such as La{sub 0.7}Sr{sub 0.3}FeO{sub 3}, are suitable oxygen sensing materials with temperature-independence conductivity, but they have low chemical stability under reducing conditions. The addition of aluminum into the perovskite structure improves the material properties in order to develop suitable oxygen sensing probes for lean burn engine control systems. Perovskite-type oxides with formula (La{sub 0.7}Sr{sub 0.3})(Al{sub x}Fe{sub 1−x})O{sub 3} was synthesized by the citrate-nitrate combustion synthesis method. XRD analyses, show that it was synthesized a phase-pure powder belonging to the perovskite structure. Aluminum affects both the unit cell parameters, by shrinking the unit cell, and the powder morphology, by promoting the synthesis of particles with small crystallite size and large specific surface area. The partial substitution of iron with aluminum improves the chemical stability under reducing gas conditions and modulates the oxygen sensitivity by affecting the relative amount of Fe{sup 4+} and Fe{sup 3+}, as confirmed from TPR profiles. In the same time, the addition of aluminum does not affects the temperature-independent properties of lanthanum strontium ferrites. Indeed, the electrical measurements show that (La{sub 0.7}Sr{sub 0.3})(Al{sub x}Fe{sub 1−x})O{sub 3} perovskites have temperature-independence conductivity from 900 K.

  17. Halogen effect for improving high temperature oxidation resistance of Ti-50Al by anodization

    Science.gov (United States)

    Mo, Min-Hua; Wu, Lian-Kui; Cao, Hua-Zhen; Lin, Jun-Pin; Zheng, Guo-Qu

    2017-06-01

    The high temperature oxidation resistance of Ti-50Al was significantly improved via halogen effect which was achieved by anodizing in an ethylene glycol solution containing with fluorine ion. The anodized Ti-50Al with holes and micro-cracks could be self-repaired during oxidation at 1000 °C. The thickness of the oxide scale increases with the prolonging of oxidation time. On the basis of halogen effect for improving the high temperature oxidation resistance of Ti-50Al by anodization, only fluorine addition into the electrolyte can effectively improve the high temperature oxidation resistance of Ti-50Al.

  18. Evolution of Near-Surface Internal and External Oxide Morphology During High-Temperature Selective Oxidation of Steels

    Science.gov (United States)

    Story, Mary E.; Webler, Bryan A.

    2018-05-01

    In this work we examine some observations made using high-temperature confocal scanning laser microscopy (HT-CSLM) during selective oxidation experiments. A plain carbon steel and advanced high-strength steel (AHSS) were selectively oxidized at high temperature (850-900°C) in either low oxygen or water vapor atmospheres. Surface evolution, including thermal grooving along grain boundaries and oxide growth, was viewed in situ during heating. Experiments investigated the influence of the microstructure and oxidizing atmosphere on selective oxidation behavior. Sequences of CSLM still frames collected during the experiment were processed with ImageJ to obtain histograms that showed a general darkening trend indicative of oxidation over time with all samples. Additional ex situ scanning electron microscopy and energy dispersive spectroscopy analysis supported in situ observations. Distinct oxidation behavior was observed for each case. Segregation, grain orientation, and extent of internal oxidation were all found to strongly influence surface evolution.

  19. Hydrogenation and high temperature oxidation of Zirconium claddings

    International Nuclear Information System (INIS)

    Novotny, T.; Perez-Feró, E.; Horváth, M.

    2015-01-01

    In the last few years a new series of experiments started for supporting the new LOCA criteria, considering the proposals of US NRC. The effects which can cause the embrittlement of VVER fuel claddings were reviewed and evaluated in the framework of the project. The purpose of the work was to determine how the fuel cladding’s hydrogen uptake under normal operating conditions, effect the behavior of the cladding under LOCA conditions. As a first step a gas system equipment with gas valves and pressure gauge was built, in which the zirconium alloy can absorb hydrogen under controlled conditions. In this apparatus E110 (produced by electrolytic method, currently used at Paks NPP) and E110G (produced by a new technology) alloys were hydrogenated to predetermined hydrogen contents. According the results of ring compression tests the E110G alloys lose their ductility above 3200 ppm hydrogen content. This limit can be applied to determine the ductile-brittle transition of the nuclear fuel claddings. After the hydrogenation, high temperature oxidation experiments were carried out on the E110G and E110 samples at 1000 °C and 1200 °C. 16 pieces of E110G and 8 samples of E110 with 300 ppm and 600 ppm hydrogen content were tested. The oxidation of the specimens was performed in steam, under isothermal conditions. Based on the ring compression tests load-displacement curves were recorded. The main objective of the compression tests was to determine the ductile-brittle transition. These results were compared to the results of our previous experiments where the samples did not contain hydrogen. The original claddings showed more ductile behavior than the samples with hydrogen content. The higher hydrogen content resulted in a more brittle mechanical behavior. However no significant difference was observed in the oxidation kinetics of the same cladding types with different hydrogen content. The experiments showed that the normal operating hydrogen uptake of the fuel claddings

  20. Kinetics of catalyzed tritium oxidation in air at ambient temperature

    International Nuclear Information System (INIS)

    Sherwood, A.E.

    1980-01-01

    Tritium/air oxidation kinetic data are derived from measurements carried out with three catalysts. All experiments were carried out at room temperature - a regime that provides a severe test for catalyst effectiveness. Each catalyst consists of a high-surface-area substrate in pelletized form, onto which precious metal has been dispersed. The metal/substrate combinations investigated are: platinum/alumina, palladium/kaolin, and paladium/zeolite. Each of the dispersed-metal catalysts is extremely effective in promoting tritium oxidation in comparison with self-catalyzed atmospheric conversion; equivalent first-order rate constants are higher by roughly nine orders of magnitude. Electron-microprobe scans reveal that the dispersed metal is deposited near the outer surface of the catalyst, with metal concentration decreasing exponentially from the pellet surface. The platinum-based catalyst is more effective than the palladium catalysts on a surface-area basis by about a factor of three. Rate coefficients are determined from concentration decay following a spike injection of tritium into an air-filled enclosure processed by recirculation through an oxidation/adsorption system. The catalytic reaction is first-order in tritium concentration in the range 10 to 10 5 μCi/m 3 (4 ppt-40 ppB). Addition of hydrogen carrier gas is unnecessary. Catalytic activity for all three catalysts declines with time of exposure to air after activation, following a power-law decay with an exponent of -1/2. Reactivation with hot hydrogen gas effectively restores initial catalytic activity

  1. Considerations in Execution of High Temperature Steam Oxidation Testing

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, Andrew T. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2014-04-01

    The Fuel Cycle Research and Development program’s Advanced Fuels Campaign is currently supporting a range of experimental efforts aimed at development and qualification of so-called ‘accident tolerant’ nuclear fuel forms. Numerous criteria have been developed by which proposed systems will be investigated; foremost among these will be their resistance to oxidation at high temperatures by steamdominated atmospheres. Experimental characterization of the various proposed systems is currently ongoing at numerous national laboratories as well as at industrial and university partners using a wide range of different laboratory equipment and techniques. This requires consideration of differences that may develop among test protocols due to both intrinsic (e.g. differences between experimental capabilities) and extrinsic (e.g. methodology of test execution) factors. These are essential to understand to provide confidence across institutions in the data collected if it is used to justify resources for further investigation. The focus of this document is to provide an initial discussion of factors that may play a role in governing the observed oxidation of a test sample. It will remain up to the principle investigator to judge whether a specific factor discussed is directly applicable to the system under investigation. The purpose of the specific experiment must also guide determination of whether a given factor requires careful consideration or not.

  2. High temperature oxidation behaviour of mullite coated C/C composites in air

    International Nuclear Information System (INIS)

    Fritze, H.; Borchardt, G.; Weber, S.; Scherrer, S.; Weiss, R.

    1997-01-01

    Based on thermogravimetric measurements on Si-SiC-mullite coated C/C material the temperature dependence of the overall rate constant is interpreted in the temperature range 400 C 1400 C), however, the oxidation behaviour of SiC limits long term application. In this temperature range, additional outer mullite coatings produced by pulsed laser deposition improve the oxidation behaviour. (orig.)

  3. Influence of temperature on oxidation behaviour of ZE41 magnesium alloy

    International Nuclear Information System (INIS)

    Lopez, M.D.; Munez, C.J.; Carboneras, M.; Rodrigo, P.; Escalera, M.D.; Otero, E.

    2010-01-01

    The influence of temperature on the oxidation behaviour of commercial ZE41 magnesium alloy has been studied. Thermogravimetric tests were carried out to determine the oxidation kinetics in the 350-500 o C range. Morphology and growth of the oxidation films were analysed by Scanning Electronic Microscopy (SEM), Energy Dispersive X-Ray Spectrometry (EDS) and X-Ray Diffraction (XRD). It was found that the oxidation kinetics initially follow a parabolic law, following a linear law for higher exposure times. Results also showed that the protective nature of the oxide layer depends on the oxidation temperature. At temperatures in the range of 350-450 o C the ZE41 alloy is covered by a protective oxide layer, very thin and compact, whereas the oxide layer formed at 500 o C exhibits a non-protective nature, showing an 'oxide sponges' morphology.

  4. Preparation of Au/Y2O3 and Au/NiO catalysts by co-precipitation and their oxidation activities

    International Nuclear Information System (INIS)

    Sreethawong, Thammanoon; Sitthiwechvijit, Norsit; Rattanachatchai, Apiwat; Ouraipryvan, Piya; Schwank, Johannes W.; Chavadej, Sumaeth

    2011-01-01

    Research highlights: → The catalytic activity of Au catalysts supported on Y 2 O 3 and NiO prepared by co-precipitation was investigated for CO and methanol oxidation. → The phase transformation of yttrium support greatly affected the CO oxidation activity. → The Au/Y 2 O 3 exhibited the same activity as Au/NiO for the methanol oxidation while the Au/NiO gave higher activity for CO oxidation. - Abstract: The objective of this work was to investigate the catalytic activity of gold catalysts supported on two metal oxides, yttrium oxide and nickel oxide, prepared by co-precipitation for CO and methanol oxidation reactions. The TGA and XRD results confirmed that yttrium hydroxide (Y(OH) 3 ) was formed at calcination temperature below 300 deg. C. When it was calcined at 400 deg. C, the Y(OH) 3 was transformed to yttrium oxide hydroxide (YOOH). Finally, when calcination temperature was raised to 600 deg. C, the YOOH was completely transformed to yttrium oxide (Y 2 O 3 ). Interestingly, the gold loaded on YOOH calcined at 400 deg. C and gold loaded on Y 2 O 3 calcined at 500 deg. C comparatively showed the highest catalytic activity for complete CO oxidation at a reaction temperature of 300 deg. C. The 0.12% Au/Y 2 O 3 catalyst calcined at 500 deg. C was employed for both CO and methanol oxidation studies. For complete CO oxidation, the reaction temperatures of Au/Y 2 O 3 and Au/NiO catalysts were 325 deg. C and 250 deg. C, respectively. The light-off temperatures of Au/Y 2 O 3 and Au/NiO catalysts for methanol oxidation were 210 deg. C and 205 deg. C, respectively. Conclusively, the Au/Y 2 O 3 clearly exhibited the same activity as that of Au/NiO for methanol oxidation while the Au/NiO gave higher activity for CO oxidation.

  5. Nb effect in the nickel oxide-catalyzed low-temperature oxidative dehydrogenation of ethane

    KAUST Repository

    Zhu, Haibo

    2012-01-01

    A method for the preparation of NiO and Nb-NiO nanocomposites is developed, based on the slow oxidation of a nickel-rich Nb-Ni gel obtained in citric acid. The resulting materials have higher surface areas than those obtained by the classical evaporation method from nickel nitrate and ammonium niobium oxalate. These consist in NiO nanocrystallites (7-13 nm) associated, at Nb contents >3 at.%., with an amorphous thin layer (1-2 nm) of a niobium-rich mixed oxide with a structure similar to that of NiNb 2O 6. Unlike bulk nickel oxides, the activity of these nanooxides for low-temperature ethane oxidative dehydrogenation (ODH) has been related to their redox properties. In addition to limiting the size of NiO crystallites, the presence of the Nb-rich phase also inhibits NiO reducibility. At Nb content >5 at.%, Nb-NiO composites are thus less active for ethane ODH but more selective, indicating that the Nb-rich phase probably covers part of the unselective, non-stoichiometric, active oxygen species of NiO. This geometric effect is supported by high-resolution transmission electron microscopy observations. The close interaction between NiO and the thin Nb-rich mixed oxide layer, combined with possible restructuration of the nanocomposite under ODH conditions, leads to significant catalyst deactivation at high Nb loadings. Hence, the most efficient ODH catalysts obtained by this method are those containing 3-4 at.% Nb, which combine high activity, selectivity, and stability. The impact of the preparation method on the structural and catalytic properties of Nb-NiO nanocomposites suggests that further improvement in NiO-catalyzed ethane ODH can be expected upon optimization of the catalyst. © 2011 Elsevier Inc. All rights reserved.

  6. Oxide glass to high temperature ceramic superconductors - a novel route

    International Nuclear Information System (INIS)

    Chaudhuri, B.K.; Som, K.K.

    1992-01-01

    Recently it has been discovered that many of transition metal oxide (TMO) glasses like Bi-Sr-Ca-Cu-O, Y-Ba-Cu-O, Bi-Pb-Sr-Ca-Cu-O etc. can be directly converted to the corresponding high temperature superconducting phases by properly annealing the respective glasses. In this review recent developements in this field are summarised. The structural, electrical, dielectrical, magnetic, optical, and other properties of these new type of (TMO) glass systems have been elucidated comparing them with the corresponding results of already known (TMO) glasses which do not become superconductors on annealing above their glass transition temperatures (T g ). The electrical properties of this novel glass system have been analysed with reference to the various existing theoretical models based on polaron hopping conduction mechanism. The electrical, magnetic, and other properties of the respective superconductors obtained from their corresponding glass phases by annealing above (T g ) and the possibility of drawing wires, ribbons etc. from these glass matrices and then converting them to their high T c superconducting phases have also been discussed. (author). 107 refs., 32 figs., 5 tabs

  7. Thermogravimetric study of oxidation of a PdCr alloy used for high-temperature sensors

    Science.gov (United States)

    Boyd, Darwin L.; Zeller, Mary V.

    1994-01-01

    In this study, the oxidation of Pd-13 weight percent Cr, a candidate alloy for high-temperature strain gages, was investigated by thermogravimetry. Although the bulk alloy exhibits linear electrical resistivity versus temperature and stable resistivity at elevated temperatures, problems attributed to oxidation occur when this material is fabricated into strain gages. In this work, isothermal thermogravimetry (TG) was used to study the oxidation kinetics. Results indicate that the oxidation of Pd-13 weight percent Cr was approximately parabolic in time at 600 C but exhibited greater passivation from 700 to 900 C. At 1100 C, the oxidation rate again increased.

  8. Evaluation of oxides formed at high temperatures in Zr-2.5Nb pressure tubing

    Energy Technology Data Exchange (ETDEWEB)

    Kiran Kumar, N.A.P.; Szpunar, J.A., E-mail: kiraniitkgp@yahoo.com [Univ. of Saskatchewan, Saskatoon, Saskatchewan (Canada)

    2012-07-01

    The oxidation behavior of Zr-2.5Nb pressure tube samples has been studied at four different temperatures, i.e., 400°, 600°, 800°, and 1000°C. The amount of tetragonal phase is found to decrease with increase of temperature. The oxide texture of (002){sub m} and (111){sub m} type increased with the temperature from 400°C to 600°C, however at temperatures above 600°C the texture strength seems to diminish and the oxide layer becomes structurally unstable. Further, the impedance response is found to be dependent on the microstructure of the oxide film. For the sample oxidized at 400°C, Electrochemical Impedance Spectroscopy (EIS) spectra exhibited a two-time constant behavior, showing the formation of two-layer oxide film on the Zr-2.5Nb alloy, which correspond to a porous outer oxide and a barrier inner oxide, respectively. In addition, the samples were oxidized at constant temperature of 600°C with varying oxidation time. The observation shows that the oxide is more protective in the early stage of oxide growth. However, further growth of oxide film has resulted in degeneration of its protective character. (author)

  9. Low-temperature carbon monoxide oxidation over zirconia-supported CuO–CeO{sub 2} catalysts: Effect of zirconia support properties

    Energy Technology Data Exchange (ETDEWEB)

    Moretti, Elisa, E-mail: elisa.moretti@unive.it [Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari Venezia, INSTM Venice Research Unit, Via Torino 155/B, 30172 Mestre Venezia (Italy); Molina, Antonia Infantes [Departamento de Química Inorgánica, Cristalografía y Mineralogía, Facultad de Ciencias, Universidad de Málaga, Campus de Teatinos, 29071 Málaga (Spain); Sponchia, Gabriele; Talon, Aldo; Frattini, Romana [Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari Venezia, INSTM Venice Research Unit, Via Torino 155/B, 30172 Mestre Venezia (Italy); Rodriguez-Castellon, Enrique [Departamento de Química Inorgánica, Cristalografía y Mineralogía, Facultad de Ciencias, Universidad de Málaga, Campus de Teatinos, 29071 Málaga (Spain); Storaro, Loretta [Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari Venezia, INSTM Venice Research Unit, Via Torino 155/B, 30172 Mestre Venezia (Italy)

    2017-05-01

    Highlights: • CuO-CeO{sub 2}/ZrO{sub 2} materials were investigated in the low temperature CO oxidation. • High surface area ZrO{sub 2} synthetized by sol-gel method. • Low ZrO{sub 2} surface area synthetized by fast precipitation. • Sol-gel samples showed, after impregnation, a severe decrease of surface area. • CuO-CeO{sub 2}/ZrO{sub 2} with precipitated ZrO{sub 2} led to a very active catalyst. - Abstract: A study was conducted to investigate the effect of the preparation route of ZrO{sub 2} in CuO–CeO{sub 2}/ZrO{sub 2} catalysts for the oxidation of carbon monoxide at low temperature (COX). Four ZrO{sub 2} supports were synthetized via either type sol-gel methodology or precipitation. The final Cu-Ce-Zr oxide catalysts were prepared by incipient wetness co-impregnation with copper and cerium solutions (with a loading of 6 wt% of CuO and 20 wt% of CeO{sub 2}). The catalyst crystalline phases, texture and active species reducibility were determined by XRD, N{sub 2} physisorption at −196 °C and H{sub 2}-TPR, respectively; meanwhile the surface composition and copper-cerium electronic states were studied by XPS. The catalytic activity was evaluated in the oxidation of CO to CO{sub 2}, in the 40–215 °C temperature range. Catalytic results evidenced that the samples prepared by a sol-gel methodology showed, after the impregnation, a severe decrease of specific surface area and pore volume attributable to a wide degree of pore blockage caused by the presence of metal oxide particles and a collapse of the structure partially burying the active sites. A simple co-impregnation of a zirconia support, obtained through facile and fast precipitation, provided instead a catalyst with very good redox properties and high dispersion of the active phases, which completely oxidizes CO in the range 115–215 °C with T{sub 50} of 65 °C. This higher observed activity was ascribed to the formation of a larger fraction of highly dispersed and easily reducible Cu

  10. Segregation across the metal/oxide interface occurring during oxidation at high temperatures of diluted iron based alloys

    International Nuclear Information System (INIS)

    Geneve, D.; Rouxel, D.; Weber, B.; Confente, M.

    2006-01-01

    Industrial steels being elaborated in air at high temperature oxidize and cover with a complex oxide layer. The oxidation reaction drastically alters the surface composition. Such modifications have been investigated, in this work, by Auger Electron Spectroscopy (AES) using an original method to characterize the composition of the metal/oxide interfaces. Analysis of the concentration gradients across the interfaces allows to better understand how the alloy elements contribute to the oxidation process. The development of new alloy phases, the interdependencies between elements and the diffusion of different species are discussed considering thermodynamic properties of each element

  11. Mottness in high-temperature copper-oxide superconductors

    International Nuclear Information System (INIS)

    Phillips, Philip; Choy, T.-P.; Leigh, Robert G

    2009-01-01

    The standard theory of metals, Fermi liquid theory, hinges on the key assumption that although the electrons interact, the low-energy excitation spectrum stands in a one-to-one correspondence with that of a non-interacting system. In the normal state of the copper-oxide high-temperature superconductors, drastic deviations from the Fermi liquid picture are obtained, highlighted by a pseudogap, broad spectral features and T-linear resistivity. A successful theory in this context must confront the highly constraining scaling argument which establishes that all 4-Fermi interactions are irrelevant (except for pairing) at a Fermi surface. This argument lays plain that new low-energy degrees of freedom are necessary. This paper focuses on the series of experiments on copper-oxide superconductors which reveal that the number of low-energy addition states per electron per spin exceeds unity, in direct violation of the key Fermi liquid tenet. These experiments point to new degrees of freedom, not made out of the elemental excitations, as the key mechanism by which Fermi liquid theory breaks down in the cuprates. A recent theoretical advance which permits an explicit integration of the high-energy scale in the standard model for the cuprates reveals the source of the new dynamical degrees of freedom at low energies, a charge 2e bosonic field which has nothing to do with pairing but rather represents the mixing with the high-energy scales. We demonstrate explicitly that at half-filling, this new degree of freedom provides a dynamical mechanism for the generation of the charge gap and antiferromagnetism in the insulating phase. At finite doping, many of the anomalies of the normal state of the cuprates including the pseudogap, T-linear resistivity and the mid-infrared band are reproduced. A possible route to superconductivity is explored

  12. High temperature oxidation behavior of SiC coating in TRISO coated particles

    International Nuclear Information System (INIS)

    Liu, Rongzheng; Liu, Bing; Zhang, Kaihong; Liu, Malin; Shao, Youlin; Tang, Chunhe

    2014-01-01

    Highlights: • High temperature oxidation tests of SiC coating in TRISO particles were carried out. • The dynamic oxidation process was established. • Oxidation mechanisms were proposed. • The existence of silicon oxycarbides at the SiO 2 /SiC interface was demonstrated. • Carbon was detected at the interface at high temperatures and long oxidation time. - Abstract: High temperature oxidation behavior of SiC coatings in tristructural-isotropic (TRISO) coated particles is crucial to the in-pile safety of fuel particles for a high temperature gas cooled reactor (HTGR). The postulated accident condition of air ingress was taken into account in evaluating the reliability of the SiC layer. Oxidation tests of SiC coatings were carried out in the ranges of temperature between 800 and 1600 °C and time between 1 and 48 h in air atmosphere. Based on the microstructure evolution of the oxide layer, the mechanisms and kinetics of the oxidation process were proposed. The existence of silicon oxycarbides (SiO x C y ) at the SiO 2 /SiC interface was demonstrated by X-ray photospectroscopy (XPS) analysis. Carbon was detected by Raman spectroscopy at the interface under conditions of very high temperatures and long oxidation time. From oxidation kinetics calculation, activation energies were 145 kJ/mol and 352 kJ/mol for the temperature ranges of 1200–1500 °C and 1550–1600 °C, respectively

  13. Partial oxidation of methane in a temperature-controlled dielectric barrier discharge reactor

    KAUST Repository

    Zhang, Xuming; Cha, Min

    2015-01-01

    We studied the relative importance of the reduced field intensity and the background reaction temperature in the partial oxidation of methane in a temperature-controlled dielectric barrier discharge reactor. We obtained important mechanistic insight

  14. Obtention of superconductivity by room temperature electrochemical oxidation of La2CuO4

    International Nuclear Information System (INIS)

    Casan-Pastor, N.; Fuertes, A.; Gomez-Romero, P.

    1993-01-01

    The undoped oxide La2CuO4 has required traditionally synthesis under high pressure of oxygen (and high temperatures) to incorporate excess oxygen into its structure and become a superconductor. The electrochemical oxidation of this same oxide at room temperature and pressure constitutes a striking example of the use of an alternative driving force for the oxidation of oxides to become superconductors. Electrochemical treatment of oxides has been frequently applied to their reduction with cationic intercalation. Oxidations of these solid with the concomitant intercalation of anions into their lattice shows also great promises. The paper reports recent results in the electrochemical oxidation of La2CuO4 and other cuprates, showing also the important role of post-oxidation thermal treatments on the properties of the resulting solids

  15. Effects of reaction temperature and inlet oxidizing gas flow rate on IG-110 graphite oxidation used in HTR-PM

    International Nuclear Information System (INIS)

    Sun Ximing; Dong Yujie; Zhou Yangping; Shi Lei; Sun Yuliang; Zhang Zuoyi; Li Zhengcao

    2017-01-01

    The oxidation behavior of a selected nuclear graphite (IG-110) used in Pebble-bed Module High Temperature gas-cooled Reactor was investigated under the condition of air ingress accident. The oblate rectangular specimen was oxidized by oxidant gas with oxygen mole fraction of 20% and flow rates of 125–500 ml/min at temperature of 400–1200°C. Experiment results indicate that the oxidation behavior can also be classified into three regimes according to temperature. The regime I at 400–550°C has lower apparent activation energies of 75.57–138.59 kJ/mol when the gas flow rate is 125–500 ml/min. In the regime II at 600–900°C, the oxidation rate restricted by the oxygen supply to graphite is almost stable with the increase of temperature. In the regime III above 900°C, the oxidation rate increases obviously with the increase of temperature.With the increase of inlet gas flow from 125 to 500 ml/min, the apparent activation energy in regime I is increased and the stableness of oxidation rate in regime II is reduced. (author)

  16. Optimization of NO oxidation by H2O2 thermal decomposition at moderate temperatures.

    Science.gov (United States)

    Zhao, Hai-Qian; Wang, Zhong-Hua; Gao, Xing-Cun; Liu, Cheng-Hao; Qi, Han-Bing

    2018-01-01

    H2O2 was adopted to oxidize NO in simulated flue gas at 100-500°C. The effects of the H2O2 evaporation conditions, gas temperature, initial NO concentration, H2O2 concentration, and H2O2:NO molar ratio on the oxidation efficiency of NO were investigated. The reason for the narrow NO oxidation temperature range near 500°C was determined. The NO oxidation products were analyzed. The removal of NOx using NaOH solution at a moderate oxidation ratio was studied. It was proven that rapid evaporation of the H2O2 solution was critical to increase the NO oxidation efficiency and broaden the oxidation temperature range. the NO oxidation efficiency was above 50% at 300-500°C by contacting the outlet of the syringe needle and the stainless-steel gas pipe together to spread H2O2 solution into a thin film on the surface of the stainless-steel gas pipe, which greatly accelerated the evaporation of H2O2. The NO oxidation efficiency and the NO oxidation rate increased with increasing initial NO concentration. This method was more effective for the oxidation of NO at high concentrations. H2O2 solution with a concentration higher than 15% was more efficient in oxidizing NO. High temperatures decreased the influence of the H2O2 concentration on the NO oxidation efficiency. The oxidation efficiency of NO increased with an increase in the H2O2:NO molar ratio, but the ratio of H2O2 to oxidized NO decreased. Over 80% of the NO oxidation product was NO2, which indicated that the oxidation ratio of NO did not need to be very high. An 86.7% NO removal efficiency was obtained at an oxidation ratio of only 53.8% when combined with alkali absorption.

  17. Speciation of Raney Copper Oxide during High-Temperature Desulfurization

    International Nuclear Information System (INIS)

    Wang, T. C.; Chen, C. Y.; Huang, H.-L.; Wang, H. Paul; Wei Yuling

    2007-01-01

    Speciation of copper in the Raney copper oxides (R-CuO) during high-temperature desulfurization has been studied by X-ray absorption spectroscopy. The preedge XANES spectra (8975-8979 eV) of R-CuO exhibit a very weak 1s-to-3d transition forbidden by the selection rule in the case of the perfect octahedral symmetry. A shoulder at 8985-8988 eV and an intense band at 8994-9002 eV can be attributed to the 1s-to-4p transition that indicates the existence of the Cu(II) species. The preedge band at 8981-8984 eV can be attributed to the dipole-allowed 1s-to-4p transition of Cu(I), suggesting an existence of Cu2S during sulfurization. An enhanced absorbance at 9003 eV shows that Cu(0) species may be formed in the sulfurized R-CuO. The main copper species in regenerated R-CuO are CuO (96%) and Cu2S (4%)

  18. Oxidation performance of high temperature materials under oxyfuel conditions

    Energy Technology Data Exchange (ETDEWEB)

    Tuurna, Satu; Pohjanne, Pekka; Yli-Olli, Sanni; Kinnunen, Tuomo [VTT Technical Research Centre of Finland, Espoo (Finland)

    2010-07-01

    Oxyfuel combustion is widely seen as a major option to facilitate carbon capture and storage (CCS) from future boiler plants utilizing clean coal technologies. Oxyfuel combustion can be expected to differ from combustion in air by e.g. modified distribution of fireside temperatures, much reduced NOx but increased levels of fireside CO{sub 2}, SO{sub 2} and water levels due to extensive flue gas recirculation. Modified flue gas chemistry results in higher gas emissivity that can increase the thermal stresses at the heat transfer surfaces of waterwalls and superheaters. In addition, increased flue gas recirculation can increase the concentration of a number of contaminants in the deposited ash and promote fouling and corrosion. There is relatively little experimental information available about the effects of oxyfuel combustion on the performance of boiler material. In this work, the oxidation performance of steels X20CrMoV11-1 and TP347HFG has been determined at 580 C/650 C under simulated oxyfuel firing conditions. The results are presented and compared to corresponding results from simulated air firing conditions. (orig.)

  19. Isothermal oxidation behavior of ternary Zr-Nb-Y alloys at high temperature

    Energy Technology Data Exchange (ETDEWEB)

    Prajitno, Djoko Hadi, E-mail: djokohp@batan.go.id [Research Center for Nuclear Materials and Radiometry, Jl. Tamansari 71, Bandung 40132 (Indonesia); Soepriyanto, Syoni; Basuki, Eddy Agus [Metallurgy Engineering, Institute Technology Bandung, Jl. Ganesha 10, Bandung 40132 (Indonesia); Wiryolukito, Slameto [Materials Engineering, Institute Technology Bandung, Jl. Ganesha 10, Bandung 40132 (Indonesia)

    2014-03-24

    The effect of yttrium content on isothermal oxidation behavior of Zr-2,5%Nb-0,5%Y, Zr-2,5%Nb-1%Y Zr-2,5%Nb-1,5%Y alloy at high temperature has been studied. High temperature oxidation carried out at tube furnace in air at 600,700 and 800°C for 1 hour. Optical microscope is used for microstructure characterization of the alloy. Oxidized and un oxidized specimen was characterized by x-ray diffraction. In this study, kinetic oxidation of Zr-2,5%Nb with different Y content at high temperature has also been studied. Characterization by optical microscope showed that microstructure of Zr-Nb-Y alloys relatively unchanged and showed equiaxed microstructure. X-ray diffraction of the alloys depicted that the oxide scale formed during oxidation of zirconium alloys is monoclinic ZrO2 while unoxidised alloy showed two phase α and β phase. SEM-EDS examination shows that depletion of Zr composition took place under the oxide layer. Kinetic rate of oxidation of zirconium alloy showed that increasing oxidation temperature will increase oxidation rate but increasing yttrium content in the alloys will decrease oxidation rate.

  20. The effect of substrate texture and oxidation temperature on oxide texture development in zirconium alloys

    Energy Technology Data Exchange (ETDEWEB)

    Garner, A., E-mail: alistair.garner@manchester.ac.uk [Materials Performance Centre, University of Manchester, Grosvenor Street, Manchester, M17HS (United Kingdom); Frankel, P. [Materials Performance Centre, University of Manchester, Grosvenor Street, Manchester, M17HS (United Kingdom); Partezana, J. [Westinghouse Electric Company, 1332 Beulah Road, Pittsburgh, PA 15235 (United States); Preuss, M. [Materials Performance Centre, University of Manchester, Grosvenor Street, Manchester, M17HS (United Kingdom)

    2017-02-15

    During corrosion of zirconium alloys a highly textured oxide is formed, the degree of this preferred orientation has previously been shown to be an important factor in determining the corrosion behaviour of these alloys. Two distinct experiments were designed in order to investigate the origin of this oxide texture development on two commercial alloys. Firstly, sheet samples of Zircaloy-4 were oxidised between 500 and 800 °C in air. The resulting monoclinic oxide texture strength was observed to decrease with increasing oxidation temperature. In a second experiment, orthogonal faces of Low Tin ZIRLO{sub ™} were oxidised in 360 °C water, providing different substrate textures but identical microstructures. The substrate texture was observed to have a negligible effect on the corrosion performance whilst the major orientation of both oxide phases was found to be independent of substrate orientation. It is concluded that the main driving force for oxide texture development in single-phase zirconium alloys is the compressive stress caused by the Zr−ZrO{sub 2} transformation. - Highlights: • Substrate orientation does not significantly affect oxide texture development. • Corrosion performance is independent of substrate texture. • Monoclinic oxide texture strength decreases with increasing oxidation temperature. • The main driving force for texture development is the oxidation-induced stress.

  1. Nanostructured oxide materials and modules for high temperature power generation from waste heat

    DEFF Research Database (Denmark)

    Van Nong, Ngo; Pryds, Nini

    2013-01-01

    are not easily satisfied by conventional thermoelectric materials. Not only they must possess a sufficient thermoelectric performance, they should also be stable at high temperatures, nontoxic and low-cost comprising elements, and must be also able to be processed and shaped cheaply. Oxides are among...... the strongest candidate materials for this purpose. In this review, the progress in the development of two representative p- and n-type novel oxide materials based on Ca3Co4O9 and doped-ZnO is presented. Thermoelectric modules built up from these oxides were fabricated, tested at high temperatures, and compared...... with other similar oxide modules reported in the literature. A maximum power density of 4.5 kW/m2 was obtained for an oxide module comprising of 8 p-n couples at a temperature difference of 496 K, an encouraging result in the context of the present high temperature oxide modules....

  2. New Cathode Materials for Intermediate Temperature Solid Oxide Fuel Cells

    Energy Technology Data Exchange (ETDEWEB)

    Allan J. Jacobson

    2006-09-30

    Operation of SOFCs at intermediate temperatures (500-800 C) requires new combinations of electrolyte and electrode materials that will provide both rapid ion transport across the electrolyte and electrode-electrolyte interfaces and efficient electrocatalysis of the oxygen reduction and fuel oxidation reactions. This project concentrates on materials and issues associated with cathode performance that are known to become limiting factors as the operating temperature is reduced. The specific objectives of the proposed research are to develop cathode materials that meet the electrode performance targets of 1.0 W/cm{sup 2} at 0.7 V in combination with YSZ at 700 C and with GDC, LSGM or bismuth oxide based electrolytes at 600 C. The performance targets imply an area specific resistance of {approx}0.5 {Omega}cm{sup 2} for the total cell. The research strategy is to investigate both established classes of materials and new candidates as cathodes, to determine fundamental performance parameters such as bulk diffusion, surface reactivity and interfacial transfer, and to couple these parameters to performance in single cell tests. The initial choices for study were perovskite oxides based on substituted LaFeO{sub 3} (P1 compositions), where significant data in single cell tests exist at PNNL for example, for La{sub 0.8}Sr{sub 0.2}FeO{sub 3} cathodes on both YSZ and CSO/YSZ. The materials selection was then extended to La{sub 2}NiO{sub 4} compositions (K1 compositions), and then in a longer range task we evaluated the possibility of completely unexplored group of materials that are also perovskite related, the ABM{sub 2}O{sub 5+{delta}}. A key component of the research strategy was to evaluate for each cathode material composition, the key performance parameters, including ionic and electronic conductivity, surface exchange rates, stability with respect to the specific electrolyte choice, and thermal expansion coefficients. In the initial phase, we did this in parallel with

  3. Low temperature oxidation and spontaneous combustion characteristics of upgraded low rank coal

    Energy Technology Data Exchange (ETDEWEB)

    Choi, H.K.; Kim, S.D.; Yoo, J.H.; Chun, D.H.; Rhim, Y.J.; Lee, S.H. [Korea Institute of Energy Research, Daejeon (Korea, Republic of)

    2013-07-01

    The low temperature oxidation and spontaneous combustion characteristics of dried coal produced from low rank coal using the upgraded brown coal (UBC) process were investigated. To this end, proximate properties, crossing-point temperature (CPT), and isothermal oxidation characteristics of the coal were analyzed. The isothermal oxidation characteristics were estimated by considering the formation rates of CO and CO{sub 2} at low temperatures. The upgraded low rank coal had higher heating values than the raw coal. It also had less susceptibility to low temperature oxidation and spontaneous combustion. This seemed to result from the coating of the asphalt on the surface of the coal, which suppressed the active functional groups from reacting with oxygen in the air. The increasing upgrading pressure negatively affected the low temperature oxidation and spontaneous combustion.

  4. Electrode Design for Low Temperature Direct-Hydrocarbon Solid Oxide Fuel Cells

    Science.gov (United States)

    Chen, Fanglin (Inventor); Zhao, Fei (Inventor); Liu, Qiang (Inventor)

    2015-01-01

    In certain embodiments of the present disclosure, a solid oxide fuel cell is described. The solid oxide fuel cell includes a hierarchically porous cathode support having an impregnated cobaltite cathode deposited thereon, an electrolyte, and an anode support. The anode support includes hydrocarbon oxidation catalyst deposited thereon, wherein the cathode support, electrolyte, and anode support are joined together and wherein the solid oxide fuel cell operates a temperature of 600.degree. C. or less.

  5. Electrode design for low temperature direct-hydrocarbon solid oxide fuel cells

    Science.gov (United States)

    Chen, Fanglin; Zhao, Fei; Liu, Qiang

    2015-10-06

    In certain embodiments of the present disclosure, a solid oxide fuel cell is described. The solid oxide fuel cell includes a hierarchically porous cathode support having an impregnated cobaltite cathode deposited thereon, an electrolyte, and an anode support. The anode support includes hydrocarbon oxidation catalyst deposited thereon, wherein the cathode support, electrolyte, and anode support are joined together and wherein the solid oxide fuel cell operates a temperature of 600.degree. C. or less.

  6. Oxidation Kinetics of Ferritic Alloys in High-Temperature Steam Environments

    Science.gov (United States)

    Parker, Stephen S.; White, Josh; Hosemann, Peter; Nelson, Andrew

    2018-02-01

    High-temperature isothermal steam oxidation kinetic parameters of several ferritic alloys were determined by thermogravimetric analysis. The oxidation kinetic constant ( k) was measured as a function of temperature from 900°C to 1200°C. The results show a marked increase in oxidation resistance compared to reference Zircaloy-2, with kinetic constants 3-5 orders of magnitude lower across the experimental temperature range. The results of this investigation supplement previous findings on the properties of ferritic alloys for use as candidate cladding materials and extend kinetic parameter measurements to high-temperature steam environments suitable for assessing accident tolerance for light water reactor applications.

  7. Oxidation Behavior of Some Cr Ferritic Steels for High Temperature Fuel Cells

    International Nuclear Information System (INIS)

    Mohamed, H.E.

    2012-01-01

    The oxidation behavior of three high Cr ferritic steels designated 1Al, RA and 5Al with different levels of Al, Si, Mn and Hf has been investigated in the present work. These steels have been developed as candidates for Solid Oxide Fuel Cell (SOFC) interconnect. Specimens of these alloys have been subjected to isothermal as well as cyclic oxidation in air. Isothermal oxidation tests are conducted in the temperature range 800 - 1000 degree C for time periods up to 1000 h. cyclic oxidation tests were carried out at 800 and 1000 degree C for twenty 25 - h cycles giving a total cyclic exposure time of 500 h. The growth rate of the oxide scales was found to follow a parabolic law over a certain oxidation period which changed with alloy composition and oxidation temperature. The value of the parabolic rate constant increased with increasing oxidation temperature. At 800 and 900 degree C alloy 1Al exhibited higher oxidation resistance compared to the other two alloys. Alloy RA showed spalling behavior when oxidized at 900 degree C and the extent of spalling increased with increasing the oxidation temperature to 1000 degree C. Alloy 5Al oxidized at 1000 degree C showed the highest oxidation resistance among the investigated alloys. Alloy 1Al and RA showed similar scale morphology and composition. X- ray diffraction analysis revealed that the scales developed on these alloys consist of Cr 2 O 3 with an outer layer of MnCr 2 O 4 and a minor amount of FeCr 2 O 4 spinels. Alloy 5Al developed scale consisting of γ- Al 2 O 3 at 800 degree C and γ and α- Al 2 O 3 at 900 degree C. Oxidation of alloy 5Al at 1000 degree C led to formation of a scale consisting mainly of the protective phase α Al 2 O 3 . The presence of 0.84 wt% Al and 0.95 wt % Si in alloy 1Al enhanced its oxidation resistance compared to alloy RA which contains only 0.29 wt% Si and is Al - free. This enhancement was attributed to formation of internal oxidation zone in alloy 1Al just beneath the oxide / alloy

  8. Facile synthesis of iron oxides/reduced graphene oxide composites: application for electromagnetic wave absorption at high temperature.

    Science.gov (United States)

    Zhang, Lili; Yu, Xinxin; Hu, Hongrui; Li, Yang; Wu, Mingzai; Wang, Zhongzhu; Li, Guang; Sun, Zhaoqi; Chen, Changle

    2015-03-19

    Iron oxides/reduced graphene oxide composites were synthesized by facile thermochemical reactions of graphite oxide and FeSO4 · 7H2O. By adjusting reaction temperature, α-Fe2O3/reduced graphene oxide and Fe3O4/reduced graphene oxide composites can be obtained conveniently. Graphene oxide and reduced graphene oxide sheets were demonstrated to regulate the phase transition from α-Fe2O3 to Fe3O4 via γ-Fe2O3, which was reported for the first time. The hydroxyl groups attached on the graphene oxide sheets and H2 gas generated during the annealing of graphene oxide are believed to play an important role during these phase transformations. These samples showed good electromagnetic wave absorption performance due to their electromagnetic complementary effect. These samples possess much better electromagnetic wave absorption properties than the mixture of separately prepared Fe3O4 with rGO, suggesting the crucial role of synthetic method in determining the product properties. Also, these samples perform much better than commercial absorbers. Most importantly, the great stability of these composites is highly advantageous for applications as electromagnetic wave absorption materials at high temperatures.

  9. Effect of temperature on the electro-oxidation of ethanol on platinum

    OpenAIRE

    Camargo, Ana Paula M.; Previdello, Bruno A. F.; Varela, Hamilton; Gonzalez, Ernesto R.

    2010-01-01

    We present in this work an experimental investigation of the effect of temperature (from 25 to 180 ºC) in the electro-oxidation of ethanol on platinum in two different phosphoric acid concentrations. We observed that the onset potential for ethanol electro-oxidation shifts to lower values and the reaction rates increase as temperature is increased for both electrolytes. The results were rationalized in terms of the effect of temperature on the adsorption of reaction intermediates, poisons, an...

  10. Phase Transformation of Hot Dipped Aluminium during High Temperature Oxidation

    International Nuclear Information System (INIS)

    Zaifol Samsu; Muhammad Daud; Hishamuddin Husain; Mohd Saari Ripin; Rusni Rejab; Zaiton Selamat; Mohd Shariff Sattar

    2014-01-01

    Low alloy carbon steel was coated by hot-dipping into a molten aluminum bath. Isothermal oxidations were carried out at 750 degree Celsius in static air to study the oxidation behaviour of the hot-dipped aluminide steel. The phase transformation in the aluminide layer during diffusion at 750 degree Celsius in static air was analyzed by SEM-EDX and XRD. After hot-dip treatment, the coating layers consisted of three phases, where Al, thinner layer of FeAl 3 , and thicker layer of Fe 2 Al 5 were detected from external topcoat to the aluminide/ steel substrate. After oxidation, the Fe 2 Al 5 formed during the immersion process completely transformed to Fe 2 Al 5 , FeAl 2 , FeAl and Al-Fe(Al) phases because of the composition gradient and the chemical diffusion by oxidation. After oxidation, there are some voids were found at the coating/ substrate interface due to the rapid inter-diffusion of iron and aluminium during oxidation. The FeAl phase kept growing with increasing exposure time at 750 degree Celsius, while the Fe 2 Al 5 was consumed during oxidation. After 168 hrs oxidation, the Fe 2 Al 5 phase was going disappeared as the aluminum layer was consumed. (author)

  11. Degradation in Solid Oxide Cells During High Temperature Electrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Manohar Sohal

    2009-05-01

    Idaho National Laboratory has an ongoing project to generate hydrogen from steam using solid oxide electrolysis cells. One goal of that project is to address the technical and degradation issues associated with solid oxide electrolysis cells. This report covers a variety of these degradation issues, which were discussed during a workshop on “Degradation in Solid Oxide Electrolysis Cells and Strategies for its Mitigation,” held in Phoenix, AZ on October 27, 2008. Three major degradation issues related to solid oxide electrolysis cells discussed at the workshop are: • Delamination of O2-electrode and bond layer on steam/O2-electrode side • Contaminants (Ni, Cr, Si, etc.) on reaction sites (triple-phase boundary) • Loss of electrical/ionic conductivity of electrolyte. This list is not all inclusive, but the workshop summary can be useful in providing a direction for future research related to the degradation of solid oxide electrolysis cells.

  12. Ultra-high temperature oxidation behavior of chemical vapor deposited silicon carbide layers

    International Nuclear Information System (INIS)

    Goto, Takashi

    2003-01-01

    The active oxidation, passive oxidation and bubble formation of CVD SiC were studied in O 2 and CO 2 at temperatures from 1650 to 2000 K. The active oxidation rates in O 2 increased with increasing oxygen partial pressure (P o2 ); however, those in CO 2 showed the maxima at specific P o2 . The passive oxidation kinetics in O 2 were either linear-parabolic or parabolic depending on temperature and P o2 , whereas that in CO 2 was always parabolic. The activation energies for the parabolic oxidation in O 2 and CO 2 were 210 and 150 kJ/mol, respectively, suggesting different rate-determining process between these atmospheres. The bubble formation was controlled by temperature and P o2 being independent of oxidant gas species. (author)

  13. [A method of temperature measurement for hot forging with surface oxide based on infrared spectroscopy].

    Science.gov (United States)

    Zhang, Yu-cun; Qi, Yan-de; Fu, Xian-bin

    2012-05-01

    High temperature large forging is covered with a thick oxide during forging. It leads to a big measurement data error. In this paper, a method of measuring temperature based on infrared spectroscopy is presented. It can effectively eliminate the influence of surface oxide on the measurement of temperature. The method can measure the surface temperature and emissivity of the oxide directly using the infrared spectrum. The infrared spectrum is radiated from surface oxide of forging. Then it can derive the real temperature of hot forging covered with the oxide using the heat exchange equation. In order to greatly restrain interference spectroscopy through included in the received infrared radiation spectrum, three interference filter system was proposed, and a group of optimal gap parameter values using spectral simulation were obtained. The precision of temperature measurement was improved. The experimental results show that the method can accurately measure the surface temperature of high temperature forging covered with oxide. It meets the requirements of measurement accuracy, and the temperature measurement method is feasible according to the experiment result.

  14. High-temperature oxidation behavior of dense SiBCN monoliths: Carbon-content dependent oxidation structure, kinetics and mechanisms

    International Nuclear Information System (INIS)

    Li, Daxin; Yang, Zhihua; Jia, Dechang; Wang, Shengjin; Duan, Xiaoming; Zhu, Qishuai; Miao, Yang; Rao, Jiancun; Zhou, Yu

    2017-01-01

    Highlights: •The scale growth for all investigated monoliths at 1500 °C cannot be depicted by a linear or parabolic rate law. •The carbon-rich monoliths oxidize at 1500 °C according to a approximately linear weight loss equation. •The excessive carbon in SiBCN monoliths deteriorates the oxidation resistance. •The oxidation resistance stems from the characteristic oxide structures and increased oxidation resistance of BN(C). -- Abstract: The high temperature oxidation behavior of three SiBCN monoliths: carbon-lean SiBCN with substantial Si metal, carbon-moderate SiBCN and carbon-rich SiBCN with excessive carbon, was investigated at 1500 °C for times up to15 h. Scale growth for carbon-lean and −moderate monoliths at 1500 °C cannot be described by a linear or parabolic rate law, while the carbon-rich monoliths oxidize according to a approximately linear weight loss equation. The microstructures of the oxide scale compose of three distinct layers. The passivating layer of carbon and boron containing amorphous SiO 2 and increased oxidation resistance of BN(C) both benefit the oxidation resistance.

  15. Nb effect on Zr-alloy oxidation under high pressure steam at high temperatures

    International Nuclear Information System (INIS)

    Park, Kwangheon; Yang, Sungwoo; Kim, Kyutae

    2005-01-01

    The high-pressure steam effects on the oxidation of Zircaloy-4 (Zry-4) and Zirlo (Zry-1%Nb) claddings at high temperature have been analyzed. Test temperature range was 700-900degC, and pressures were 1-150 bars. High pressure-steam enhances oxidation of Zry-4, and the dependency of enhancement looks exponential to steam pressure. The origin of the oxidation enhancement turned out to be the formation of cracks in oxide. The loss of tetragonal phase by high-pressure steam seems related to the crack formation. Addition of Nb as an alloying element to Zr alloy reduces significantly the steam pressure effects on oxidation. The higher compressive stresses and the smaller fraction of tetragonal oxides in Zry-1%Nb seem to be the diminished effect of high-pressure steam on oxidation. (author)

  16. Aluminum-Oxide Temperatures on the Mark VB, VE, VR, 15, and Mark 25 Assemblies

    International Nuclear Information System (INIS)

    Aleman, S.E.

    2001-01-01

    The task was to compute the maximum aluminum-oxide and oxide-coolant temperatures of assemblies cladded in 99+ percent aluminum. The assemblies considered were the Mark VB, VE, V5, 15 and 25. These assemblies consist of nested slug columns with individual uranium slugs cladded in aluminum cans. The CREDIT code was modified to calculate the oxide film thickness and the aluminum-oxide temperature at each axial increment. This information in this report will be used to evaluate the potential for cladding corrosion of the Mark 25 assembly

  17. Temperature controls oxidative phosphorylation and reactive oxygen species production through uncoupling in rat skeletal muscle mitochondria.

    Science.gov (United States)

    Jarmuszkiewicz, Wieslawa; Woyda-Ploszczyca, Andrzej; Koziel, Agnieszka; Majerczak, Joanna; Zoladz, Jerzy A

    2015-06-01

    Mitochondrial respiratory and phosphorylation activities, mitochondrial uncoupling, and hydrogen peroxide formation were studied in isolated rat skeletal muscle mitochondria during experimentally induced hypothermia (25 °C) and hyperthermia (42 °C) compared to the physiological temperature of resting muscle (35 °C). For nonphosphorylating mitochondria, increasing the temperature from 25 to 42 °C led to a decrease in membrane potential, hydrogen peroxide production, and quinone reduction levels. For phosphorylating mitochondria, no temperature-dependent changes in these mitochondrial functions were observed. However, the efficiency of oxidative phosphorylation decreased, whereas the oxidation and phosphorylation rates and oxidative capacities of the mitochondria increased, with increasing assay temperature. An increase in proton leak, including uncoupling protein-mediated proton leak, was observed with increasing assay temperature, which could explain the reduced oxidative phosphorylation efficiency and reactive oxygen species production. Copyright © 2015 Elsevier Inc. All rights reserved.

  18. Influence of temperature on oxidation mechanisms of fiber-textured AlTiTaN coatings.

    Science.gov (United States)

    Khetan, Vishal; Valle, Nathalie; Duday, David; Michotte, Claude; Delplancke-Ogletree, Marie-Paule; Choquet, Patrick

    2014-03-26

    The oxidation kinetics of AlTiTaN hard coatings deposited at 265 °C by DC magnetron sputtering were investigated between 700 and 950 °C for various durations. By combining dynamic secondary ion mass spectrometry (D-SIMS), X-ray diffraction (XRD), and transmission electron microscopy (TEM) investigations of the different oxidized coatings, we were able to highlight the oxidation mechanisms involved. The TEM cross-section observations combined with XRD analysis show that a single amorphous oxide layer comprising Ti, Al, and Ta formed at 700 °C. Above 750 °C, the oxide scale transforms into a bilayer oxide comprising an Al-rich upper oxide layer and a Ti/Ta-rich oxide layer at the interface with the coated nitride layer. From the D-SIMS analysis, it could be proposed that the oxidation mechanism was governed primarily by inward diffusion of O for temperatures of ≤700 °C, while at ≥750 °C, it is controlled by outward diffusion of Al and inward diffusion of O. Via a combination of structural and chemical analysis, it is possible to propose that crystallization of rutile lattice favors the outward diffusion of Al within the AlTiTa mixed oxide layer with an increase in the temperature of oxidation. The difference in the mechanisms of oxidation at 700 and 900 °C also influences the oxidation kinetics with respect to oxidation time. Formation of a protective alumina layer decreases the rate of oxidation at 900 °C for long durations of oxidation compared to 700 °C. Along with the oxidation behavior, the enhanced thermal stability of AlTiTaN compared to that of the TiAlN coating is illustrated.

  19. Multiferroic iron oxide thin films at room temperature

    Czech Academy of Sciences Publication Activity Database

    Gich, M.; Fina, I.; Morelli, Alessio; Sánchez, F.; Alexe, M.; Gazquez, J.; Fontcuberta, J.; Roig, A.

    2014-01-01

    Roč. 26, č. 27 (2014), s. 4645-4652 ISSN 0935-9648 Institutional support: RVO:68378271 Keywords : multiferroic * iron oxide * thin film Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 17.493, year: 2014

  20. Platinum redispersion on metal oxides in low temperature fuel cells

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Cerri, Isotta; Nagami, Tetsuo

    2013-01-01

    We have analyzed the aptitude of several metal oxide supports (TiO2, SnO2, NbO2, ZrO2, SiO2, Ta2O5 and Nb2O5) to redisperse platinum under electrochemical conditions pertinent to the Proton Exchange Membrane Fuel Cell (PEMFC) cathode. The redispersion on oxide supports in air has been studied in ...

  1. Low Temperature Synthesis and Properties of Gadolinium-Doped Cerium Oxide Nanoparticles

    DEFF Research Database (Denmark)

    Machado, M. F. S.; Moraes, L. P. R.; Monteiro, N. K.

    2017-01-01

    Gadolinium-doped cerium oxide (GDC) is an attractive ceramic material for solid oxide fuel cells (SOFCs) both as the electrolyte and in composite electrodes operating at low and intermediate temperatures. GDC exhibits high oxygen ion conductivity at a wide range of temperatures and displays a high...... resistance to carbon deposition when hydrocarbons are used as fuels. However, an inconvenience of ceria-based oxides is the high sintering temperature needed to obtain a fully dense ceramic body. In this study, a green chemistry route for the synthesis of 10 mol% GDC nanoparticles is proposed. The aqueous...

  2. Effect of temperature on the electro-oxidation of ethanol on platinum

    Directory of Open Access Journals (Sweden)

    Ana Paula M. Camargo

    2010-01-01

    Full Text Available We present in this work an experimental investigation of the effect of temperature (from 25 to 180 ºC in the electro-oxidation of ethanol on platinum in two different phosphoric acid concentrations. We observed that the onset potential for ethanol electro-oxidation shifts to lower values and the reaction rates increase as temperature is increased for both electrolytes. The results were rationalized in terms of the effect of temperature on the adsorption of reaction intermediates, poisons, and anions. The formation of oxygenated species at high potentials, mainly in the more diluted electrolyte, also contributes to increase the electro-oxidation reaction rate.

  3. High Temperature Oxidation Behavior of T91 Steel in Dry and Humid Condition

    Directory of Open Access Journals (Sweden)

    Yonghao Leong

    2016-09-01

    Full Text Available High temperature oxidation behavior of T91 ferritic/martensitic steel was examined over the temperature range of 500 to 700°C in dry and humid environments.  The weight gain result revealed that oxidation occurs at all range of temperatures and its rate is accelerated by increasing the temperature. The weight gain of the oxidized steel at 700°C in steam condition was six times bigger than the dry oxidation.. SEM/EDX of the cross-sectional image showed that under dry condition, a protective and steady growth of the chromium oxide (Cr2O3 layer was formed on the steel with the thickness of 2.39±0.34 µm. Meanwhile for the humid environment, it is found that the iron oxide layer, which consists of the hematite (Fe2O3 and magnetite (Fe3O4 was formed as the outer scale, and spinnel as inner scale. This result indicated that the oxidation behavior of T91 steel was affected by its oxidation environment. The existence of water vapor in steam condition may prevent the formation of chromium oxide as protective layer.

  4. High-temperature steam oxidation kinetics of the E110G cladding alloy

    International Nuclear Information System (INIS)

    Király, Márton; Kulacsy, Katalin; Hózer, Zoltán; Perez-Feró, Erzsébet; Novotny, Tamás

    2016-01-01

    In the course of recent years, several experiments were performed at MTA EK (Centre for Energy Research, Hungarian Academy of Sciences) on the isothermal high-temperature oxidation of the improved Russian cladding alloy E110G in steam/argon atmosphere. Using these data and designing additional supporting experiments, the oxidation kinetics of the E110G alloy was investigated in a wide temperature range, between 600 °C and 1200 °C. For short durations (below 500 s) or high temperatures (above 1065 °C) the oxidation kinetics was found to follow a square-root-of-time dependence, while for longer durations and in the intermediate temperature range (800–1000 °C) it was found to approach a cube-root-of-time dependence rather than a square-root one. Based on the results a new best-estimate and a conservative oxidation kinetics model were created. - Highlights: • Steam oxidation kinetics of E110G was studied at MTA EK based on old and new data. • New best-estimate and conservative steam oxidation kinetics were proposed for E110G. • The exponent of oxidation time changed depending on oxidation temperature. • A simple exponential curve was used instead of Arrhenius-type curve for the factor.

  5. Comparative study of high temperature oxidation behaviour in AISI 304 and AISI 439 stainless steels

    Directory of Open Access Journals (Sweden)

    Antônio Claret Soares Sabioni

    2003-06-01

    Full Text Available This work deals with a comparison of high temperature oxidation behaviour in AISI 304 austenitic and AISI 439 ferritic stainless steels. The oxidation experiments were performed between 850 and 950 °C, in oxygen and Ar (100 vpm H2. In most cases, it was formed a Cr2O3 protective scale, whose growth kinetics follows a parabolic law. The exception was for the the AISI 304 steel, at 950 °C, in oxygen atmosphere, which forms an iron oxide external layer. The oxidation resistance of the AISI 439 does not depend on the atmosphere. The AISI 304 has the same oxidation resistance in both atmospheres, at 850 °C, but at higher temperatures, its oxidation rate strongly increases in oxygen atmosphere. Concerning the performance of these steels under oxidation, our results show that the AISI 439 steel has higher oxidation resistance in oxidizing atmosphere, above 850 °C, while, in low pO2 atmosphere, the AISI 304 steel has higher oxidation resistance than the AISI 439, in all the temperature range investigated.

  6. Temperature estimates from the zircaloy oxidation kinetics in the α plus β phase region

    International Nuclear Information System (INIS)

    Olsen, C.S.

    1981-01-01

    Oxidation rates of zircaloy in steam were measured at temperatures between 961 and 1264 K and for duration times between 25 and 1900 seconds in order to calculate, in conjunction with measurements from postirradiation metallographic examination, the prior peak temperatures of zircaloy fuel rod cladding. These temperature estimates will be used in light water reactor research programs to assess (a) the accuracy of temperature measurements of fuel rod cladding peak temperatures from thermocouples attached to the surface during loss-of-coolant experiments (LOCEs), (b) the perturbation of the fuel rod cladding LOCE temperature history caused by the presence of thermocouples, and (c) the measurements of cladding azimuthal temperature gradients near thermocouple locations

  7. High temperature oxidation of thin FeCrAl strips

    International Nuclear Information System (INIS)

    Andrieu, E.; Germidis, A.; Molins, R.

    1997-01-01

    This study concerns the oxidation behaviour between 850 and 1100 C of FeCrAl thin strips. Oxidation kinetics have been continuously recorded on a thermobalance as well as discontinuously in an ''industrial'' furnace. Detailed observations of oxide layers have been performed in transmission electron microscopy on oxidized thin foil cross-sections. Oxide morphologies are correlated with kinetics: Slow kinetics and columnar α alumina grains above 950 C, fast kinetics and transition alumina platelets (γ-alumina) at 850 C and 900 C, followed by small α-alumina grains formation underneath. The weight gains in the industrial furnace displayed significant scatter and were generally greater than those measured in the thermobalance. The effect of extrinsic factors such as specimen size and shape, atmosphere, air flow conditions on the early formation of transition aluminas explains the observed differences. It appears then that in given cases parabolic constant identification from TGA recordings is difficult, or even impossible. This might contribute to explain the differences in the results presented in the literature. (orig.)

  8. Reducibility of ceria-lanthana mixed oxides under temperature programmed hydrogen and inert gas flow conditions

    International Nuclear Information System (INIS)

    Bernal, S.; Blanco, G.; Cifredo, G.; Perez-Omil, J.A.; Pintado, J.M.; Rodriguez-Izquierdo, J.M.

    1997-01-01

    The present paper deals with the preparation and characterization of La/Ce mixed oxides, with La molar contents of 20, 36 and 57%. We carry out the study of the structural, textural and redox properties of the mixed oxides, comparing our results with those for pure ceria. For this aim we use temperature programmed reduction (TPR), temperature programmed desorption (TPD), nitrogen physisorption at 77 K, X-ray diffraction and high resolution electron microscopy. The mixed oxides are more easy to reduce in a flow of hydrogen than ceria. Moreover, in an inert gas flow they release oxygen in higher amounts and at lower temperatures than pure CeO 2 . The textural stability of the mixed oxides is also improved by incorporation of lanthana. All these properties make the ceria-lanthana mixed oxides interesting alternative candidates to substitute ceria in three-way catalyst formulations. (orig.)

  9. Study of the oxidation of Fe-Cr alloys at high temperatures

    International Nuclear Information System (INIS)

    Carneiro, J.F.; Sabioni, A.C.S.

    2010-01-01

    The high temperature oxidation behavior of Fe-1.5%Cr, Fe-5.0%Cr, Fe-10%Cr and Fe- 15%Cr model alloys were investigated from 700 to 850 deg C, in air atmosphere. The oxidation treatments were performed in a thermobalance with a sensitivity of 1μg. The oxide films grown by oxidation of the alloys were characterized by scanning electronic microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD). The oxide films are Fe-Cr spinels with variable composition depending on the alloy composition. For all conditions studied, the oxidation kinetics of these alloys follow a parabolic law. The comparison of the oxidation rates of the four alloys, at 700 deg C, shows that the parabolic oxidation constants decrease from 1.96x10 -9 g 2 .cm -4 .s -1 , for the alloy Fe-1.5% Cr, to 1.18 x 10-14g 2 .cm -4 .s -1 for the alloy Fe-15% Cr. Comparative analysis of the oxidation behavior of the Fe-10%Cr and Fe-15%Cr alloys, between 700 and 850 deg C, shows that the oxidation rates of these alloys are comparable to 800 deg C, above this temperature the Fe-10%Cr alloy shows lower resistance to oxidation. (author)

  10. High temperature oxidation of copper and copper aluminium alloys: Impact on furnace side wall cooling systems

    Science.gov (United States)

    Plascencia Barrera, Gabriel

    The high temperature oxidation behaviours of copper and dilute Cu-Al alloys were investigated. Experiments were carried out by: (i) Oxidizing under various oxygen potentials at different temperatures using a combined TG-DTA apparatus. (ii) Oxidizing in a muffle furnace (in air) at different temperatures for extended periods of time. The oxidation mechanisms were evaluated based upon the kinetic data obtained as well as by X-ray diffraction and microscopical (SEM and optical) analyses. It was found that oxidation of copper strongly depends on the temperature. Two distinct mechanisms were encountered. Between 300 and 500°C, the oxidation rate is controlled by lateral growth of the oxide on the metal surface, whereas between 600 and 1000°C oxidation is controlled by lattice diffusion of copper ions through the oxide scale. On the other hand, the partial pressure of oxygen only has a small effect on the oxidation of copper. Alloy oxidation is also dependent on the temperature. As temperature increases, more aluminium is required to protect copper from being oxidized. It was shown that if the amount of oxygen that dissolves in the alloy exceeds the solubility limit of oxygen in copper, an internal oxidation layer will develop, leading to the formation of a tarnishing scale. On the other hand if the oxygen content in the alloy lies below the solubility limit of oxygen in copper, no oxidation products will form since a tight protective alumina layer will form on the alloy surface. Surface phenomena may affect the oxidation behaviour of dilute Cu-Al alloys. Immersion tests in molten copper matte and copper converting slag, using laboratory scale cooling elements with various copper based materials, were conducted. Results from these tests showed that alloying copper with 3 to 4 wt% Al decreases the oxidation rate of pure copper by 4 orders of magnitude; however due to a significant drop in thermal conductivity, the ability to extract heat is compromised, leading to

  11. Surface chemistry of metals and their oxides in high temperature water

    International Nuclear Information System (INIS)

    Tomlinson, M.

    1975-01-01

    Examination of oxide and metal surfaces in water at high temperature by a broad spectrum of techniques is bringing understanding of corrosion product movement and alleviation of activity transport in CANDU-type reactor primary coolant circuits. (Author)

  12. Solid Oxide Fuel Cell Based Upon Colloidal Deposition of Thin Films for Lower Temperature Operation (Preprint)

    National Research Council Canada - National Science Library

    Reitz, T. L; Xiao, H

    2006-01-01

    In order to reduce the operating temperature of solid oxide fuel cells (SOFCs), anode-supported cells incorporating thin film electrolytes in conjunction with anode/electrolyte and cathode/electrolyte interlayers were studied...

  13. Surface characterization of low-temperature grown yttrium oxide

    Science.gov (United States)

    Krawczyk, Mirosław; Lisowski, Wojciech; Pisarek, Marcin; Nikiforow, Kostiantyn; Jablonski, Aleksander

    2018-04-01

    The step-by-step growth of yttrium oxide layer was controlled in situ using X-ray photoelectron spectroscopy (XPS). The O/Y atomic concentration (AC) ratio in the surface layer of finally oxidized Y substrate was found to be equal to 1.48. The as-grown yttrium oxide layers were then analyzed ex situ using combination of Auger electron spectroscopy (AES), elastic-peak electron spectroscopy (EPES) and scanning electron microscopy (SEM) in order to characterize their surface chemical composition, electron transport phenomena and surface morphology. Prior to EPES measurements, the Y oxide surface was pre-sputtered by 3 kV argon ions, and the resulting AES-derived composition was found to be Y0.383O0.465C0.152 (O/Y AC ratio of 1.21). The SEM images revealed different surface morphology of sample before and after Ar sputtering. The oxide precipitates were observed on the top of un-sputtered Y oxide layer, whereas the oxide growth at the Ar ion-sputtered surface proceeded along defects lines normal to the layer plane. The inelastic mean free path (IMFP) characterizing electron transport was evaluated as a function of energy in the range of 0.5-2 keV from the EPES method. Two reference materials (Ni and Au) were used in these measurements. Experimental IMFPs determined for the Y0.383O0.465C0.152 and Y2O3 surface compositions, λ, were uncorrected for surface excitations and approximated by the simple function λ = kEp at electron energies E between 500 eV and 2000 eV, where k and p were fitted parameters. These values were also compared with IMFPs resulting from the TPP-2 M predictive equation for both oxide compositions. The fitted functions were found to be reasonably consistent with the measured and predicted IMFPs. In both cases, the average value of the mean percentage deviation from the fits varied between 5% and 37%. The IMFPs measured for Y0.383O0.465C0.152 surface composition were found to be similar to the IMFPs for Y2O3.

  14. Epitaxial heterojunctions of oxide semiconductors and metals on high temperature superconductors

    Science.gov (United States)

    Vasquez, Richard P. (Inventor); Hunt, Brian D. (Inventor); Foote, Marc C. (Inventor)

    1994-01-01

    Epitaxial heterojunctions formed between high temperature superconductors and metallic or semiconducting oxide barrier layers are provided. Metallic perovskites such as LaTiO3, CaVO3, and SrVO3 are grown on electron-type high temperature superconductors such as Nd(1.85)Ce(0.15)CuO(4-x). Alternatively, transition metal bronzes of the form A(x)MO(3) are epitaxially grown on electron-type high temperature superconductors. Also, semiconducting oxides of perovskite-related crystal structures such as WO3 are grown on either hole-type or electron-type high temperature superconductors.

  15. High-temperature oxidation of tungsten covered by layer of glass-enamel melt

    International Nuclear Information System (INIS)

    Vasnetsova, V.B.; Shardakov, N.T.; Kudyakov, V.Ya.; Deryabin, V.A.

    1997-01-01

    Corrosion losses of tungsten covered by the layer of glass-enamel melt were determined at 800, 850, 900, 950 deg C. It is shown that the rate of high-temperature oxidation of tungsten decreases after application of glass-enamel melt on its surface. This is probably conditioned by reduction of area of metal interaction with oxidizing atmosphere

  16. Gold-Catalyzed Aerobic Oxidation of 5-Hydroxymethylfurfural in Water at Ambient Temperature

    DEFF Research Database (Denmark)

    Gorbanev, Yury; Kegnæs, Søren; Woodley, John

    2009-01-01

    The aerobic oxidation of 5-hydroxymethylfurfural, a versatile biomass-derived chemical, is examined in water with a titania-supported gold-nanoparticle catalyst at ambient temperature (30 degrees C). The selectivity of the reaction towords 2,5-furandicarboxylic acid and the intermediate oxidation...

  17. Microstructure and elevated-temperature erosion-oxidation behaviour of aluminized 9Cr-1Mo Steel

    OpenAIRE

    Huttunen, E.; Honkanen, M.; Tsipas, Sophia Alexandra; Omar, H.; Tsipas, D.

    2012-01-01

    Degradation of materials by a combination of erosive wear and atmospheric oxidation at elevated temperatures constitutes a problem in some power generation processes, such as fluidized-bed combustion. In this work, 9Cr-1Mo steel, a common tube material in combustion chambers, is coated by a pack cementation method from an Al-containing pack in order to improve the resistance to erosion-oxidation at elevated temperatures. The resulting coating is studied in terms of microstructure and microhar...

  18. An unusual temperature dependence in the oxidation of oxycarbide layers on uranium

    Science.gov (United States)

    Ellis, Walton P.

    1981-09-01

    An anomalous temperature dependence has been observed for the oxidation kinetics of outermost oxycarbide layers on polycrystalline uranium metal. Normally, oxidation or corrosion reactions are expected to proceed more rapidly as the temperature is elevated. Thus, it came as a surprise when we observed that the removal of the outermost atomic layers of carbon from uranium oxycarbide by O 2 reproducibly proceeds at a much faster rate at 25°C than at 280°C.

  19. Kinetics of high-temperature oxidation of (Ti,Ta)(C,N)-based cermets

    International Nuclear Information System (INIS)

    Chicardi, E.; Córdoba, J.M.; Gotor, F.J.

    2016-01-01

    Highlights: • The kinetic of high-temperature oxidation of (Ti,Ta)(C,N)-Co cermets was studied. • A parabolic oxidation kinetic was determined in cermets between 700 °C and 1200 °C. • This parabolic kinetic behaviour is due to the existence of a protective layer. • The protective layer formed was a complex Ti_xTa_1_−_xO_2 oxide with rutile structure. • The oxidation rate is controlled by the Ti and O_2 diffusion through the Ti_xTa_1_−_xO_2. - Abstract: The kinetics of the high-temperature oxidation of titanium–tantalum carbonitride-based cermets with different Ti/Ta ratios was studied. Isothermal oxidation tests were conducted under static air for 48 h at temperatures between 700 °C and 1200 °C. The oxidation satisfied the parabolic kinetics, characteristic of the existence of a protective oxide layer. The apparent activation energy suggests the rate-controlling process during oxidation is the simultaneous inward and outward diffusion of oxygen and titanium, respectively, through the formed protective layer, consisting mainly of a rutile phase. A higher Ta(V) content in the rutile decreased the oxygen diffusivity due to the reduction of oxygen vacancy concentration.

  20. Ammonia oxidation kinetics and temperature sensitivity of a natural marine community dominated by Archaea

    Science.gov (United States)

    Horak, Rachel E A; Qin, Wei; Schauer, Andy J; Armbrust, E Virginia; Ingalls, Anitra E; Moffett, James W; Stahl, David A; Devol, Allan H

    2013-01-01

    Archaeal ammonia oxidizers (AOAs) are increasingly recognized as prominent members of natural microbial assemblages. Evidence that links the presence of AOA with in situ ammonia oxidation activity is limited, and the abiotic factors that regulate the distribution of AOA natural assemblages are not well defined. We used quantitative PCR to enumerate amoA (encodes α-subunit of ammonia monooxygenase) abundances; AOA amoA gene copies greatly outnumbered ammonia-oxidizing bacteria and amoA transcripts were derived primarily from AOA throughout the water column of Hood Canal, Puget Sound, WA, USA. We generated a Michaelis–Menten kinetics curve for ammonia oxidation by the natural community and found that the measured Km of 98±14 nmol l−1 was close to that for cultivated AOA representative Nitrosopumilus maritimus SCM1. Temperature did not have a significant effect on ammonia oxidation rates for incubation temperatures ranging from 8 to 20 °C, which is within the temperature range for depths of measurable ammonia oxidation at the site. This study provides substantial evidence, through both amoA gene copies and transcript abundances and the kinetics response, that AOA are the dominant active ammonia oxidizers in this marine environment. We propose that future ammonia oxidation experiments use a Km for the natural community to better constrain ammonia oxidation rates determined with the commonly used 15NH4+ dilution technique. PMID:23657360

  1. Effects of porosity and temperature on oxidation behavior in air of selected nuclear graphites

    International Nuclear Information System (INIS)

    Chen Dongyue; Li Zhengcao; Miao Wei; Zhang Zhengjun

    2012-01-01

    Nuclear graphite endures gas oxidation in High Temperature Gas-cooled Reactor (HTGR), which may threaten the safety of reactor. To study the oxidation behavior of nuclear graphite, weight loss curve is usually measured through Thermo Gravimetric Analysis (TGA) method. In this work, three brands of nuclear graphite for HTGR (i.e., HSM-SC, IG-11, and NBG-18) are oxidized under 873 and 1073 K in open air, and their weight loss curves are obtained. The acceleration of oxidizing rate is observed for both HSM-SC and IG-11, and is attributed to the large porosity increase during oxidation process. For HSM-SC, the porosity increase comes from preferential binder oxidation, and thus its binder quality shall be improved to obtain better oxidation resistance. Temperature effects on oxidation for HSM-SC are also studied, which shows that oxidizing gas tends to be exhausted at graphite surface at high temperature instead of penetrate into the interior of bulk. (author)

  2. High temperature oxidation behaviour of nanostructured cermet coatings in a mixed CO2 - O2 environment

    Science.gov (United States)

    Farrokhzad, M. A.; Khan, T. I.

    2014-06-01

    Nanostructured ceramic-metallic (cermet) coatings composed of nanosized ceramic particles (α-Al2O3 and TiO2) dispersed in a nickel matrix were co-electrodeposited and then oxidized at 500°C, 600°C and 700°C in a mixed gas using a Thermo-gravimetric Analysis (TGA) apparatus. The mixed gas was composed of 15% CO2, 10% O2 and 75% N2. This research investigates the effects of CO2 and O2 partial pressures on time-depended oxidation rates for coatings and compared them to the results from atmospheric oxidation under similar temperatures. The increase in partial pressure of oxygen due to the presence of CO2 at each tested temperature was calculated and correlated to the oxidation rate of the coatings. The results showed that the presence of CO2 in the system increased the oxidation rate of cermet coatings when compared to atmospheric oxidation at the same temperature. It was also shown that the increase in the oxidation rate is not the result of CO2 acting as the primary oxidant but as a secondary oxidant which results in an increase of the total partial pressure of oxygen and consequently higher oxidation rates. The WDS and XRD analyses results showed that the presence of nanosized TiO2 particles in a nickel matrix can improve oxidation behaviour of the coatings by formation of Ni-Ti compounds on oxidizing surface of the coating which was found beneficiary in reducing the oxidation rates for cermet coatings.

  3. Low temperature delayed recombination decay in complex oxide scintillating crystals

    Czech Academy of Sciences Publication Activity Database

    Mihóková, Eva; Jarý, Vítězslav; Schulman, L. S.; Nikl, Martin

    2014-01-01

    Roč. 61, č. 1 (2014), 257-261 ISSN 0018-9499 R&D Projects: GA MŠk LH12150; GA MŠk LH12185 Grant - others:AVČR(CZ) M100101212 Institutional support: RVO:68378271 Keywords : luminescence * oxides * scintillator * tunneling Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.283, year: 2014

  4. Optimized high temperature oxidation and cleaning at Bugey 3

    International Nuclear Information System (INIS)

    Ranchoux, Gilles; Wintergerst, Matthieu; Bachet, Martin; Leclercq, Stephanie; Duron, Jean-Daniel; Meunier, Jean-Pierre; Blond, Serge; Dacquait Frederic

    2012-09-01

    As a part of the EDF Source Term Reduction project, an experimental procedure was carried out at Bugey 3 further to the steam generator replacement. This innovative procedure consists in theory in two complementary phases /1/: - Phase 1: a SG tubes optimized oxidation performed during pre-critical hot functional tests (basic and reducing chemistry) aims to generate an as protective as possible inner oxide layer allowing to reduce the later nickel release, - Phase 2: a cleaning procedure of the primary circuit performed under acid and reducing chemical conditioning at 170 deg. C intends to dissolve and eliminate the outer oxide layer by a simultaneous purification. The objective of such a procedure is to reduce corrosion products inventory (mainly nickel) generated by the first SG tube oxidation during hot functional tests and first operation months by carrying out an appropriate cleaning procedure. Gains were expected not only on RCS and auxiliary systems contamination, dose rates and thus collective dose but also on next outages duration. The objective of this paper is to describe the process implementation at Bugey 3: effective procedure put in place, monitoring program (chemistry and dose rate measurements, EMECC campaign) and firsts results. (authors)

  5. Ni–Ta–O mixed oxide catalysts for the low temperature oxidative dehydrogenation of ethane to ethylene

    KAUST Repository

    Zhu, Haibo

    2015-09-01

    The "wet" sol-gel and "dry" solid-state methods were used to prepare Ni-Ta-O mixed oxide catalysts. The resulting Ni-Ta oxides exhibit high activity and selectivity for the low temperature oxidative dehydrogenation of ethane to ethylene. The Ta/(Ni + Ta) atomic ratios (varying from 0 to 0.11 in "wet" sol-gel method, and from 0 to 0.20 in "dry" solid-state method) as well as the preparation methods used in the synthesis, play important roles in controlling catalyst structure, activity, selectivity and stability in the oxidative dehydrogenation of ethane. Electron microscopy characterizations (TEM, EELS mapping, and HAADF-STEM) clearly demonstrate that the Ta atoms are inserted into NiO crystal lattice, resulting in the formation of a new Ni-Ta oxide solid solution. More Ta atoms are found to be located at the lattice sites of crystal surface in sol-gel catalyst. While, a small amount of thin layer of Ta2O5 clusters are detected in solid-state catalyst. Further characterization by XRD, N2 adsorption, SEM, H2-TPR, XPS, and Raman techniques reveal different properties of these two Ni-Ta oxides. Due to the different properties of the Ni-Ta oxide catalysts prepared by two distinct approaches, they exhibit different catalytic behaviors in the ethane oxidative dehydrogenation reaction at low temperature. Thus, the catalytic performance of Ni-Ta-O mixed oxide catalysts can be systematically modified and tuned by selecting a suitable synthesis method, and then varying the Ta content. ©2015 Elsevier Inc. All rights reserved.

  6. Oxidation kinetics of zircaloy-4 in the temperature range correspondent to alpha phase

    International Nuclear Information System (INIS)

    Medeiros, L.F.

    1975-12-01

    Oxidation kinetics of Zry-4 in the alpha phase is isothermally studied in the temperature range from 600 0 C to 800 0 C, by continuous and discontinuous gravimetric methods. The total mass gain during the oxidation takes place by two distinct ways: oxide formation and solid solution formation. The first one has been studied by microscopy: the latter by microhardness. The oxygen diffusion coefficients in the zirconium are experimentally determined by microhardness measurements and are compared with those obtained by the oxide layer thickness and by oxygen mass in the oxide. The oxygen diffusion coefficients in the oxide are obtained too by oxide layer thickness and by oxygen diffusivities in the alpha phase and compared with literature. (author)

  7. Kinetics and mechanism of the oxidation of cerium in air at ambient temperature

    International Nuclear Information System (INIS)

    Wheeler, D.W.

    2016-01-01

    Highlights: • XRD and transverse sections suggest Ce_2O_3 forms on Ce before being overlaid by CeO_2. • XRD and oxide thickness measurements both indicate linear oxidation. • Extensive cracking on oxide surface which sustains continuing oxidation. • Electron microscopy has shown features indicative of nodular oxidation. • Oxide growth rate determined to be 0.1 μm day"−"1 under the conditions in this study. - Abstract: This paper describes a study of the oxidation of cerium in air at ambient temperature. Specimens were exposed for up to 60 days, during which they were analysed by X-ray diffraction (XRD) at regular intervals. Both XRD and oxide thickness measurements indicate linear oxidation over the duration of this study. Under the conditions employed in this study, the rate of oxide growth has been determined to be 0.1 μm day"−"1. The oxidation process appears to be assisted by extensive cracking in the oxide layer which acts as a non-protective film for the underlying metal.

  8. Determination of surface coverage of catalysts : temperature programmed experiments on platinum and iridium sponge catalysts after low temperature ammonia oxidation

    NARCIS (Netherlands)

    van den Broek, A.C.M.; Grondelle, van J.; Santen, van R.A.

    1999-01-01

    The activity of iridium and platinum sponge catalysts was studied in the low temperature gas phase oxidation of ammonia with oxygen. Under the reaction conditions used, iridium was found to be more active and more selective to nitrogen than platinum. Furthermore it was established from activity

  9. Oxidation characteristics of MgF2 in air at high temperature

    Science.gov (United States)

    Chen, H. K.; Jie, Y. Y.; Chang, L.

    2017-02-01

    High temperature oxidation properties of MgF2 in air were studied. The changes of phase composition, macro surface morphology, weight and elemental composition of MgF2 samples with temperature were investigated by using XRD, EDS and gravimetric analyses. The results show that the oxidation reaction of MgF2 converted to MgO occurred at high temperature, and the reaction was accelerated by the increase of temperature and the presence of impurities. This result clarifies the understanding of the high temperature oxidation behavior of MgF2 in air, and provides a theoretical basis for the reasonable application of MgF2 in optical coating materials, electronic ceramic materials and magnesium melt protection.

  10. Partial oxidation of methane in a temperature-controlled dielectric barrier discharge reactor

    KAUST Repository

    Zhang, Xuming

    2015-01-01

    We studied the relative importance of the reduced field intensity and the background reaction temperature in the partial oxidation of methane in a temperature-controlled dielectric barrier discharge reactor. We obtained important mechanistic insight from studying high-temperature and low-pressure conditions with similar reduced field intensities. In the tested range of background temperatures (297 < T < 773 K), we found that the conversion of methane and oxygen depended on both the electron-induced chemistry and the thermo-chemistry, whereas the chemical pathways to the products were overall controlled by the thermo-chemistry at a given temperature. We also found that the thermo-chemistry enhanced the plasma-assisted partial oxidation process. Our findings expand our understanding of the plasma-assisted partial oxidation process and may be helpful in the design of cost-effective plasma reformers. © 2014 The Combustion Institute.

  11. Nanotubes of rare earth cobalt oxides for cathodes of intermediate-temperature solid oxide fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Sacanell, Joaquin [Departamento de Fisica, Centro Atomico Constituyentes, CNEA, Av. Gral. Paz 1499, 1650 San Martin, Buenos Aires (Argentina); CINSO (Centro de Investigaciones en Solidos), CITEFA-CONICET, J.B. de La Salle 4397, 1603 Villa Martelli, Buenos Aires (Argentina); Leyva, A. Gabriela [Departamento de Fisica, Centro Atomico Constituyentes, CNEA, Av. Gral. Paz 1499, 1650 San Martin, Buenos Aires (Argentina); Escuela de Ciencia y Tecnologia, UNSAM. Av. Gral. Paz 1499, 1650 San Martin, Buenos Aires (Argentina); Bellino, Martin G.; Lamas, Diego G. [CINSO (Centro de Investigaciones en Solidos), CITEFA-CONICET, J.B. de La Salle 4397, 1603 Villa Martelli, Buenos Aires (Argentina)

    2010-04-02

    In this work we studied the electrochemical properties of cathodes for intermediate-temperature solid oxide fuel cells (IT-SOFCs) prepared with nanotubes of La{sub 0.6}Sr{sub 0.4}CoO{sub 3} (LSCO). Their nanostructures consist of agglomerated nanoparticles in tubular structures of sub-micrometric diameter. The resulting cathodes are highly porous both at the micro- and the nanoscale. This fact increases significantly the access to active sites for the oxygen reduction. We investigated the influence of the diameter of the precursor nanotubes on the polarization resistance of the LSCO cathodes on CeO{sub 2}-10 mol.% Sm{sub 2}O{sub 3} (SDC) electrolytes under air atmosphere, evaluated in symmetrical [LSCO/SDC/LSCO] cells. Our results indicate an optimized performance when the diameter of precursor nanotubes is sufficiently small to become dense nanorods after cathode sintering. We present a phenomenological model that successfully explains the behavior observed and considers that a small starting diameter acts as a barrier that prevents grains growth. This is directly related with the lack of contact points between nanotubes in the precursor, which are the only path for the growth of ceramic grains. We also observed that a conventional sintering process (of 1 h at 1000 C with heating and cooling rates of 10 C min{sup -1}) has to be preferred against a fast firing one (1 or 2 min at 1100 C with heating and cooling rates of 100 C min{sup -1}) in order to reach a higher performance. However, a good adhesion of the cathode can be achieved with both methods. Our results suggest that oxygen vacancy diffusion is enhanced while decreasing LSCO particle size. This indicates that the high performance of our nanostructured cathodes is not only related with the increase of the number of active sites for oxygen reduction but also to the fact that the nanotubes are formed by nanoparticles. (author)

  12. High-temperature oxidation kinetics of sponge-based E110 cladding alloy

    Science.gov (United States)

    Yan, Yong; Garrison, Benton E.; Howell, Mike; Bell, Gary L.

    2018-02-01

    Two-sided oxidation experiments were recently conducted at 900°C-1200 °C in flowing steam with samples of sponge-based Zr-1Nb alloy E110. Although the old electrolytic E110 tubing exhibited a high degree of susceptibility to nodular corrosion and experienced breakaway oxidation rates in a relatively short time, the new sponge-based E110 demonstrated steam oxidation behavior comparable to Zircaloy-4. Sample weight gain and oxide layer thickness measurements were performed on oxidized E110 specimens and compared to oxygen pickup and oxide layer thickness calculations using the Cathcart-Pawel correlation. Our study shows that the sponge-based E110 follows the parabolic law at temperatures above 1015 °C. At or below 1015 °C, the oxidation rate was very low when compared to Zircaloy-4 and can be represented by a cubic expression. No breakaway oxidation was observed at 1000 °C for oxidation times up to 10,000 s. Arrhenius expressions are given to describe the parabolic rate constants at temperatures above 1015 °C and cubic rate constants are provided for temperatures below 1015 °C. The weight gains calculated by our equations are in excellent agreement with the measured sample weight gains at all test temperatures. In addition to the as-fabricated E110 cladding sample, prehydrided E110 cladding with hydrogen concentrations in the 100-150 wppm range was also investigated. The effect of hydrogen content on sponge-based E110 oxidation kinetics was minimal. No significant difference was found between as-fabricated and hydrided samples with regard to oxygen pickup and oxide layer thickness for hydrogen contents below 150 wppm.

  13. On the influence of cold work on the oxidation behavior of some austenitic stainless steels: High temperature oxidation

    NARCIS (Netherlands)

    Langevoort, J.C.; Fransen, T.; Gellings, P.J.

    1984-01-01

    AISI 304, 314, 321, and Incoloy 800H have been subjected to several pretreatments: polishing, milling, grinding, and cold drawing. In the temperature range 800–1400 K, cold work improves the oxidation resistance of AISI 304 and 321 slightly, but has a relatively small negative effect on the

  14. An Aurivillius Oxide Based Cathode with Excellent CO2 Tolerance for Intermediate-Temperature Solid Oxide Fuel Cells.

    Science.gov (United States)

    Zhu, Yinlong; Zhou, Wei; Chen, Yubo; Shao, Zongping

    2016-07-25

    The Aurivillius oxide Bi2 Sr2 Nb2 MnO12-δ (BSNM) was used as a cobalt-free cathode for intermediate-temperature solid oxide fuel cells (IT-SOFCs). To the best of our knowledge, the BSNM oxide is the only alkaline-earth-containing cathode material with complete CO2 tolerance that has been reported thus far. BSNM not only shows favorable activity in the oxygen reduction reaction (ORR) at intermediate temperatures but also exhibits a low thermal expansion coefficient, excellent structural stability, and good chemical compatibility with the electrolyte. These features highlight the potential of the new BSNM material as a highly promising cathode material for IT-SOFCs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Studies on room temperature electrochemical oxidation and its effect on the transport properties of TBCCO films

    International Nuclear Information System (INIS)

    Shirage, P M; Shivagan, D D; Pawar, S H

    2004-01-01

    A novel room temperature electrochemical process for the synthesis of single-phase Tl 2 Ba 2 Ca 2 Cu 3 O 10 (TBCCO/Tl-2223) superconducting films has been developed. Electrochemical parameters were optimized by studying linear sweep voltammetry (LSV), cyclic voltammetry (CV) and chronoamperometry (CA) for the deposition of Tl-Ba-Ca-Cu alloy at room temperature. The superconducting films of the TBCCO were obtained by two oxidation techniques. In the first technique, the electrodeposited Tl-Ba-Ca-Cu alloyed films were oxidized at various temperatures in flowing oxygen atmosphere. In the second technique, stoichiometric electrocrystallization to get Tl 2 Ba 2 Ca 2 Cu 3 O 10 (Tl-2223) was completed by electrochemically intercalating oxygen species into Tl-Ba-Ca-Cu alloy at room temperature for various lengths of time. The oxygen content in the samples was varied by varying the electrochemical oxidation period, and the changes in the crystal structure, superconducting transition temperature (T c ) and critical current density (J c ) were recorded. The high temperature furnace oxidation technique was replaced by the room temperature electrochemical oxidation technique. The dependence of superconducting parameters on oxygen content is correlated with structure-property relations

  16. Kinetic and reaction pathways of methanol oxidation on platinum

    International Nuclear Information System (INIS)

    McCabe, R.W.; McCready, D.F.

    1986-01-01

    Methanol oxidation kinetics were measured on Pt wires in a flow reactor at pressures between 30 and 130 Pa. The kinetics were measured as a function of oxygen-to-methanol equivalence ratio phi and wire temperature. In methanol-lean feeds (phi 2 CO, CO 2 , and H 2 O were the only products; in methanol-rich feeds (phi > 1), CO, H 2 , H 2 CO, CO 2 , and H 2 O were observed. Experiments with 18 O 2 showed that the principal methanol oxidation pathway does not involve C-O bond dissociation. However, the 18 O 2 experiments, together with other features of the methanol oxidation data, also provided evidence for a minor oxidation pathway (accounting for less than 1% of the product CO 2 ) which proceeds through a carbon intermediate. A mathematical model is presented which describes the principal CH 3 OH oxidation pathway as a series reaction involving adsorbed H 2 CO and CO intermediates. Consistent with experimental results, the model predicts that inhibition by adsorbed CO should be weaker for CH 3 OH and H 2 CO oxidation than for CO oxidation. 34 references, 10 figures, 2 tables

  17. Oxidation resistance of nickel alloys at high temperature

    International Nuclear Information System (INIS)

    Tyuvin, Yu.D.; Rogel'berg, I.L.; Ryabkina, M.M.; Plakushchaya, A.F.

    1977-01-01

    The heat resistance properties of nickel alloys Ni-Cr-Si, Ni-Si-Al, Ni-Si-Mn and Ni-Al-Mn have been studied by the weight method during oxidation in air at 1000 deg and 1200 deg C. It is demonstrated that manganese reduces the heat resistance properties of Ni-Si and Ni-Al alloys, whilst the addition of over 3% aluminium enhances the heat resistance properties of Ni-Si (over 1.5%) alloys. The maximum heat resistance properties are shown by Ni-Si-Al and Ni-Cr-Si alloys with over 2% Si. These alloys offer 3 to 4 times better oxidation resistance as compared with pure nickel at 1000 deg C and 10 times at 1200 deg C

  18. Effects of water turbidity and different temperatures on oxidative stress in caddisfly (Stenopsyche marmorata) larvae.

    Science.gov (United States)

    Suzuki, Jumpei; Imamura, Masahiro; Nakano, Daisuke; Yamamoto, Ryosuke; Fujita, Masafumi

    2018-07-15

    Anthropogenic water turbidity derived from suspended solids (SS) is caused by reservoir sediment management practices such as drawdown flushing. Turbid water induces stress in many aquatic organisms, but the effects of turbidity on oxidative stress responses in aquatic insects have not yet been demonstrated. Here, we examined antioxidant responses, oxidative damage, and energy reserves in caddisfly (Stenopsyche marmorata) larvae exposed to turbid water (0 mg SS L -1 , 500 mg SS L -1 , and 2000 mg SS L -1 ) at different temperatures. We evaluated the combined effects of turbid water and temperature by measuring oxidative stress and using metabolic biomarkers. No turbidity level was significantly lethal to S. marmorata larvae. Moreover, there were no significant differences in antioxidant response or oxidative damage between the control and turbid water treatments at a low temperature (10 °C). However, at a high temperature (25 °C), turbid water modulated the activity of the antioxidant enzymes superoxide dismutase and catalase and the oxygen radical absorbance capacity as an indicator of the redox state of the insect larvae. Antioxidant defenses require energy, and high temperature was associated with low energy reserves, which might limit the capability of organisms to counteract reactive oxygen species. Moreover, co-exposure to turbid water and high temperature caused fluctuation of antioxidant defenses and increased the oxidative damage caused by the production of reactive oxygen species. Furthermore, the combined effect of high temperature and turbid water on antioxidant defenses and oxidative damage was larger than the individual effects. Therefore, our results demonstrate that exposure to both turbid water and high temperature generates additive and synergistic interactions causing oxidative stress in this aquatic insect species. Copyright © 2018. Published by Elsevier B.V.

  19. Electrochemical characterization of oxide film formed at high temperature on Alloy 690

    Energy Technology Data Exchange (ETDEWEB)

    Abraham, Geogy J., E-mail: gja@barc.gov.in [Materials Science Division, BARC, Mumbai 400 085 (India); Bhambroo, Rajan [Deptt. of Metallurgical Engg. and Mat. Sci., IIT Bombay, Mumbai 400 076 (India); Kain, V. [Materials Science Division, BARC, Mumbai 400 085 (India); Shekhar, R. [CCCM, BARC, Hyderabad 500 062 (India); Dey, G.K. [Materials Science Division, BARC, Mumbai 400 085 (India); Raja, V.S. [Deptt. of Metallurgical Engg. and Mat. Sci., IIT Bombay, Mumbai 400 076 (India)

    2012-02-15

    Highlights: Black-Right-Pointing-Pointer GD-QMS studies of high temperature oxide film formed on Alloy 690. Black-Right-Pointing-Pointer Defect density reduced with increase in temperature. Black-Right-Pointing-Pointer Electrochemical behaviour of oxide film correlated to the Cr-content in oxide. - Abstract: High temperature passivation studies on Alloy 690 were carried out in lithiated water at 250 Degree-Sign C, 275 Degree-Sign C and 300 Degree-Sign C for 72 h. The passive films were characterized by glow discharge-quadrupole mass spectroscopy (GD-QMS) for compositional variation across the depth and micro laser Raman spectroscopy for oxide composition on the surface. The defect density in the oxide films was established from the Mott-Schottky analysis using electrochemical impedance spectroscopy. Electrochemical experiments at room temperature in chloride medium revealed best passivity behaviour by the oxide film formed at 300 Degree-Sign C for 72 h. The electrochemical studies were correlated to the chromium (and oxygen) content of the oxide films. Autoclaving at 300 Degree-Sign C resulted in the best passive film formation on Alloy 690 in lithiated water.

  20. Green synthesis of Ni-Nb oxide catalysts for low-temperature oxidative dehydrogenation of ethane

    KAUST Repository

    Zhu, Haibo; Rosenfeld, Devon C.; Anjum, Dalaver H.; Caps, Valerie; Basset, Jean-Marie

    2015-01-01

    The straightforward solid-state grinding of a mixture of Ni nitrate and Nb oxalate crystals led to, after mild calcination (T<400°C), nanostructured Ni-Nb oxide composites. These new materials efficiently catalyzed the oxidative dehydrogenation (ODH

  1. Effect of calcination temperature on formaldehyde oxidation performance of Pt/TiO2 nanofiber composite at room temperature

    Science.gov (United States)

    Xu, Feiyan; Le, Yao; Cheng, Bei; Jiang, Chuanjia

    2017-12-01

    Catalytic oxidation at room temperature over well-designed catalysts is an environmentally friendly method for the abatement of indoor formaldehyde (HCHO) pollution. Herein, nanocomposites of platinum (Pt) and titanium dioxide (TiO2) nanofibers with various phase compositions were prepared by calcining the electrospun TiO2 precursors at different temperatures and subsequently depositing Pt nanoparticles (NPs) on the TiO2 through a NaBH4-reduction process. The phase compositions and structures of Pt/TiO2 can be easily controlled by varying the calcination temperature. The Pt/TiO2 nanocomposites showed a phase-dependent activity towards the catalytic HCHO oxidation. Pt/TiO2 containing pure rutile phase showed enhanced activity with a turnover frequency (TOF) of 16.6 min-1 (for a calcination temperature of 800 °C) as compared to those containing the anatase phase or mixed phases. Density functional theory calculation shows that TiO2 nanofibers with pure rutile phase have stronger adsorption ability to Pt atoms than anatase phase, which favors the reduction of Pt over rutile phase TiO2, leading to higher contents of metallic Pt in the nanocomposite. In addition, the Pt/TiO2 with rutile phase possesses more abundant oxygen vacancies, which is conducive to the activation of adsorbed oxygen. Consequently, the Pt/rutile-TiO2 nanocomposite exhibited better catalytic activity towards HCHO oxidation at room temperature.

  2. Low temperature self-assembled growth of rutile TiO2/manganese oxide nanocrystalline films

    Science.gov (United States)

    Sun, Zhenya; Zhou, Daokun; Du, Jianhua; Xie, Yuxing

    2017-10-01

    We report formation of rutile TiO2 nanocrystal at low temperature range in the presence of α-MnO2 which self-assembled onto sulfanyl radical activated silicon oxide substrate. SEM, HRTEM, XPS and Raman spectroscopy were used to study the morphology and oxidation state of synthesised crystals. The results showed that when the α-MnO2 was reduced to Mn3O4, it induced the formation of rutile instead of anatase phase in the TiCl4-HCl aqueous system. The finding will promote the understanding of phase transformation mechanism when manganese oxide and titanium oxide co-exist in soil and water environment.

  3. Low-temperature oxidation effects on the morphological and structural properties of hexagonal Zn nano disks

    Energy Technology Data Exchange (ETDEWEB)

    Lopez, R.; Villa S, G.; Rosales D, J. [Tecnologico de Estudios Superiores de Jocotitlan, Carretera Toluca-Atlacomulco Km 44.8, Jocotitlan, Estado de Mexico (Mexico); Vigueras S, E.; Hernandez L, S. [Universidad Autonoma del Estado de Mexico, Laboratorio de Investigacion y Desarrollo de Materiales Avanzados, Paseo Colon esquina Paseo Tollocan, Toluca, Estado de Mexico (Mexico); Acuna, P. [Universidad Autonoma del Estado de Mexico, Programa de Doctorado en Ciencia de Materiales, Paseo Colon esquina Paseo Tollocan, Toluca, Estado de Mexico (Mexico); Argueta V, A.; Colin B, N., E-mail: lorr810813@gmail.com [Tecnologico de Estudios Superiores de Jocotitlan, Programa de Ingenieria Mecatronica, Carretera Toluca-Atlacomulco Km 44.8, Jocotitlan, Estado de Mexico (Mexico)

    2017-11-01

    Ambient-atmosphere oxidation in the temperature range of 90-450 degrees Celsius was performed over Zn films composed by well-faceted hexagonal nano disks, which were deposited by thermal evaporation. Morphological and structural properties of oxidized Zn nano disks were studied by scanning electron microscopy, transmission electron microscopy, energy dispersive spectroscopy, X-ray diffraction and Raman scattering measurements. It was found that Zn nano disks keep its original shape only when they are annealed at 90 or 150 degrees Celsius. Smooth oxidation occurred only on the rectangular faces of Zn nano disks heated at 150 degrees Celsius. Thermal oxidation at 250 degrees Celsius favored growth of Zn O nano needles over the surface of the Zn nano disks. Hexagonal-shape of Zn nano disks was transformed completely into a complex morphology composed by different shaped particles, with further increase in oxidation temperature to 450 degrees Celsius. (Author)

  4. Low-temperature atmospheric oxidation of mixtures of titanium and carbon black or brown

    International Nuclear Information System (INIS)

    Elizarova, V.A.; Babaitsev, I.V.; Barzykin, V.V.; Gerusova, V.P.; Rozenband, V.I.

    1984-01-01

    This article reports on the thermogravimetric investigation of mixtures of titanium no. 2 and carbon black with various mass carbon contents. Adding carbon black (as opposed to boron) to titanium leads to an increase in the rate of heat release of the oxidation reaction. An attempt is made to clarify the low-temperature oxidation mechanism of titanium mixtures in air. An x-ray phase and chemical (for bound carbon) analysis of specimens of a stoichiometric Ti + C mixture after heating in air to a temperature of 650 0 C at the rate of 10 0 /min was conducted. The results indicate that the oxidation of the titanium-carbon mixture probably proceeds according to a more complex mechanism associated with the transport of the gaseous carbon oxidation products and their participation in the titanium oxidation

  5. Low-temperature oxidation effects on the morphological and structural properties of hexagonal Zn nano disks

    International Nuclear Information System (INIS)

    Lopez, R.; Villa S, G.; Rosales D, J.; Vigueras S, E.; Hernandez L, S.; Acuna, P.; Argueta V, A.; Colin B, N.

    2017-01-01

    Ambient-atmosphere oxidation in the temperature range of 90-450 degrees Celsius was performed over Zn films composed by well-faceted hexagonal nano disks, which were deposited by thermal evaporation. Morphological and structural properties of oxidized Zn nano disks were studied by scanning electron microscopy, transmission electron microscopy, energy dispersive spectroscopy, X-ray diffraction and Raman scattering measurements. It was found that Zn nano disks keep its original shape only when they are annealed at 90 or 150 degrees Celsius. Smooth oxidation occurred only on the rectangular faces of Zn nano disks heated at 150 degrees Celsius. Thermal oxidation at 250 degrees Celsius favored growth of Zn O nano needles over the surface of the Zn nano disks. Hexagonal-shape of Zn nano disks was transformed completely into a complex morphology composed by different shaped particles, with further increase in oxidation temperature to 450 degrees Celsius. (Author)

  6. Change in the work function of zirconium by oxidation at high temperatures and low oxygen pressures

    International Nuclear Information System (INIS)

    Maeno, Yutaka; Yamamoto, Masahiro; Naito, Shizuo; Mabuchi, Mahito; Hashino, Tomoyasu

    1991-01-01

    Changes in the work function of zirconium on oxidation are measured at oxygen pressures of 3.0 x 10 -6 - 3.0 x 10 -4 Pa and at temperatures in the range 426-775 K. The work function first decreases then increases until a final saturation stage is reached. Use of secondary-ion mass spectroscopy (SIMS) shows that the changes correspond to oxygen adsorption, oxide nucleation and oxide growth, respectively. The initial decrease in work function is interpreted by the incorporation of oxygen adatoms into the subsurface. The oxygen adsorption potential of zirconium is evaluated by an effective medium theory, and the physical origin of the incorporation of oxygen adatoms is discussed. The positive change in the work function caused by oxide formation and the temperature and pressure dependences of the change in the work function by oxidation are explained qualitatively. (author)

  7. Induction of enhanced methane oxidation in compost: Temperature and moisture response

    International Nuclear Information System (INIS)

    Mor, Suman; Visscher, Alex de; Ravindra, Khaiwal; Dahiya, R.P.; Chandra, A.; Cleemput, Oswald van

    2006-01-01

    Landfilling is one of the most common ways of municipal solid waste disposal. Degradation of organic waste produces CH 4 and other landfill gases that significantly contribute to global warming. However, before entering the atmosphere, part of the produced CH 4 can be oxidised while passing through the landfill cover. In the present study, the oxidation rate of CH 4 was studied with various types of compost as possible landfill cover. The influence of incubation time, moisture content and temperature on the CH 4 oxidation capacity of different types of compost was examined. It was observed that the influence of moisture content and temperature on methane oxidation is time-dependent. Maximum oxidation rates were observed at moisture contents ranging from 45% to 110% (dry weight basis), while the optimum temperature ranged from 15 to 30 deg. C

  8. Irradiation effects of high temperature superconductor of lanthanoid oxides

    Energy Technology Data Exchange (ETDEWEB)

    Ueda, Koh-ichi; Kohara, Takao [Himeji Inst. of Tech., Hyogo (Japan)

    1996-04-01

    Neutron irradiation effects on excess oxygen were studied by neutron irradiation on La{sub 2}CuO{sub 4} treated with high pressure oxygen. La{sub 2}CuO{sub 4} was prepared by the usual method and annealed for 10 h under the oxygen pressure of 800-2000 atm. at 600degC. The superconducting transition temperature (Tc) is 27-32K before irradiation (La{sub 2}CuO{sub 4+d}, amount of excess oxygen d=0.03-0.12). Neutron irradiation was carried out by two kinds of experiments. Low irradiation dose test at low temperature (LTL: {approx}20-200K, storage in LN{sub 2}) showed Tc decreased more slowly than that of high temperature range. Experiment at high temperature (Hyd:{approx}80deg{yields}, storage at room temperature) showed -10K/10{sup 18}n/cm{sup 2}, the decrease of Tc was three times larger than that of YBCO type superconductor. (S.Y.)

  9. Investigation of NOx Reduction by Low Temperature Oxidation Using Ozone Produced by Dielectric Barrier Discharge

    DEFF Research Database (Denmark)

    Stamate, Eugen; Irimiea, Cornelia; Salewski, Mirko

    2013-01-01

    NOx reduction by low temperature oxidation using ozone produced by a dielectric barrier discharge generator is investigated for different process parameters in a 6m long reactor in serpentine arrangement using synthetic dry flue gas with NOx levels below 500 ppm, flows up to 50 slm and temperatures...

  10. Temperatures In Compost Landfill Covers As Result Of Methane Oxidation And Compost Respiration

    DEFF Research Database (Denmark)

    Scheutz, Charlotte; Merono, A. R.; Pedersen, Rasmus Broen

    2011-01-01

    This study investigated the influence of the temperature on methane (CH4) oxidation and respiration in compost sampled at a full scale biocover implemented at Klintholm landfill exhibiting high temperatures. Compost material was collected at Klintholm landfill and incubated with and without CH4...

  11. Long-Term Cyclic Oxidation Behavior of Wrought Commercial Alloys at High Temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Li, Bingtao [Iowa State Univ., Ames, IA (United States)

    2003-01-01

    The oxidation resistance of a high-temperature alloy is dependent upon sustaining the formation of a protective scale, which is strongly related to the alloying composition and the oxidation condition. The protective oxide scale only provides a finite period of oxidation resistance owing to its eventual breakdown, which is especially accelerated under thermal cycling conditions. This current study focuses on the long-term cyclic oxidation behavior of a number of commercial wrought alloys. The alloys studied were Fe- and Ni-based, containing different levels of minor elements, such as Si, Al, Mn, and Ti. Oxidation testing was conducted at 1000 and 1100 C in still air under both isothermal and thermal cycling conditions (1-day and 7-days). The specific aspects studied were the oxidation behavior of chromia-forming alloys that are used extensively in industry. The current study analyzed the effects of alloying elements, especially the effect of minor element Si, on cyclic oxidation resistance. The behavior of oxide scale growth, scale spallation, subsurface changes, and chromium interdiffusion in the alloy were analyzed in detail. A novel model was developed in the current study to predict the life-time during cyclic oxidation by simulating oxidation kinetics and chromium interdiffusion in the subsurface of chromia-forming alloys.

  12. 9% Cr steel high temperature oxidation. Solutions investigated for improving corrosion resistance of the steel

    Energy Technology Data Exchange (ETDEWEB)

    Evin, Harold Nicolas; Heintz, Olivier; Chevalier, Sebastien [UMR 5209 CNRS-Bourgogne Univ. (France). Lab. Interdisciplinaire Carnot de Bourgogne; Foejer, Cecilia; Jakani, Saad; Dhont, Annick; Claessens, Serge [OCAS N.V. ArcelorMittal Global R and D, Gent (Belgium)

    2010-07-01

    The improvement of high temperature oxidation resistance of low chromium content steels, such as T/P91, is of great interest in regards with their application in thermal power generating plants. Indeed, they possess good creep properties, but are facing their limits of use at temperature higher than 600 C, due to accelerated corrosion phenomena. Good knowledge of the mechanisms involved during their oxidation process is needed to prevent the degradation of the materials and to extend life time of the power plants components. Oxide layers thermally grown, on 9% Cr steels (provided by OCAS N.V), during isothermal tests between 600 C and 750 C in laboratory air under atmospheric pressure were investigated, by Scanning Electron Microscopy (SEM) and X-ray diffraction (XRD). The oxidation behaviour appeared very limited at 750 C, due to the presence of a breakaway, which can be linked to iron porous oxide grown over the surface of the samples. ''In situ'' X-ray Photoelectron spectroscopy (XPS) analyses were performed in air at 600 C after short exposures (between 5 min and 25 h). A complex mixture of iron oxide, Cr{sub 2}O{sub 3} and Cr (VI) species were characterized in the scales. The in-situ analyses were compared and related to XPS analyses performed on thick oxide scales formed on samples oxidized in air at 600 C for 100h. An oxidation mechanism is then proposed to understand the oxide scale growth in the temperature range 600 - 750 C. The second step of this study consists in improving the high temperature corrosion resistance of these steels without modifying their mechanical properties. Thus several solutions were investigated such as MOCVD coatings, pack cementation coatings, and tested in cycle conditions prior. (orig.)

  13. Investigation of TiN thin film oxidation depending on the substrate temperature at vacuum break

    Energy Technology Data Exchange (ETDEWEB)

    Piallat, Fabien, E-mail: fabien.piallat@gmail.com [STMicroelectronics, 850 rue Jean Monnet, 38920 Crolles (France); CEA, LETI, Campus Minatec, F-38054 Grenoble (France); LTM-CNRS, 17 rue des Martyrs, 38054 Grenoble (France); Gassilloud, Remy [CEA, LETI, Campus Minatec, F-38054 Grenoble (France); Caubet, Pierre [STMicroelectronics, 850 rue Jean Monnet, 38920 Crolles (France); Vallée, Christophe [LTM-CNRS, 17 rue des Martyrs, 38054 Grenoble (France)

    2016-09-15

    Due to the reduction of the thickness of the layers used in the advanced technology nodes, there is a growing importance of the surface phenomena in the definition of the general properties of the materials. One of the least controlled and understood phenomenon is the oxidation of metals after deposition, at the vacuum break. In this study, the influence of the sample temperature at vacuum break on the oxidation level of TiN deposited by metalorganic chemical vapor deposition is investigated. TiN resistivity appears to be lower for samples which underwent vacuum break at high temperature. Using X-ray photoelectron spectrometry analysis, this change is correlated to the higher oxidation of the TiN layer. Moreover, angle resolved XPS analysis reveals that higher is the temperature at the vacuum break, higher is the surface oxidation of the sample. This surface oxidation is in turn limiting the diffusion of oxygen in the volume of the layer. Additionally, evolution of TiN layers resistivity was monitored in time and it shows that resistivity increases until a plateau is reached after about 10 days, with the lowest temperature at vacuum break resulting in the highest increase, i.e., the resistivity of the sample released to atmosphere at high temperature increased by a factor 1.7 whereas the resistivity of the sample cooled down under vacuum temperature increased by a factor 2.7.

  14. A study on the improvement of oxidation resistance of OAE-added stainless steels for high temperature applications

    International Nuclear Information System (INIS)

    Kim, Dae Hwan; Kim, Gil Moo

    1996-01-01

    Since the manufacturing temperature of stainless steels is relatively high, oxidation at the elevated temperature becomes important. The chemical and physical properties of the protective oxide film which was formed on the stainless steels at high temperature for the oxidation resistance are important in determining the rate of oxidation and the life of equipment exposed to high temperature oxidizing environments. In this study, the oxidation behavior of STS 309S and STS 409L added by a small amount of oxygen active element(each + 0.5wt% Hf and Y) was studied to improve oxidation resistance. In the cyclic oxidation, while OAE-free specimens showed relatively poor oxidation resistance due to spallations and cracks of Cr-rich oxide layer, OAE-added specimens improved cyclic oxidation resistance assumably due to constant oxidation rate with stable oxide layers at high temperature. Especially Hf improved cyclic oxidation resistance by forming Cr-rich oxide layer preventing internal oxidation in STS 309S. (author)

  15. Effect of hydrogen on the integrity of aluminium–oxide interface at elevated temperatures

    KAUST Repository

    Li, Meng; Xie, De-Gang; Ma, Evan; Li, Ju; Zhang, Xixiang; Shan, Zhi-Wei

    2017-01-01

    Hydrogen can facilitate the detachment of protective oxide layer off metals and alloys. The degradation is usually exacerbated at elevated temperatures in many industrial applications; however, its origin remains poorly understood. Here by heating hydrogenated aluminium inside an environmental transmission electron microscope, we show that hydrogen exposure of just a few minutes can greatly degrade the high temperature integrity of metal–oxide interface. Moreover, there exists a critical temperature of ∼150 °C, above which the growth of cavities at the metal–oxide interface reverses to shrinkage, followed by the formation of a few giant cavities. Vacancy supersaturation, activation of a long-range diffusion pathway along the detached interface and the dissociation of hydrogen-vacancy complexes are critical factors affecting this behaviour. These results enrich the understanding of hydrogen-induced interfacial failure at elevated temperatures.

  16. Effect of hydrogen on the integrity of aluminium–oxide interface at elevated temperatures

    KAUST Repository

    Li, Meng

    2017-02-20

    Hydrogen can facilitate the detachment of protective oxide layer off metals and alloys. The degradation is usually exacerbated at elevated temperatures in many industrial applications; however, its origin remains poorly understood. Here by heating hydrogenated aluminium inside an environmental transmission electron microscope, we show that hydrogen exposure of just a few minutes can greatly degrade the high temperature integrity of metal–oxide interface. Moreover, there exists a critical temperature of ∼150 °C, above which the growth of cavities at the metal–oxide interface reverses to shrinkage, followed by the formation of a few giant cavities. Vacancy supersaturation, activation of a long-range diffusion pathway along the detached interface and the dissociation of hydrogen-vacancy complexes are critical factors affecting this behaviour. These results enrich the understanding of hydrogen-induced interfacial failure at elevated temperatures.

  17. High-Temperature Oxidation Behavior and Kinetics of Forged 12Cr-MoVW Steel

    Directory of Open Access Journals (Sweden)

    Kim Yong Hwan

    2017-06-01

    Full Text Available The oxidation kinetics of forged 12Cr-MoVW steel was investigated in an air (N2+O2 atmosphere at 873-1073 K (Δ50 K using thermogravimetric analysis. The oxidized samples were characterized using X-ray diffraction, and the surface and cross-sectional morphologies were examined using scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy. The forged 12Cr-MoVW steel samples exhibited parabolic behavior and a low oxidation rate compared with their as-cast counterparts. A protective oxide layer was uniformly formed at relatively low temperature (≤973 K for the forged samples, which thus exhibited better oxidation resistance than the as-cast ones. These oxides are considered solid-solution compounds such as (Fe, Cr2O3.

  18. Combining Raman Microprobe and XPS to Study High Temperature Oxidation of Metals

    International Nuclear Information System (INIS)

    Windisch, Charles F.; Henager, Charles H.; Engelhard, Mark H.; Bennett, Wendy D.

    2011-01-01

    Raman microprobe spectroscopy was applied in studies of high-temperature air oxidation of a ferritic alloy (HT-9) in the absence and presence of zirconia coatings with the objective of evaluating the technique as a way to quickly screen candidate cladding materials and actinide-based mixed oxide fuel mixtures for advanced nuclear reactors. When oxidation was relatively uniform, Raman spectra collected using microscope optics with low spatial resolution were found to be similar to those collected with conventional Raman spectroscopy. These spectra could be used to identify major oxide corrosion products and follow changes in the composition of the oxides due to heating. However, when the oxidation films were comprised of multiple layers of varying composition, or with layers containing metallic phases, techniques with higher depth resolution and sensitivity to zero-valence metals were necessary. The requirements were met by combining Raman microprobe using different optical configurations and x-ray photoelectron spectroscopy.

  19. High-temperature complementary metal oxide semiconductors (CMOS)

    International Nuclear Information System (INIS)

    McBrayer, J.D.

    1979-10-01

    Silicon CMOS devices were studied, tested, and evaluated at high temperatures to determine processing, geometric, operating characteristics, and stability parameters. After more than 1000 hours at 300 0 C, most devices showed good stability, reliability, and operating characteristics. Processing and geometric parameters were evaluated and optimization steps discussed

  20. Low temperature oxidation of hydrocarbons using an electrochemical reactor

    DEFF Research Database (Denmark)

    Ippolito, Davide

    conversion was a complex function of multiple variables: the microstructure of the backbone, the polarization resistance of the electrodes, both at OCV and under polarization, the electrical and morphological properties of the infiltrated material and the specific reaction conditions like the propene......This study investigated the use of a ceramic porous electrochemical reactor for the deep oxidation of propene. Two electrode composites, La0.85Sr0.15MnO3±d/Ce0.9Gd0.1O1.95 (LSM/CGO) and La0.85Sr0.15FeMnO3/Ce0.9Gd0.1O1.95 (LSF/CGO), were produced in a 5 single cells stacked configuration and used...... prolonged polarization was able to partially counteract the instability of the infiltrated Ce0.9Gd0.1O1.95. This project demonstrated the possibility to enhance the oxidation of propene by polarization in a porous ceramic reactor. The infiltration of different active materials helped to increase...

  1. Room temperature plasma oxidation: A new process for preparation of ultrathin layers of silicon oxide, and high dielectric constant materials

    International Nuclear Information System (INIS)

    Tinoco, J.C.; Estrada, M.; Baez, H.; Cerdeira, A.

    2006-01-01

    In this paper we present basic features and oxidation law of the room temperature plasma oxidation (RTPO), as a new process for preparation of less than 2 nm thick layers of SiO 2 , and high-k layers of TiO 2 . We show that oxidation rate follows a potential law dependence on oxidation time. The proportionality constant is function of pressure, plasma power, reagent gas and plasma density, while the exponent depends only on the reactive gas. These parameters are related to the physical phenomena occurring inside the plasma, during oxidation. Metal-Oxide-Semiconductor (MOS) capacitors fabricated with these layers are characterized by capacitance-voltage, current-voltage and current-voltage-temperature measurements. Less than 2.5 nm SiO 2 layers with surface roughness similar to thermal oxide films, surface state density below 3 x 10 11 cm -2 and current density in the expected range for each corresponding thickness, were obtained by RTPO in a parallel-plate reactor, at 180 mW/cm 2 and pressure range between 9.33 and 66.5 Pa (0.07 and 0.5 Torr) using O 2 and N 2 O as reactive gases. MOS capacitors with TiO 2 layers formed by RTPO of sputtered Ti layers are also characterized. Finally, MOS capacitors with stacked layers of TiO 2 over SiO 2 , both layers obtained by RTPO, were prepared and evaluated to determine the feasibility of the use of TiO 2 as a candidate for next technology nodes

  2. The oxidation behavior of classical thermal barrier coatings exposed to extreme temperature

    Directory of Open Access Journals (Sweden)

    Alina DRAGOMIRESCU

    2017-03-01

    Full Text Available Thermal barrier coatings (TBC are designed to protect metal surfaces from extreme temperatures and improve their resistance to oxidation during service. Currently, the most commonly used systems are those that have the TBC structure bond coat (BC / top coat (TC layers. The top coat layer is a ceramic layer. Oxidation tests are designed to identify the dynamics of the thermally oxide layer (TGO growth at the interface of bond coat / top coat layers, delamination mechanism and the TBC structural changes induced by thermal conditions. This paper is a short study on the evolution of aluminum oxide protective layer along with prolonged exposure to the testing temperature. There have been tested rectangular specimens of metal super alloy with four surfaces coated with a duplex thermal barrier coating system. The specimens were microscopically and EDAX analyzed before and after the tests. In order to determine the oxide type, the samples were analyzed using X-ray diffraction. The results of the investigation are encouraging for future studies. The results show a direct relationship between the development of the oxide layer and long exposure to the test temperature. Future research will focus on changing the testing temperature to compare the results.

  3. Processing, Structure and High Temperature Oxidation Properties of Polymer-Derived and Hafnium Oxide Based Ceramic Systems

    Science.gov (United States)

    Terauds, Kalvis

    Demands for hypersonic aircraft are driving the development of ultra-high temperature structural materials. These aircraft, envisioned to sustain Mach 5+, are expected to experience continuous temperatures of 1200--1800°C on the aircraft surface and temperatures as high as 2800°C in combustion zones. Breakthroughs in the development of fiber based ceramic matrix composites (CMCs) are opening the door to a new class of high-tech UHT structures for aerospace applications. One limitation with current carbon fiber or silicon carbide fiber based CMC technology is the inherent problem of material oxidation, requiring new approaches for protective environmental barrier coatings (EBC) in extreme environments. This thesis focuses on the development and characterization of SiCN-HfO2 based ceramic composite EBC systems to be used as a protective layer for silicon carbide fiber based CMCs. The presented work covers three main architectures for protection (i) multilayer films, (ii) polymer-derived HfSiCNO, and (iii) composite SiCN-HfO 2 infiltration. The scope of this thesis covers processing development, material characterization, and high temperature oxidation behavior of these three SiCN-HfO2 based systems. This work shows that the SiCN-HfO 2 composite materials react upon oxidation to form HfSiO4, offering a stable EBC in streaming air and water vapor at 1600°C.

  4. Low-temperature capacitive sensor based on perovskite oxides

    International Nuclear Information System (INIS)

    Zaza, F.; Serra, E.; Caprioli, F.; Orio, G.; Pasquali, M.

    2014-01-01

    Energy, environmental and social issues drive towards the green political economy and the development of advanced technologies, promoting renewable energy sources, improving energy conversion efficiency and reducing exhaust gas emissions. The development of sustainable technologies requires strategic research in the area of gas sensors for monitoring air quality, controlling gas emissions and optimizing combustion processes. Solid state sensors are the most attractive one because of their simplicity in function, small size and low cost. The aim of this work is to synthetize and characterize strontium titanate and test its sensing performance. The prepared sensor device shows significant sensitivity and response rate at room-temperature. However, because of the low recovery rate, the regeneration of the sensor has to be made at high temperature for promoting the decomposition of the carbonates formed on the perovkite surface

  5. Low-temperature capacitive sensor based on perovskite oxides

    Energy Technology Data Exchange (ETDEWEB)

    Zaza, F., E-mail: fabio.zaza@enea.it; Serra, E.; Caprioli, F. [ENEA-Casaccia R.C. via Anguillarese 301, 00123 Rome (Italy); Orio, G.; Pasquali, M. [Department of Basic and Applied Sciences for Engineering, La Sapienza University, Via A. Scarpa 14/16, 00161 Rome (Italy)

    2015-06-23

    Energy, environmental and social issues drive towards the green political economy and the development of advanced technologies, promoting renewable energy sources, improving energy conversion efficiency and reducing exhaust gas emissions. The development of sustainable technologies requires strategic research in the area of gas sensors for monitoring air quality, controlling gas emissions and optimizing combustion processes. Solid state sensors are the most attractive one because of their simplicity in function, small size and low cost. The aim of this work is to synthetize and characterize strontium titanate and test its sensing performance. The prepared sensor device shows significant sensitivity and response rate at room-temperature. However, because of the low recovery rate, the regeneration of the sensor has to be made at high temperature for promoting the decomposition of the carbonates formed on the perovkite surface.

  6. Low-temperature capacitive sensor based on perovskite oxides

    Science.gov (United States)

    Zaza, F.; Orio, G.; Serra, E.; Caprioli, F.; Pasquali, M.

    2015-06-01

    Energy, environmental and social issues drive towards the green political economy and the development of advanced technologies, promoting renewable energy sources, improving energy conversion efficiency and reducing exhaust gas emissions. The development of sustainable technologies requires strategic research in the area of gas sensors for monitoring air quality, controlling gas emissions and optimizing combustion processes. Solid state sensors are the most attractive one because of their simplicity in function, small size and low cost. The aim of this work is to synthetize and characterize strontium titanate and test its sensing performance. The prepared sensor device shows significant sensitivity and response rate at room-temperature. However, because of the low recovery rate, the regeneration of the sensor has to be made at high temperature for promoting the decomposition of the carbonates formed on the perovkite surface.

  7. Low-temperature creep of nanocrystalline titanium(IV) oxide

    Energy Technology Data Exchange (ETDEWEB)

    Hahn, H.; Averback, R.S. (Dept. of Materials Sceince and Engineering, Univ. of Illinois, Urbana, IL (United States))

    1991-11-01

    This paper reports that nanocrystalline TiO[sub 2] with densities higher than 99% of rutile has been deformed in compression without fracture at temperatures between 600[degrees] and 800[degrees] C. The total strains exceed 0.6 at strain rates as high as 10[sup [minus]3] s[sup [minus]1]. The original average grain size of 40 nm increases during the creep deformation to final values in the range of 120 to 1000 nm depending on the temperature and total deformation. The stress exponent of the strain rate, n, is approximately 3 and the grain size dependence is d[sup [minus]q] with q in the range of 1 to 1.5. It is concluded that the creep deformation occurs by an interface reaction controlled mechanism.

  8. Temperature Dependent Variations of Phonon Interactions in Nanocrystalline Cerium Oxide

    Directory of Open Access Journals (Sweden)

    Sugandha Dogra Pandey

    2015-01-01

    Full Text Available The temperature dependent anharmonic behavior of the phonon modes of nanocrystalline CeO2 was investigated in the temperature range of 80–440 K. The anharmonic constants have been derived from the shift in phonon modes fitted to account for the anharmonic contributions as well as the thermal expansion contribution using the high pressure parameters derived from our own high pressure experimental data reported previously. The total anharmonicity has also been estimated from the true anharmonicity as well as quasiharmonic component. In the line-width variation analysis, the cubic anharmonic term was found to dominate the quartic term. Finally, the phonon lifetime also reflected the trend so observed.

  9. Zircaloy-4 and M5 high temperature oxidation and nitriding in air

    Energy Technology Data Exchange (ETDEWEB)

    Duriez, C. [Institut de Radioprotection et Surete Nucleaire, Direction de Prevention des Accidents Majeurs, Centre de Cadarache, 13115 St Paul Lez Durance (France)], E-mail: christian.duriez@irsn.fr; Dupont, T.; Schmet, B.; Enoch, F. [Universite Technologique de Troyes, BP 2060, 10010 Troyes (France)

    2008-10-15

    For the purpose of nuclear power plant severe accident analysis, degradation of Zircaloy-4 and M5 cladding tubes in air at high temperature was investigated by thermo-gravimetric analysis, in isothermal conditions, in a 600-1200 deg. C temperature range. Alloys were investigated either in a 'as received' bare state, or after steam pre-oxidation at 500 {sup o}C to simulate in-reactor corrosion. At the beginning of air exposure, the oxidation rate obeys a parabolic law, characteristic of solid-state diffusion limited regime. Parabolic rate constants compare, for Zircaloy-4 as well as for M5, with recently assessed correlations for high temperature Zircaloy-4 steam-oxidation. A thick layer of dense protective zirconia having a columnar structure forms during this diffusion-limited regime. Then, a kinetic transition (breakaway type) occurs, due to radial cracking along the columnar grain boundaries of this protective dense oxide scale. The breakaway is observed for a scale thickness that strongly increases with temperature. At the lowest temperatures, the M5 alloy appears to be breakaway-resistant, showing a delayed transition compared to Zircaloy-4. However, for both alloys, a pre-existing corrosion scale favours the transition, which occurs much earlier. The post transition kinetic regime is linear only for the lowest temperatures investigated. From 800 deg. C, a continuously accelerated regime is observed and is associated with formation of a strongly porous non-protective oxide. A mechanism of nitrogen-assisted oxide growth, involving formation and re-oxidation of ZrN particles, as well as nitrogen associated zirconia phase transformations, is proposed to be responsible for this accelerated degradation.

  10. Oxidation Behavior of AlN/h-BN Nano Composites at High Temperature

    International Nuclear Information System (INIS)

    Jin Haiyun; Huang Yinmao; Feng Dawei; He Bo; Yang Jianfeng

    2011-01-01

    Both AlN/ nano h-BN composites and AlN/ micro h-BN composites were fabricated. The high temperature oxidation behaviors were investigated at 1000deg. C and 1300deg. C using a cycle-oxidation method. The results showed that there were little changes of both nano composites and monolithic AlN ceramic at temperature of 1000deg. C. And at 1300deg. C, the oxidation dynamics curve of composites could be divided into two courses: a slowly weight increase and a rapid weight decrease, but the oxidation behavior of nano composites was better than micro composites. It was due to that the uniform distribution of oxidation production (Al 18 B 4 O 33 ) surround the AlN grains in nano composites and the oxidation proceeding was retarded. The XRD analysis and SEM observations showed that there was no BN remained in the composites surface after 1300deg. C oxidation and the micropores remain due to the vaporizing of B 2 O 3 oxidized by BN.

  11. A review of the oxidation of uranium dioxide at temperatures below 400oC

    International Nuclear Information System (INIS)

    McEachern, R.J.; Taylor, P.

    1997-01-01

    A critical review of the extensive literature on the air oxidation Of U0 2 at temperatures below 400 o C is presented. The key parameters that affect the rate Of U0 2 oxidation are examined systematically, and their importance to the reaction rate is evaluated. The formation of U 30 7/U 4 0 9 on unirradiated U0 2 powders follows the discrete-layer mechanism and displays diffusion-controlled kinetics. In contrast, U 3 0 8 formation on unirradiated U0 2 displays sigmoidal 'nucleation-and-growth' kinetics. Low-temperature oxidation of used fuel tends to proceed by rapid grain-boundary oxidation followed by simultaneous intragranular oxidation throughout the sample. The activation energy for the formation Of U 3 0 7 /U 4 0 9 is 96 kJ mol -1 for U0 2 powders, 99 kJ mol -1 for sintered pellets and 106 kJ mol -1 for used fuel. The activation energy for the formation Of U 3 0 8 is temperature dependent. The best estimate of the activation energy below ∼325 o C is 154 kJ mol -1 , but all the kinetic data incorporate substantial approximations so that further study is required to properly predict the behaviour of used fuel under low-temperature ( o C) dry-air storage conditions, based on high-temperature (200 to 350 o C) laboratory data. (author). 204 refs., 5 tabs., 4 figs

  12. Test plan for long-term, low-temperature oxidation of spent fuel, Series 1

    International Nuclear Information System (INIS)

    Einziger, R.E.

    1986-06-01

    Preliminary studies indicated the need for more spent fuel oxidation data in order to determine the probable behavior of spent fuel in a tuff repository. Long-term, low-temperature testing was recommended in a comprehensive technical approach to: (1) confirm the findings of the short-term thermogravimetric analyses scoping experiments; (2) evaluate the effects of variables such as burnup, atmospheric moisture and fuel type on the oxidation rate; and (3) extend the oxidation data base ot representative repository temperatures and better define the temperature dependence of the operative oxidation mechanisms. This document presents the Series 1 test plan to study, on a large number of samples, the effects of atmospheric moisture and temperature on oxidation rate and phase formation. Tests will run for up to two years, use characterized fragmented, and pulverized fuel samples, cover a temperature range of 110 0 C to 175 0 C and be conducted with an atmospheric moisture content rangeing from 0 C to approx. 80 0 C dew point. After testing, the samples will be examined and made available for leaching testing

  13. Effects of temperature on the heterogeneous oxidation of sulfur dioxide by ozone on calcium carbonate

    Directory of Open Access Journals (Sweden)

    L. Y. Wu

    2011-07-01

    Full Text Available The heterogeneous oxidation of sulfur dioxide by ozone on CaCO3 was studied as a function of temperature (230 to 298 K at ambient pressure. Oxidation reactions were followed in real time using diffuse reflectance infrared Fourier transform spectrometry (DRIFTS to obtain kinetic and mechanistic data. From the analysis of the spectral features, the formation of sulfate was identified on the surface in the presence of O3 and SO2 at different temperatures from 230 to 298 K. The results showed that the heterogeneous oxidation and the rate of sulfate formation were sensitive to temperature. An interesting stage-transition region was observed at temperatures ranging from 230 to 257 K, but it became ambiguous gradually above 257 K. The reactive uptake coefficients at different temperatures from 230 to 298 K were acquired for the first time, which can be used directly in atmospheric chemistry modeling studies to predict the formation of secondary sulfate aerosol in the troposphere. Furthermore, the rate of sulfate formation had a turning point at about 250 K. The sulfate concentration at 250 K was about twice as large as that at 298 K. The rate of sulfate formation increased with decreasing temperature at temperatures above 250 K, while there is a contrary temperature effect at temperatures below 250 K. The activation energy for heterogeneous oxidation at temperatures from 245 K to 230 K was determined to be 14.63 ± 0.20 kJ mol−1. A mechanism for the temperature dependence was proposed and the atmospheric implications were discussed.

  14. Self-sustained carbon monoxide oxidation oscillations on size-selected platinum nanoparticles at atmospheric pressure

    DEFF Research Database (Denmark)

    Jensen, Robert; Andersen, Thomas; Nierhoff, Anders Ulrik Fregerslev

    2013-01-01

    High-quality mass spectrometry data of the oscillatory behavior of CO oxidation on SiO2 supported Pt-nanoparticles at atmospheric pressure have been acquired as a function of pressure, coverage, gas composition and nanoparticle size. The oscillations are self-sustained for several days at constant......, temperature, pressure and CO/O2 ratio. The frequency of the oscillations is very well defined and increases over time. The oscillation frequency is furthermore strongly temperature dependent with increasing temperature resulting in increasing frequency. A plausible mechanism for the oscillations is proposed...

  15. Temperature and Oxidative Stress as Triggers for Virulence Gene Expression in Pathogenic Leptospira spp.

    Directory of Open Access Journals (Sweden)

    Tricia Fraser

    2017-05-01

    Full Text Available Leptospirosis is a zooanthroponosis aetiologically caused by pathogenic bacteria belonging to the genus, Leptospira. Environmental signals such as increases in temperatures or oxidative stress can trigger response regulatory modes of virulence genes during infection. This study sought to determine the effect of temperature and oxidative stress on virulence associated genes in highly passaged Leptospira borgpeterseneii Jules and L. interrogans Portlandvere. Bacteria were grown in EMJH at 30°C, 37°C, or at 30°C before being transferred to 37°C. A total of 14 virulence-associated genes (fliY, invA, lenA, ligB, lipL32, lipL36, lipL41, lipL45, loa22, lsa21, mce, ompL1, sph2, and tlyC were assessed using endpoint PCR. Transcriptional analyses of lenA, lipL32, lipL41, loa22, sph2 were assessed by quantitative real-time RT-PCR at the temperature conditions. To assess oxidative stress, bacteria were exposed to H2O2 for 30 and 60 min with or without the temperature stress. All genes except ligB (for Portlandvere and ligB and mce (for Jules were detectable in the strains. Quantitatively, temperature stress resulted in significant changes in gene expression within species or between species. Temperature changes were more influential in gene expression for Jules, particularly at 30°C and upshift conditions; at 37°C, expression levels were higher for Portlandvere. However, compared to Jules, where temperature was influential in two of five genes, temperature was an essential element in four of five genes in Portlandvere exposed to oxidative stress. At both low and high oxidative stress levels, the interplay between genetic predisposition (larger genome size and temperature was biased towards Portlandvere particularly at 30°C and upshift conditions. While it is clear that expression of many virulence genes in highly passaged strains of Leptospira are attenuated or lost, genetic predisposition, changes in growth temperature and/or oxidative intensity and

  16. Oxidation behavior of 304 stainless steel exposed to steam at high temperature

    Energy Technology Data Exchange (ETDEWEB)

    Jeong, H.; Ryu, J. R.; Park, G. H. [Kyunghee Univ., Yongin (Korea, Republic of); Yoo, T. G. [FNC Technology, Seoul (Korea, Republic of)

    2003-10-01

    An experiment was conducted on 304 stainless steel(SUS304L) at the LOCA(Lost of Coolant Accident) requirement temperature, 800 .deg. C to 1100 deg. C. SUS304L was used as clothing material and structural frame of LWR. Oxidation behavior of SUS304L by temperature and time was examined after the mechanical and chemical polishing of SUS304L plate. After oxidation, change in weight showed a linear pattern for the first 20 minutes and a parabolic pattern afterwards. Then, fine structure and oxidation layer of SUS304L plate were observed through OM photographing and oxidation characteristics of SUS304L were found through hardness measurement by depth of each plate and XRD(X-Ray Diffraction) photographing.

  17. Crystallographic and oxidation kinetic study of uranium dioxide by high temperature X-ray diffractometry

    International Nuclear Information System (INIS)

    Teixeira, S.R.

    1981-01-01

    The structural behavior of UO 2 sintered plates was studied as a function of temperature by X-ray diffractometry. All the experiments were carried out under an inert atmosphere with low oxygen content (approximated 140 ppm). The thermal expansion coefficient of UO 2 05 was found to be 10,5 x 10 - 6 0 C - 1 for temperatures above 165 0 C. Structural transformations during oxidation were observed at 170,235 and 275 0 C. The isothermal oxidation of UO 2 to U 3 O 7 follows a parabolic form and the diffusion of oxygen through the product layer U 4 O 9 is the mechanism controlling the oxidation rate. The phases observed were UO 2 (cubic) - U 4 O 9 (cubic) - U 3 O 7 (tetragonal). Activation energies of oxidation were found for different crystallographic planes (hkl). From this one can conclude that there is a preferential occupation of interstitial oxygen within the UO 2 structure. (Author) [pt

  18. Effects of alloying and temperature on the high-temperature oxidation of Cr-Cr{sub 2}Nb

    Energy Technology Data Exchange (ETDEWEB)

    Tortorelli, P.F.; DeVan, J.H. [Oak Ridge National Lab., TN (United States); Carson, L.J. [Lincoln Univ., PA (United States)

    1993-06-01

    Effects of alloying additions and temperature on isothermal and cyclic oxidation resistance of Cr-Cr{sub 2}Nb alloys were examined for air exposures. An isothermal exposure temperature of 1100C led to rapid reaction of binary Cr-12 at.% Nb as manifested a high oxidation rate and nonprotective behavior. Generally parabolic kinetics, complicated by some isothermal scale cracking, were observed at 900--1000C. Scale damage was exacerbated by thermal cycling. The addition of 8 at.% Al to Cr-12 at.% Nb did not effect cyclic oxidation resistance, but there was some evidence that scale adherence on Cr-6 at.% Nb-8 at.% Al was better than that for binary Cr-6 at.% Nb. Alloying additions of Al (up to 18 at.%) or Re (2 at.%) did not improve the isothermal oxidation resistance of Cr-12 at.% Nb. However, the tendency for scale damage during both isothermal and thermal cycling exposures suggests that alloying additions that specifically improve scale plasticity or modify growth stresses could be effective for Cr-Nb alloys. 10 refs, 9 figs, 1 tab.

  19. Magnetron sputtered transparent conductive zinc-oxide stabilized amorphous indium oxide thin films on polyethylene terephthalate substrates at ambient temperature

    International Nuclear Information System (INIS)

    Yan, Y.; Zhang, X.-F.; Ding, Y.-T.

    2013-01-01

    Amorphous transparent conducting zinc-oxide stabilized indium oxide thin films, named amorphous indium zinc oxide (a-IZO), were deposited by direct current magnetron sputtering at ambient temperature on flexible polyethylene terephthalate substrates. It has been demonstrated that the electrical resistivity could attain as low as ∼ 5 × 10 −4 Ω cm, which was noticeably lower than amorphous indium tin oxide films prepared at the same condition, while the visible transmittance exceeded 84% with the refractive index of 1.85–2.00. In our experiments, introduction of oxygen gas appeared to be beneficial to the improvement of the transparency and electrical conductivity. Both free carrier absorption and indirect transition were observed and Burstein–Moss effect proved a-IZO to be a degenerated amorphous semiconductor. However, the linear relation between the optical band gap and the band tail width which usually observed in covalent amorphous semiconductor such as a-Si:H was not conserved. Besides, porosity could greatly determine the resistivity and optical constants for the thickness variation at this deposition condition. Furthermore, a broad photoluminescence peak around 510 nm was identified when more than 1.5 sccm oxygen was introduced. - Highlights: ► Highly conducting amorphous zinc-oxide stabilized indium oxide thin films were prepared. ► The films were fabricated on polyethylene terephthalate at ambient temperature. ► Introduction of oxygen can improve the transparency and electrical conductivity. ► The linear relation between optical band gap and band tail width was not conserved

  20. Codeposition of deuterium ions with beryllium oxide at elevated temperatures

    CERN Document Server

    Markin, A V; Gorodetsky, A E; Negodaev, M A; Rozhanskii, N V; Scaffidi-Argentina, F; Werle, H; Wu, C H; Zalavutdinov, R K; Zakharov, A P

    2000-01-01

    Deuterium-loaded BeO films were produced by sputtering the beryllium target with 10 keV Ne ions in D sub 2 gas at a pressure of approximately 1 Pa. The sputtered beryllium reacts - on the substrate surface - with the residual oxygen, thus forming a beryllium oxide layer. Biasing the substrate negatively with respect to the target provides the simultaneous bombardment of the growing film surface with D ions formed by Ne-D sub 2 collisions. Substrate potential governs the maximum energy of ions striking the growing film surface while its size governs the flux density. According to X-ray photoelectron spectroscopy (XPS), electron probe microanalysis (EPMA) and reflection high energy electron diffraction (RHEED) data, the beryllium is deposited in the form of polycrystalline hcp-BeO layers with negligible (about 1 at.%) carbon and neon retention. Thermal desorption spectroscopy (TDS) data shows a strong deuterium bonding, with a desorption peak at 950 K, in the films deposited at -50 and -400 V substrate potentia...

  1. HIGH-TEMPERATURE TUBULAR SOLID OXIDE FUEL CELL GENERATOR DEVELOPMENT

    Energy Technology Data Exchange (ETDEWEB)

    S.E. Veyo

    1998-09-01

    During the Westinghouse/USDOE Cooperative Agreement period of November 1, 1990 through November 30, 1997, the Westinghouse solid oxide fuel cell has evolved from a 16 mm diameter, 50 cm length cell with a peak power of 1.27 watts/cm to the 22 mm diameter, 150 cm length dimensions of today's commercial prototype cell with a peak power of 1.40 watts/cm. Accompanying the increase in size and power density was the elimination of an expensive EVD step in the manufacturing process. Demonstrated performance of Westinghouse's tubular SOFC includes a lifetime cell test which ran for a period in excess of 69,000 hours, and a fully integrated 25 kWe-class system field test which operated for over 13,000 hours at 90% availability with less than 2% performance degradation over the entire period. Concluding the agreement period, a 100 kW SOFC system successfully passed its factory acceptance test in October 1997 and was delivered in November to its demonstration site in Westervoort, The Netherlands.

  2. The Effect of Annealing Temperature on Nickel on Reduced Graphene Oxide Catalysts on Urea Electrooxidation

    International Nuclear Information System (INIS)

    Glass, Dean E.; Galvan, Vicente; Prakash, G.K. Surya

    2017-01-01

    Highlights: •Nickel was reduced on graphene oxide and annealed under argon from 300 to 700 °C. •Nickel was oxidized from the removal of oxygen groups on the graphene oxide. •Higher annealed catalysts displayed decreased urea electrooxidation currents. •Micro direct urea/hydrogen peroxide fuel cells were employed for the first time. •Ni/rGO catalysts displayed enhanced fuel cell performance than the bare nickel. -- Abstract: The annealing temperature effects on nickel on reduced graphene oxide (Ni/rGO) catalysts for urea electrooxidation were investigated. Nickel chloride was directly reduced in an aqueous solution of graphene oxide (GO) followed by annealing under argon at 300, 400, 500, 600, and 700 °C, respectively. X-ray Diffraction (XRD) patterns revealed an increase in the crystallite size of the nickel nanoparticles while the Raman spectra displayed an increase in the graphitic disorder of the reduced graphene oxide at higher annealing temperatures due to the removal of oxygen functional groups. The Ni/rGO catalysts annealed at higher temperatures displayed oxidized nickel surface characteristics from the Ni 2p X-ray Photoelectron Spectra (XPS) due to the oxidation of the nickel from the oxygen functional groups in the graphitic lattice. In the half-cell testing, the onset potential of urea electrooxidation decreased while the urea electrooxidation currents decreased as the annealing temperature was increased. The nickel catalyst annealed at 700 °C displayed a 31% decrease in peak power density while the catalyst annealed at 300 °C displayed a 13% increase compared with the unannealed Ni/rGO catalyst in the micro direct urea/hydrogen peroxide fuel cells tests.

  3. Homogenization Pressure and Temperature Affect Protein Partitioning and Oxidative Stability of Emulsions

    DEFF Research Database (Denmark)

    Horn, Anna Frisenfeldt; Barouh, Nathalie; Nielsen, Nina Skall

    2013-01-01

    The oxidative stability of 10 % fish oil-in-water emulsions was investigated for emulsions prepared under different homogenization conditions. Homogenization was conducted at two different pressures (5 or 22.5 MPa), and at two different temperatures (22 and 72 °C). Milk proteins were used...... prior to homogenization did not have any clear effect on lipid oxidation in either of the two types of emulsions....

  4. Indium oxide octahedrons based on sol–gel process enhance room temperature gas sensing performance

    Energy Technology Data Exchange (ETDEWEB)

    Mu, Xiaohui [Key Laboratory of Chemical Sensing & Analysis in Universities of Shandong, School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, Shandong (China); Chen, Changlong, E-mail: chem.chencl@hotmail.com [Key Laboratory of Chemical Sensing & Analysis in Universities of Shandong, School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, Shandong (China); Han, Liuyuan [Key Laboratory of Chemical Sensing & Analysis in Universities of Shandong, School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, Shandong (China); Shao, Baiqi [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Graduate School of the Chinese Academy of Sciences, Beijing 100049 (China); Wei, Yuling [Instrumental Analysis Center, Qilu University of Technology, Jinan 250353, Shandong (China); Liu, Qinglong; Zhu, Peihua [Key Laboratory of Chemical Sensing & Analysis in Universities of Shandong, School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, Shandong (China)

    2015-07-15

    Highlights: • In{sub 2}O{sub 3} octahedron films are prepared based on sol–gel technique for the first time. • The preparation possesses merits of low temperature, catalyst-free and large production. • It was found that the spin-coating process in film fabrication was key to achieve the octahedrons. • The In{sub 2}O{sub 3} octahedrons could significantly enhance room temperature NO{sub 2} gas sensing performance. - Abstract: Indium oxide octahedrons were prepared on glass substrates through a mild route based on sol–gel technique. The preparation possesses characteristics including low temperature, catalyst-free and large production, which is much distinguished from the chemical-vapor-deposition based methods that usually applied to prepare indium oxide octahedrons. Detailed characterization revealed that the indium oxide octahedrons were single crystalline, with {1 1 1} crystal facets exposed. It was found that the spin-coating technique was key for achieving the indium oxide crystals with octahedron morphology. The probable formation mechanism of the indium oxide octahedrons was proposed based on the experiment results. Room temperature NO{sub 2} gas sensing measurements exhibited that the indium oxide octahedrons could significantly enhance the sensing performance in comparison with the plate-like indium oxide particles that prepared from the dip-coated gel films, which was attributed to the abundant sharp edges and tips as well as the special {1 1 1} crystal facets exposed that the former possessed. Such a simple wet-chemical based method to prepare indium oxide octahedrons with large-scale production is promising to provide the advanced materials that can be applied in wide fields like gas sensing, solar energy conversion, field emission, and so on.

  5. Indium oxide octahedrons based on sol–gel process enhance room temperature gas sensing performance

    International Nuclear Information System (INIS)

    Mu, Xiaohui; Chen, Changlong; Han, Liuyuan; Shao, Baiqi; Wei, Yuling; Liu, Qinglong; Zhu, Peihua

    2015-01-01

    Highlights: • In 2 O 3 octahedron films are prepared based on sol–gel technique for the first time. • The preparation possesses merits of low temperature, catalyst-free and large production. • It was found that the spin-coating process in film fabrication was key to achieve the octahedrons. • The In 2 O 3 octahedrons could significantly enhance room temperature NO 2 gas sensing performance. - Abstract: Indium oxide octahedrons were prepared on glass substrates through a mild route based on sol–gel technique. The preparation possesses characteristics including low temperature, catalyst-free and large production, which is much distinguished from the chemical-vapor-deposition based methods that usually applied to prepare indium oxide octahedrons. Detailed characterization revealed that the indium oxide octahedrons were single crystalline, with {1 1 1} crystal facets exposed. It was found that the spin-coating technique was key for achieving the indium oxide crystals with octahedron morphology. The probable formation mechanism of the indium oxide octahedrons was proposed based on the experiment results. Room temperature NO 2 gas sensing measurements exhibited that the indium oxide octahedrons could significantly enhance the sensing performance in comparison with the plate-like indium oxide particles that prepared from the dip-coated gel films, which was attributed to the abundant sharp edges and tips as well as the special {1 1 1} crystal facets exposed that the former possessed. Such a simple wet-chemical based method to prepare indium oxide octahedrons with large-scale production is promising to provide the advanced materials that can be applied in wide fields like gas sensing, solar energy conversion, field emission, and so on

  6. Fluorine-enhanced low-temperature wafer bonding of native-oxide covered Si wafers

    Science.gov (United States)

    Tong, Q.-Y.; Gan, Q.; Fountain, G.; Enquist, P.; Scholz, R.; Gösele, U.

    2004-10-01

    The bonding energy of bonded native-oxide-covered silicon wafers treated in the HNO3/H2O/HF or the HNO3/HF solution prior to room-temperature contact is significantly higher than bonded standard RCA1 cleaned wafer pairs after low-temperature annealing. The bonding energy reaches over 2000mJ/m2 after annealing at 100 °C. The very slight etching and fluorine in the chemically grown oxide are believed to be the main contributors to the enhanced bonding energy. Transmission-electron-microscopic images have shown that the chemically formed native oxide at bonding interface is embedded with many flake-like cavities. The cavities can absorb the by-products of the interfacial reactions that result in covalent bond formation at low temperatures allowing the strong bond to be retained.

  7. Surface coating of ceria nanostructures for high-temperature oxidation protection

    Science.gov (United States)

    Aadhavan, R.; Bhanuchandar, S.; Babu, K. Suresh

    2018-04-01

    Stainless steels are used in high-temperature structural applications but suffer from degradation at an elevated temperature of operation due to thermal stress which leads to spallation. Ceria coating over chromium containing alloys induces protective chromia layer formation at alloy/ceria interface thereby preventing oxidative degradation. In the present work, three metals of differing elemental composition, namely, AISI 304, AISI 410, and Inconel 600 were tested for high-temperature stability in the presence and absence of ceria coating. Nanoceria was used as the target to deposit the coating through electron beam physical vapor deposition method. After isothermal oxidation at 1243 K for 24 h, Ceria coated AISI 304 and Inconel 600 exhibited a reduced rate of oxidation by 4 and 1 orders, respectively, in comparison with the base alloy. The formation of spinel structure was found to be lowered in the presence of ceria due to the reduced migration of cations from the alloy.

  8. Fabrication of cathode supported tubular solid oxide electrolysis cell for high temperature steam electrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Shao, Le; Wang, Shaorong; Qian, Jiqin; Xue, Yanjie; Liu, Renzhu

    2011-01-15

    In recent years, hydrogen has been identified as a potential alternative fuel and energy carrier for the future energy supply. Water electrolysis is one of the important hydrogen production technologies which do not emit carbon dioxide. High temperature steam electrolysis (HTSE) consumes even less electrical energy than low temperature water electrolysis. Theoretically, HTSE using solid oxide electrolysis cells (SOEC) can efficiently utilize renewable energy to produce hydrogen, and it is also possible to operate the SOEC in reverse mode as the solid oxide fuel cell (SOFC) to produce electricity. Tubular SOFC have been widely investigated. In this study, tubular solid oxide cells were fabricated by dip-coating and cosintering techniques. In SOEC mode, results suggested that steam ratio had a strong impact on the performance of the tubular cell; the tubular SOEC preferred to be operated at high steam ratio in order to avoid concentration polarization. The microstructure of the tubular SOEC should therefore be optimized for high temperature steam electrolysis.

  9. High performance solution processed zirconium oxide gate dielectric appropriate for low temperature device application

    Energy Technology Data Exchange (ETDEWEB)

    Hasan, Musarrat; Nguyen, Manh-Cuong; Kim, Hyojin; You, Seung-Won; Jeon, Yoon-Seok; Tong, Duc-Tai; Lee, Dong-Hwi; Jeong, Jae Kyeong; Choi, Rino, E-mail: rino.choi@inha.ac.kr

    2015-08-31

    This paper reports a solution processed electrical device with zirconium oxide gate dielectric that was fabricated at a low enough temperature appropriate for flexible electronics. Both inorganic dielectric and channel materials were synthesized in the same organic solvent. The dielectric constant achieved was 13 at 250 °C with a reasonably low leakage current. The bottom gate transistor devices showed the highest mobility of 75 cm{sup 2}/V s. The device is operated at low voltage with high-k dielectric with excellent transconductance and low threshold voltage. Overall, the results highlight the potential of low temperature solution based deposition in fabricating more complicated circuits for a range of applications. - Highlights: • We develop a low temperature inorganic dielectric deposition process. • We fabricate oxide semiconductor channel devices using all-solution processes. • Same solvent is used for dielectric and oxide semiconductor deposition.

  10. Oxidation characteristics of the electron beam surface-treated Alloy 617 in high temperature helium environments

    International Nuclear Information System (INIS)

    Lee, Ho Jung; Sah, Injin; Kim, Donghoon; Kim, Hyunmyung; Jang, Changheui

    2015-01-01

    The oxidation characteristics of the electron beam surface-treated Alloy 617, which has an Al-rich surface layer, were evaluated in high temperature helium environments. Isothermal oxidation tests were performed in helium (99.999% purity) and VHTR-helium (helium of prototypical VHTR chemistry containing impurities like CO, CO 2 , CH 4 , and H 2 ) environments at 900 °C for up to 1000 h. The surface-treated Alloy 617 showed an initial transient oxidation stage followed by the steady-state oxidation in all test environments. In addition, the steady-state oxidation kinetics of the surface-treated Alloy 617 was 2-order of magnitude lower than that of the as-received Alloy 617 in both helium environments as well as in air. The improvement in oxidation resistance was primarily due to the formation of the protective Al 2 O 3 layer on the surface. The weight gain was larger in the order of air, helium, and VHTR-helium, while the parabolic rate constants (k p ) at steady-state were similar for all test environments. In both helium environments, the oxide structure consisted of the outer transition Al 2 O 3 with a small amount of Cr 2 O 3 and inner columnar structured Al 2 O 3 without an internal oxide. In the VHTR-helium environment, where the impurities were added to helium, the initial transient oxidation increased but the steady state kinetics was not affected

  11. Effects of high temperature surface oxides on room temperature aqueous corrosion and environmental embrittlement of iron aluminides

    Energy Technology Data Exchange (ETDEWEB)

    Buchanan, R.A.; Perrin, R.L.

    1996-09-01

    Studies were conducted to determine the effects of high-temperature surface oxides, produced during thermomechanical processing, heat treatment (750 {degrees}C in air, one hour) or simulated in-service-type oxidation (1000{degrees}C in air, 24 hours) on the room-temperature aqueous-corrosion and environmental-embrittlement characteristics of iron aluminides. Materials evaluated included the Fe{sub 3}Al-based iron aluminides, FA-84, FA-129, FAL and FAL-Mo, a FeAl-based iron aluminide, FA-385, and a disordered low-aluminum Fe-Al alloy, FAPY. Tests were performed in a mild acid-chloride solution to simulate aggressive atmospheric corrosion. Cyclic-anodic-polarization tests were employed to evaluate resistances to localized aqueous corrosion. The high-temperature oxide surfaces consistently produced detrimental results relative to mechanically or chemically cleaned surfaces. Specifically, the pitting corrosion resistances were much lower for the as-processed and 750{degrees} C surfaces, relative to the cleaned surfaces, for FA-84, FA-129, FAL-Mo, FA-385 and FAPY. Furthermore, the pitting corrosion resistances were much lower for the 1000{degrees}C surfaces, relative to cleaned surfaces, for FA-129, FAL and FAL-Mo.

  12. The Mechanism of Low-Temperature Oxidation of Carbon Monoxide by Oxygen over the PdCl2–CuCl2/γ-Al2O3 Nanocatalyst

    KAUST Repository

    Bruk, Lev

    2018-04-03

    The state of palladium and copper on the surface of the PdCl2–CuCl2/γ-Al2O3 nanocatalyst for the low-temperature oxidation of CO by molecular oxygen was studied by various spectroscopic techniques. Using X-ray absorption spectroscopy (XAS), powder X-ray diffraction (XRD), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), freshly prepared samples of the catalyst were studied. The same samples were also evaluated after interaction with CO, O2, and H2O vapor in various combinations. It was shown that copper exists in the form of Cu2Cl(OH)3 (paratacamite) nanophase on the surface of the catalyst. No palladium-containing crystalline phases were identified. Palladium coordination initially is comprised of four chlorine atoms. It was shown by XAS that this catalyst is not capable of oxidizing CO at room temperature in the absence of H2O and O2 over 12 h. Copper(II) and palladium(II) are reduced to Cu(I) and Pd(I,0) species, respectively, in the presence of CO and H2O vapor (without O2). It was found by DRIFTS that both linear (2114 cm−1, 1990 cm−1) and bridging (1928 cm−1) forms of coordinated CO were formed upon adsorption onto the catalyst surface. Moreover, the formation of CO2 was detected upon the interaction of the coordinated CO with oxygen. The kinetics of CO oxidation was studied at 18–38 °C at an atmospheric pressure for CO, O2, N2, and H2O (gas) mixtures in a flow reactor (steady state conditions).

  13. The Mechanism of Low-Temperature Oxidation of Carbon Monoxide by Oxygen over the PdCl2–CuCl2/γ-Al2O3 Nanocatalyst

    Directory of Open Access Journals (Sweden)

    Lev Bruk

    2018-04-01

    Full Text Available The state of palladium and copper on the surface of the PdCl2–CuCl2/γ-Al2O3 nanocatalyst for the low-temperature oxidation of CO by molecular oxygen was studied by various spectroscopic techniques. Using X-ray absorption spectroscopy (XAS, powder X-ray diffraction (XRD, and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS, freshly prepared samples of the catalyst were studied. The same samples were also evaluated after interaction with CO, O2, and H2O vapor in various combinations. It was shown that copper exists in the form of Cu2Cl(OH3 (paratacamite nanophase on the surface of the catalyst. No palladium-containing crystalline phases were identified. Palladium coordination initially is comprised of four chlorine atoms. It was shown by XAS that this catalyst is not capable of oxidizing CO at room temperature in the absence of H2O and O2 over 12 h. Copper(II and palladium(II are reduced to Cu(I and Pd(I,0 species, respectively, in the presence of CO and H2O vapor (without O2. It was found by DRIFTS that both linear (2114 cm−1, 1990 cm−1 and bridging (1928 cm−1 forms of coordinated CO were formed upon adsorption onto the catalyst surface. Moreover, the formation of CO2 was detected upon the interaction of the coordinated CO with oxygen. The kinetics of CO oxidation was studied at 18–38 °C at an atmospheric pressure for CO, O2, N2, and H2O (gas mixtures in a flow reactor (steady state conditions.

  14. The Mechanism of Low-Temperature Oxidation of Carbon Monoxide by Oxygen over the PdCl2–CuCl2/γ-Al2O3 Nanocatalyst

    KAUST Repository

    Bruk, Lev; Titov, Denis; Ustyugov, Alexander; Zubavichus, Yan; Chernikova, Valeriya; Tkachenko, Olga; Kustov, Leonid; Murzin, Vadim; Oshanina, Irina; Temkin, Oleg

    2018-01-01

    The state of palladium and copper on the surface of the PdCl2–CuCl2/γ-Al2O3 nanocatalyst for the low-temperature oxidation of CO by molecular oxygen was studied by various spectroscopic techniques. Using X-ray absorption spectroscopy (XAS), powder X-ray diffraction (XRD), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), freshly prepared samples of the catalyst were studied. The same samples were also evaluated after interaction with CO, O2, and H2O vapor in various combinations. It was shown that copper exists in the form of Cu2Cl(OH)3 (paratacamite) nanophase on the surface of the catalyst. No palladium-containing crystalline phases were identified. Palladium coordination initially is comprised of four chlorine atoms. It was shown by XAS that this catalyst is not capable of oxidizing CO at room temperature in the absence of H2O and O2 over 12 h. Copper(II) and palladium(II) are reduced to Cu(I) and Pd(I,0) species, respectively, in the presence of CO and H2O vapor (without O2). It was found by DRIFTS that both linear (2114 cm−1, 1990 cm−1) and bridging (1928 cm−1) forms of coordinated CO were formed upon adsorption onto the catalyst surface. Moreover, the formation of CO2 was detected upon the interaction of the coordinated CO with oxygen. The kinetics of CO oxidation was studied at 18–38 °C at an atmospheric pressure for CO, O2, N2, and H2O (gas) mixtures in a flow reactor (steady state conditions).

  15. Numerical predictions of dry oxidation of iron and low-carbon steel at moderately elevated temperatures

    International Nuclear Information System (INIS)

    Henshall, G.A.

    1996-11-01

    Wrought and cast low-carbon steel are candidate materials for the thick (e.g. 10 cm) outer barrier of nuclear waste packages being considered for use in the potential geological repository at Yucca Mountain. Dry oxidation is possible at the moderately elevated temperatures expected at the container surface (323-533 K or 50-260 C). Numerical predictions of dry oxidation damage were made based on experimental data for iron and low-carbon steel and parabolic oxidation theory. The Forward Euler method was implemented to integrate the parabolic rate law for arbitrary, complex temperature histories. Assuming growth of a defect-free, adherent oxide, the surface penetration of a low-carbon steel barrier following 5000 years of exposure to a severe, but repository-relevant, temperature history is predicted to be only about 0.127 mm, less than 0.13% of the expected container thickness of 10 cm. Allowing the oxide to spall upon reaching a critical thickness increases the predicted metal penetration values, but degradation is still computed to be negligible. Thus, dry oxidation is not expected to significantly degrade the performance of thick, corrosion allowance barriers constructed of low-carbon steel

  16. Oxidation behavior of TD-NiCr in a dynamic high temperature environment

    Science.gov (United States)

    Tenney, D. R.; Young, C. T.; Herring, H. W.

    1974-01-01

    The oxidation behavior of TD-NiCr has been studied in static and high-speed flowing air environments at 1100 and 1200 C. It has been found that the stable oxide morphologies formed on the specimens exposed to the static and dynamic environments were markedly different. The faceted crystal morphology characteristic of static oxidation was found to be unstable under high-temperature, high-speed flow conditions and was quickly replaced by a porous NiO 'mushroom' type structure. Also, it was found that the rate of formation of CrO3 from Cr2O3 was greatly enhanced by high gas velocity conditions. The stability of Cr2-O3 was found to be greatly improved by the presence of an outer NiO layer, even though the NiO layer was very porous. An oxidation model is proposed to explain the observed microstructures and overall oxidation behavior of TD-NiCr alloys.

  17. Dislocation motion and high temperature plasticity of binary and ternary oxides

    International Nuclear Information System (INIS)

    Bretheau, T.; Castaing, J.; Rabier, J.; Veyssiere, P.

    1979-01-01

    Literature dealing with the plasticity of single crystal oxides deformed at elevated temperatures and the associated mobility of dislocations is reviewed. The experimental approach to the subject is examined critically by selecting oxides and deforming samples and by studying their specific mechanical behaviour, characterizing the deformation substructures and modelling the rate controlling processes. Since oxides with the simple rocksalt structure (Mg0, Ni0, Co0, Fe0,...) are not representative of all oxides, examples of other structures are also examined in detail, including Ti0 2 and Cu 2 0 oxides with fluorite (Zr0 2 , U0 2 ), with corundum (A1 2 0 3 ) and with spinel (MgA1 2 0 4 ternary) structures. Occasionally work on more exotic compounds like Y 2 0 3 or some with the garnet structure is included. (UK)

  18. Effect of Sintering Temperature on the Properties of Aluminium-Aluminium Oxide Composite Materials

    Directory of Open Access Journals (Sweden)

    Dewan Muhammad Nuruzzaman

    2016-12-01

    Full Text Available In this study, aluminium-aluminium oxide (Al-Al2O3 metal matrix composites of different weight percentage reinforcements of aluminium oxide were processed at different sintering temperatures. In order to prepare these composite specimens, conventional powder metallurgy (PM method was used. Three types specimens of different compositions such as 95%Al+5%Al2O3, 90%Al+10%Al2O3 and 85%Al+15%Al2O3 were prepared under 20 Ton compaction load. Then, all the specimens were sintered in a furnace at two different temperatures 550oC and 580oC. In each sintering process, two different heating cycles were used. After the sintering process, it was observed that undistorted flat specimens were successfully prepared for all the compositions. The effects of sintering temperature and weight fraction of aluminium oxide particulates on the density, hardness and microstructure of Al-Al2O3 composites were observed. It was found that density and hardness of the composite specimens were significantly influenced by sintering temperature and percentage aluminium oxide reinforcement. Furthermore, optical microscopy revealed that almost uniform distribution of aluminium oxide reinforcement within the aluminium matrix was achieved.

  19. An investigation on high-temperature electrical transport properties of graphene-oxide nano-thinfilms

    International Nuclear Information System (INIS)

    Venugopal, Gunasekaran; Krishnamoorthy, Karthikeyan; Kim, Sang-Jae

    2013-01-01

    High-temperature electrical transport properties are investigated for graphene-oxide nano thinfilms. The graphene-oxide nanoparticles are synthesized by modified Hummers method and characterized by UV–vis, Raman and X-ray diffraction techniques. The surface morphology of graphene-oxide film is analyzed using scanning electron and atomic force microscopy. The experimental results on high-temperature electrical studies of thinfilms exhibit metallic behavior followed by three-dimensional variable range hopping mechanism. The current–voltage characteristics at various temperatures (from 293 K to 573 K) were investigated. The effect of high-temperature on the functional groups of graphene-oxide film is evidently examined using X-ray photoelectron, thermal gravimetric analysis and Fourier transform infra-red spectroscopy. Transistor characteristics were performed after heat treatment resulting ambipolar behavior with holes and electron mobility of 127 and 66.9 cm 2 V −1 s −1 respectively. Our results are comparable to reduced graphene-oxide, indicating the advantage of our approach requires no further reduction to develop graphene-based transparent and conductive electrodes for dye-sensitized solar cells and ultra-capacitor applications.

  20. Oxidation Study of an Ultra High Temperature Ceramic Coatings Based on HfSiCN

    Science.gov (United States)

    Sacksteder, Dagny; Waters, Deborah L.; Zhu, Dongming

    2018-01-01

    High temperature fiber-reinforced ceramic matrix composites (CMCs) are important for aerospace applications because of their low density, high strength, and significantly higher-temperature capabilities compared to conventional metallic systems. The use of the SiCf/SiC and Cf/SiC CMCs allows the design of lighter-weight, more fuel efficient aircraft engines and also more advanced spacecraft airframe thermal protection systems. However, CMCs have to be protected with advanced environmental barrier coatings when they are incorporated into components for the harsh environments such as in aircraft engine or spacecraft applications. In this study, high temperature oxidation kinetics of an advanced HfSiCN coating on Cf/SiC CMC substrates were investigated at 1300 C, 1400 C, and 1500 C by using thermogravimetric analysis (TGA). The coating oxidation reaction parabolic rate constant and activation energy were estimated from the experimental results. The oxidation reaction studies showed that the coatings formed the most stable, predominant HfSiO4-HfO2 scales at 1400 C. A peroxidation test at 1400 C then followed by subsequent oxidation tests at various temperatures also showed more adherent scales and slower scale growth because of reduced the initial transient oxidation stage and increased HfSiO4-HfO2 content in the scales formed on the HfSiCN coatings.

  1. Nb effect in the nickel oxide-catalyzed low-temperature oxidative dehydrogenation of ethane

    KAUST Repository

    Zhu, Haibo; Ould-Chikh, Samy; Anjum, Dalaver Hussain; Sun, Miao; Biausque, Gregory; Basset, Jean-Marie; Caps, Valerie

    2012-01-01

    evaporation method from nickel nitrate and ammonium niobium oxalate. These consist in NiO nanocrystallites (7-13 nm) associated, at Nb contents >3 at.%., with an amorphous thin layer (1-2 nm) of a niobium-rich mixed oxide with a structure similar

  2. High temperature cyclic oxidation of Ti-Al based intermetallic in static laboratory air

    International Nuclear Information System (INIS)

    Astuty Amrin; Esah Hamzah; Nurfashahidayu Mohd Badri; Hafida Hamzah

    2007-01-01

    The objective of this study is to investigate the oxidation behaviour of binary γ-Ti Al based intermetallics with composition (at%) of 45A, 48Al and 50 Al, and ternary alloys of Ti-48Al containing 2Cr and 4Cr. Thermal cyclic oxidation was conducted discontinuously at temperatures of 700 degree Celsius and 900 degree Celsius in static laboratory air. Optical microscopy, Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Analysis (EDX) and X-ray diffraction (XRD) techniques were employed for the analysis. SEM examination of cross-sectional samples using secondary electron and line-scan analysis after exposure at 700 degree Celsius showed that non-adherent oxides scales formed due to the spallation caused by cyclic condition. For exposure to 900 degree Celsius, only binary alloys exhibited breakaway oxidation whereas the oxide scales formed on the ternary alloys were well-adhered on the substrate alloy. Overall, exposure at 900 degree Celsius resulted in thicker and harder oxide scales and addition of Cr seems to improve oxidation resistance of Ti-Al based intermetallics at higher temperature. (author)

  3. Air oxidation of Zircaloy-4, M5 (registered) and ZIRLOTM cladding alloys at high temperatures

    International Nuclear Information System (INIS)

    Steinbrueck, M.; Boettcher, M.

    2011-01-01

    The paper presents the results of isothermal and transient oxidation experiments of the advanced cladding alloys M5 (registered) and ZIRLO TM in comparison to Zircaloy-4 in air at temperatures from 973 to 1853 K. Generally, oxidation in air leads to a strong degradation of the cladding material. The main mechanism of this process is the formation of zirconium nitride and its re-oxidation. From the point of view of safety, the barrier effect of the fuel cladding is lost much earlier than during accident transients with a steam atmosphere only. Comparison of the three alloys investigated reveals a qualitatively similar, but quantitatively varying oxidation behavior in air. The mainly parabolic oxidation kinetics, where applicable, is comparable for the three alloys. Strong differences of up to 500% in oxidation rates were observed after transition to linear kinetics at temperatures below 1300 K. The paper presents kinetic rate constants as well as critical times and oxide scale thicknesses at the point of transition from parabolic to linear kinetics.

  4. Some observations on the high temperature oxidation behaviour of plasma sprayed Ni3Al coatings

    International Nuclear Information System (INIS)

    Singh, H.; Prakash, S.; Puri, D.

    2007-01-01

    High temperature oxidation resistance of the superalloys can be greatly enhanced by plasma sprayed coatings and this is a growing industry of considerable economic importance. The purpose of these coatings is to form long-lasting oxidation protective scales. In the current investigation, Ni 3 Al powder was prepared by mechanical mixing of pure nickel and aluminium powders in a ball mill. Subsequently Ni 3 Al powder was deposited on three Ni-base superalloys: Superni 600, Superni 601 and Superni 718 and, one Fe-base superalloy, Superfer 800H by shrouded plasma spray process. Oxidation studies were conducted on the coated superalloys in air at 900 deg. C under cyclic conditions for 50 cycles. Each cycle consisted of 1 h heating followed by 20 min of cooling in air. The thermogravimetric technique was used to approximate the kinetics of oxidation. All the coated superalloys nearly followed parabolic rate law of oxidation. X-ray diffraction, SEM/EDAX and EPMA techniques were used to analyse the oxidation products. The Ni 3 Al coating was found to be successful in maintaining its adherence to the superalloy substrates in all the cases. The oxide scales formed on the oxidised coated superalloys were found to be intact and spallation-free. XRD analysis revealed the presence of phases like NiO, Al 2 O 3 and NiAl 2 O 4 in the oxide scales, which are reported as protective oxides against high temperature oxidation. The XRD results were further supported by SEM/EDAX and EPMA

  5. Microstructural characterization of thermal barrier coating on Inconel 617 after high temperature oxidation

    Directory of Open Access Journals (Sweden)

    Mohammadreza Daroonparvar

    2013-06-01

    Full Text Available A turbine blade was protected against high temperature corrosion and oxidation by thermal barrier coatings (TBCsusing atmospheric plasma spraying technique (APS on a Ni-based superalloy (Inconel 617. The coatings (NiCr6AlY/ YSZ and NiCr10AlY/YSZ consist of laminar structure with substantial interconnected porosity transferred oxygen from Yittria stabilized Zirconia (YSZ layer toward the bond coat (NiCrAlY. Hence, a thermally grown oxide layer (TGO was formed on the metallic bond coat and internal oxidation of the bond coat occurred during oxidation. The TBC systems were oxidized in a normal electrically heated furnace at 1150 °C for 18, 22, 26, 32 and 40h.Microstructural characterization of coatings demonstrated that the growth of the TGO layer on the nickel alloy with 6wt. % Al is more rapid than TGO with 10wt. % Al. In addition, many micro-cracks were observed at the interface of NiCr6AlY/YSZ. X-ray diffraction analysis (XRD showed the existence of detrimental oxides such as NiCr2O4, NiCrO3 and NiCrO4 in the bond coat containing 6wt. % Al, accompanied by rapid volume expansion causing the destruction of TBC. In contrast, in the bond coat with 10wt. % Al, NiO, Al2O3and Cr2O3 oxides were formed while very low volume expansion occurred. The oxygen could not penetrate into the TGO layer of bond coat with 10 wt. % Al during high temperature oxidation and the detrimental oxides were not extensively formed within the bond coat as more oxygen was needed. The YSZ with higher Al content showed higher oxidation resistance.

  6. Low temperature phase transition of the stoichiometric Ln2NiO4 oxides

    International Nuclear Information System (INIS)

    Fernandez, F.; Saez-Puche, R.; Botto, I.L.; Baran, E.J.

    1991-01-01

    In this paper we will present a comparative study of the structural phase transition in Ln 2 NiO 4 oxides, by means of neutron diffraction and infrared(IR) spectroscopy. In the Ln 2 NiO 4 oxides (Ln=La, Pr and Nd), there is a low temperature structural phase transition from the orthorhombic symmetry to a tetragonal phase, of first order character. The IR spectra show, at low temperature, a splitting of the bands related with the stretching Ni-O, strongly correlated with the phase transformation. From the neutron data, the phase transition can be visualized as a sudden tilt of the nickel octahedra

  7. Low Temperature Synthesis and Properties of Gadolinium-Doped Cerium Oxide Nanoparticles

    DEFF Research Database (Denmark)

    Machado, Marina F. S.; P. R. Moraes, Leticia; Monteiro, Natalia K.

    2017-01-01

    Gadolinium-doped cerium oxide (GDC) is an attractive ceramic material for solid oxide fuel cells (SOFCs) both as the electrolyte or in composite electrodes. The Ni/GDC cermet can be tuned as a catalytic layer, added to the conventional Ni/yttria-stabilized zirconia (YSZ), for the internal steam...... sintering temperature needed to obtain a fully dense ceramic body, which can result in undesired reactions with YSZ. In this study, a green chemistry route for the synthesis of 10 mol% GDC nanoparticles is proposed. Such a low temperature synthesis provides control over particle size and sinterability...

  8. Note: A method for minimizing oxide formation during elevated temperature nanoindentation

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, I. C.; Hodge, A. M., E-mail: ahodge@usc.edu [Department of Aerospace and Mechanical Engineering, University of Southern California, 3650 McClintock Avenue OHE430, Los Angeles, California 90089 (United States); Garcia-Sanchez, E. [Department of Aerospace and Mechanical Engineering, University of Southern California, 3650 McClintock Avenue OHE430, Los Angeles, California 90089 (United States); Facultad de Ingeniería Mecánica y Eléctrica, Universidad Autónoma de Nuevo León, Av. Universidad S/N, San Nicolás de los Garza, NL 66450 (Mexico)

    2014-09-15

    A standardized method to protect metallic samples and minimize oxide formation during elevated-temperature nanoindentation was adapted to a commercial instrument. Nanoindentation was performed on Al (100), Cu (100), and W (100) single crystals submerged in vacuum oil at 200 °C, while the surface morphology and oxidation was carefully monitored using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The results were compared to room temperature and 200 °C nanoindentation tests performed without oil, in order to evaluate the feasibility of using the oil as a protective medium. Extensive surface characterization demonstrated that this methodology is effective for nanoscale testing.

  9. The temperature coefficient of the resonance integral for uranium metal and oxide

    Energy Technology Data Exchange (ETDEWEB)

    Blomberg, P; Hellstrand, E; Homer, S

    1960-06-15

    The temperature coefficient of the resonance integral in uranium metal and oxide has been measured over a wide temperature range for rods with three different diameters. The results for metal agree with most earlier results from activation measurements but differ as much as a factor of two from results obtained with reactivity methods. For oxide only one measurement has been reported recently. Our value is considerably lower than the result of that measurement. The experiments will continue in order to find the reason for the large discrepancy mentioned above.

  10. The temperature coefficient of the resonance integral for uranium metal and oxide

    International Nuclear Information System (INIS)

    Blomberg, P.; Hellstrand, E.; Homer, S.

    1960-06-01

    The temperature coefficient of the resonance integral in uranium metal and oxide has been measured over a wide temperature range for rods with three different diameters. The results for metal agree with most earlier results from activation measurements but differ as much as a factor of two from results obtained with reactivity methods. For oxide only one measurement has been reported recently. Our value is considerably lower than the result of that measurement. The experiments will continue in order to find the reason for the large discrepancy mentioned above

  11. Thermodynamic Studies of the Phase Relationships of Nonstoichiometric Cerium Oxides at Higher Temperatures

    DEFF Research Database (Denmark)

    Sørensen, Ole Toft

    1976-01-01

    Partial molar thermodynamic quantities for oxygen in nonstoichiometric cerium oxides were determined by thermogravimetric analysis in CO/CO2 mixtures in the temperature range 900–1400°C. Under these conditions compositions within the range 2.00 greater-or-equal, slanted O/M greater-or-equal, slan......Partial molar thermodynamic quantities for oxygen in nonstoichiometric cerium oxides were determined by thermogravimetric analysis in CO/CO2 mixtures in the temperature range 900–1400°C. Under these conditions compositions within the range 2.00 greater-or-equal, slanted O/M greater...

  12. The effect of reaction temperature on the room temperature ferromagnetic property of sol-gel derived tin oxide nanocrystal

    Science.gov (United States)

    Sakthiraj, K.; Hema, M.; Balachandra Kumar, K.

    2018-06-01

    In the present study, nanocrystalline tin oxide materials were prepared using sol-gel method with different reaction temperatures (25 °C, 50 °C, 75 °C & 90 °C) and the relation between the room temperature ferromagnetic property of the sample with processing temperature has been analysed. The X-ray diffraction pattern and infrared absorption spectra of the as-prepared samples confirm the purity of the samples. Transmission electron microscopy images visualize the particle size variation with respect to reaction temperature. The photoluminescence spectra of the samples demonstrate that luminescence process in materials is originated due to the electron transition mediated by defect centres. The room temperature ferromagnetic property is observed in all the samples with different amount, which was confirmed using vibrating sample magnetometer measurements. The saturation magnetization value of the as-prepared samples is increased with increasing the reaction temperature. From the photoluminescence & magnetic measurements we accomplished that, more amount of surface defects like oxygen vacancy and tin interstitial are created due to the increase in reaction temperature and it controls the ferromagnetic property of the samples.

  13. Temperature estimates from the Zircaloy oxidation kinetics in the α plus β phase region

    International Nuclear Information System (INIS)

    Olsen, C.S.

    1981-01-01

    Oxidation rates of Zircaloy in steam were measured at temperatures between 961 and 1264 K and for duration times between 25 and 1900 seconds in order to calculate, in conjunction with measurements from postirradiation metallographic examination, the prior peak temperatures of Zircaloy fuel rod cladding. These temperature estimates will be used in light water reactor research programs to assess (a) the accuracy of temperature measurements of fuel rod cladding peak temperatures from thermocouples attached to the surface during loss-of-coolant experiments (LOCEs), (b) the perturbation of the fuel rod cladding LOCE temperature history caused by the presence of thermocouples, and (c) the measurements of cladding azimuthal temperature gradients near the thermocouple locations

  14. Mid-infrared response of reduced graphene oxide and its high-temperature coefficient of resistance

    Directory of Open Access Journals (Sweden)

    Haifeng Liang

    2014-10-01

    Full Text Available Much effort has been made to study the formation mechanisms of photocurrents in graphene and reduced graphene oxide films under visible and near-infrared light irradiation. A built-in field and photo-thermal electrons have been applied to explain the experiments. However, much less attention has been paid to clarifying the mid-infrared response of reduced graphene oxide films at room temperature. Thus, mid-infrared photoresponse and annealing temperature-dependent resistance experiments were carried out on reduced graphene oxide films. A maximum photocurrent of 75 μA was observed at room temperature, which was dominated by the bolometer effect, where the resistance of the films decreased as the temperature increased after they had absorbed light. The electrons localized in the defect states and the residual oxygen groups were thermally excited into the conduction band, forming a photocurrent. In addition, a temperature increase of 2 °C for the films after light irradiation for 2 minutes was observed using absorption power calculations. This work details a way to use reduced graphene oxide films that contain appropriate defects and residual oxygen groups as bolometer-sensitive materials in the mid-infrared range.

  15. High-temperature oxidation of Zircaloy-2 and Zircaloy-4 in steam

    International Nuclear Information System (INIS)

    Urbanic, V.F.; Heidrick, T.R.

    1978-01-01

    At temperatures above the (α + β)/β transformation temperature for zirconium alloys, steam reacts with β-Zr to form a superficial layer of zirconium oxide (ZrO 2 ) and an intermediate layer of oxygen-stabilized α-Zr. Reaction kinetics and the rate of growth of the combined (ZrO 2 + α-Zr) layer for Zircaloy-2 and Zircaloy-4 oxidation in steam were measured over the temperature range 1050-1850 o C. The reaction rates for both alloys were similar, obeyed parabolic kinetics and were not limited by gas phase diffusion. The parabolic rate constants were consistently less than those given by the Baker and Just correlation for zirconium oxidation in steam. A discontinuity was found in the temperature dependence of both the reaction rate and the rate of growth of the combined (ZrO 2 + α-Zr) layer. The discontinuity is attributed to a change in the oxide microstructure at the discontinuity temperature, an observation which is consistent with the zirconium-oxygen phase diagram. (author)

  16. CO2 as an Oxidant for High Temperature Reactions

    Directory of Open Access Journals (Sweden)

    Sibudjing eKawi

    2015-03-01

    Full Text Available This paper presents a review on the developments in catalyst technology for the reactions utilizing CO2 for high temperature applications. These include dehydrogenation of alkanes to olefins, the dehydrogenation of ethylbenzene to styrene and finally CO2 reforming of hydrocarbon feedstock (i.e. methane and alcohols. Aspects on the various reaction pathways are also highlighted. The literature on the role of promoters and catalyst development is critically evaluated. Most of the reactions discussed in this review are exploited in industries and related to on-going processes, thus providing extensive data from literature. However some reactions, such as CO2 reforming of ethanol and glycerol which have not reached industrial scale are also reviewed owing to their great potential in terms of sustainability which are essential as energy for the future. This review further illustrates the building-up of knowledge which shows the role of support and catalysts for each reaction and the underlying linkage between certain catalysts which can be adapted for the multiple CO2-related reactions.

  17. Oxidation of Inconel 625 superalloy upon treatment with oxygen or hydrogen plasma at high temperature

    Energy Technology Data Exchange (ETDEWEB)

    Vesel, Alenka; Drenik, Aleksander; Elersic, Kristina; Mozetic, Miran; Kovac, Janez [Jozef Stefan Institute, Jamova 39, SI-1000 Ljubljana (Slovenia); Gyergyek, Tomaz [University of Ljubljana, Faculty of Electrical Engineering, Trzaska 25, SI-1000 Ljubljana (Slovenia); Stockel, Jan; Varju, Jozef; Panek, Radomir [Institute of Plasma Physics, Academy of Sciences of the Czech Republic, Ze Slovankou 3, Praha 8 (Czech Republic); Balat-Pichelin, Marianne, E-mail: marianne.balat@promes.cnrs.fr [PROMES-CNRS Laboratory, 7 rue du four solaire, 66120 Font Romeu Odeillo (France)

    2014-06-01

    Initial stages of Inconel 625 superalloy (Ni{sub 60}Cr{sub 30}Mo{sub 10}Ni{sub 4}Nb{sub 1}) oxidation upon short treatment with gaseous plasma at different temperatures up to about 1600 K were studied. Samples were treated for different periods up to a minute by oxygen or hydrogen plasma created with a microwave discharge in the standing-wave mode at a pressure of 40 Pa and a power 500 W. Simultaneous heating of the samples was realized by focusing concentrated solar radiation from a 5 kW solar furnace directly onto the samples. The morphological changes upon treatment were monitored using scanning electron microscopy, compositional depth profiling was performed using Auger electron spectroscopy, while structural changes were determined by X-ray diffraction. The treatment in oxygen plasma caused formation of metal oxide clusters of three dimensional crystallites initially rich in nickel oxide with the increasing chromium oxide content as the temperature was increasing. At about 1100 K iron and niobium oxides prevailed on the surface causing a drop of the material emissivity at 5 μm. Simultaneously the NiCr{sub 2}O{sub 4} compound started growing at the interface between the oxide film and bulk alloy and the compound persisted up to temperatures close to the Inconel melting point. Intensive migration of minority alloying elements such as Fe and Ti was observed at 1600 K forming mixed surface oxides of sub-micrometer dimensions. The treatment in hydrogen plasma with small admixture of water vapor did not cause much modification unless the temperature was close to the melting point. At such conditions aluminum segregated on the surface and formed well-defined Al{sub 2}O{sub 3} crystals.

  18. Oxidation of Inconel 625 superalloy upon treatment with oxygen or hydrogen plasma at high temperature

    Science.gov (United States)

    Vesel, Alenka; Drenik, Aleksander; Elersic, Kristina; Mozetic, Miran; Kovac, Janez; Gyergyek, Tomaz; Stockel, Jan; Varju, Jozef; Panek, Radomir; Balat-Pichelin, Marianne

    2014-06-01

    Initial stages of Inconel 625 superalloy (Ni60Cr30Mo10Ni4Nb1) oxidation upon short treatment with gaseous plasma at different temperatures up to about 1600 K were studied. Samples were treated for different periods up to a minute by oxygen or hydrogen plasma created with a microwave discharge in the standing-wave mode at a pressure of 40 Pa and a power 500 W. Simultaneous heating of the samples was realized by focusing concentrated solar radiation from a 5 kW solar furnace directly onto the samples. The morphological changes upon treatment were monitored using scanning electron microscopy, compositional depth profiling was performed using Auger electron spectroscopy, while structural changes were determined by X-ray diffraction. The treatment in oxygen plasma caused formation of metal oxide clusters of three dimensional crystallites initially rich in nickel oxide with the increasing chromium oxide content as the temperature was increasing. At about 1100 K iron and niobium oxides prevailed on the surface causing a drop of the material emissivity at 5 μm. Simultaneously the NiCr2O4 compound started growing at the interface between the oxide film and bulk alloy and the compound persisted up to temperatures close to the Inconel melting point. Intensive migration of minority alloying elements such as Fe and Ti was observed at 1600 K forming mixed surface oxides of sub-micrometer dimensions. The treatment in hydrogen plasma with small admixture of water vapor did not cause much modification unless the temperature was close to the melting point. At such conditions aluminum segregated on the surface and formed well-defined Al2O3 crystals.

  19. Shape-Dependent Activity of Ceria for Hydrogen Electro-Oxidation in Reduced-Temperature Solid Oxide Fuel Cells.

    Science.gov (United States)

    Tong, Xiaofeng; Luo, Ting; Meng, Xie; Wu, Hao; Li, Junliang; Liu, Xuejiao; Ji, Xiaona; Wang, Jianqiang; Chen, Chusheng; Zhan, Zhongliang

    2015-11-04

    Single crystalline ceria nanooctahedra, nanocubes, and nanorods are hydrothermally synthesized, colloidally impregnated into the porous La0.9Sr0.1Ga0.8Mg0.2O3-δ (LSGM) scaffolds, and electrochemically evaluated as the anode catalysts for reduced temperature solid oxide fuel cells (SOFCs). Well-defined surface terminations are confirmed by the high-resolution transmission electron microscopy--(111) for nanooctahedra, (100) for nanocubes, and both (110) and (100) for nanorods. Temperature-programmed reduction in H2 shows the highest reducibility for nanorods, followed sequentially by nanocubes and nanooctahedra. Measurements of the anode polarization resistances and the fuel cell power densities reveal different orders of activity of ceria nanocrystals at high and low temperatures for hydrogen electro-oxidation, i.e., nanorods > nanocubes > nanooctahedra at T ≤ 450 °C and nanooctahedra > nanorods > nanocubes at T ≥ 500 °C. Such shape-dependent activities of these ceria nanocrystals have been correlated to their difference in the local structure distortions and thus in the reducibility. These findings will open up a new strategy for design of advanced catalysts for reduced-temperature SOFCs by elaborately engineering the shape of nanocrystals and thus selectively exposing the crystal facets. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Study about uranium oxides at high temperature by X-ray diffraction

    International Nuclear Information System (INIS)

    Costa, M.I.

    1978-01-01

    In this work a technique to study the lattice parameters in the crystalline substances at hight temperature by X-rays diffraction is developed. The results obtained agree very well with the experimental data found in the literature. The crystalline structure of uranium oxide at different temperature is studied in detail by this technique. At the range of the temperature investigated, i.e., 20 0 C to 640 0 C, the following forms for uranium oxide: U 3 O 8 in its hexagonal modification, cubic UO 2 , cubic U 4 O 9 and tetragonal U 3 O 7 is observed. The appearance of two hexagonal units observed in this work is identified by Milne. A good reproducibillity is observed for measurements at the same temperature [pt

  1. Decarburization behavior and mechanical properties of Inconel 617 during high temperature oxidation in He environment

    International Nuclear Information System (INIS)

    Kim, Young Do; Kim, Dae Gun; Jo, Tae Sun; Kim, Hoon Sup; Lim, Jeong Hun

    2010-04-01

    Among Generation IV reactor concepts, high temperature gas-cooled reactors (HTGRs) are high-efficiency systems designed for the economical production of hydrogen and electricity. Inconel 617 is a solid-solution strengthening Ni-based superalloy that shows excellent strength, creep-rupture strength, and oxidation resistance at high temperatures. Thus, it is a desirable candidate for tube material of IHX and HGD in HTGRs. In spite of these excellent properties, aging degradation by long time exposure at high temperature induced to deterioration of mechanical properties and furthermore alloys' lifetime because of Cr-depleted zone and carbide free zone below external scale. Also, machinability of Inconel 617 is a important property for system design. In this study, oxidation and decarbrization behavior were evaluated at various aging temperature and environment. Also, cold rolling was carried out for the machinability evaluation of Inconel 617 and then microstructure change was evaluated

  2. Exchange of hydrogen isotopes in oxide ceramics at room temperature

    International Nuclear Information System (INIS)

    Suzuki, H.; Morita, K.; Soda, K.

    2001-01-01

    The decay curves of D and up-take curves of H on the exchange of D implanted into Li 2 TiO 3 for H in H 2 O vapor caused by exposure to normal-air at room temperature have been measured as a function of exposure time at different implantation concentrations by means of the elastic recoil detection technique. The re-emission curves of D retained and H up-taken in a specimen by isochronal annealing for 10 min have been also measured. It is found that the thermal re-emission of D and H takes place uniformly over the whole specimen due to local molecular recombination in the bulk and that the re-emission rates of H and D in the near-surface layers are slower than those in the deeper layers. It is also found that the decay of D caused by the D-H exchange takes place rapidly in the beginning and the retained amount of D attains at a constant level and the retained fraction of D are higher as the initial implantation concentrations of D are lower. The decay curves of D and the up-take curves of H have been analysed using the mass balance equations, in which the elementary processes are taken into account according to the exchange model of one way diffusion from the surface into the bulk. It is shown that the solution of the mass balance equations reproduces well the experimental data. The rate constants of the elementary processes determined are discussed. (orig.)

  3. Influence of oxidation temperature on the interfacial properties of n-type 4H-SiC MOS capacitors

    Energy Technology Data Exchange (ETDEWEB)

    Jia, Yifan; Lv, Hongliang [School of Microelectronics, Xidian University, Key Laboratory of Wide Band Gap Semiconductor Materials and Devices, Xi’an 710071 (China); Song, Qingwen, E-mail: qwsong@xidian.edu.cn [School of Microelectronics, Xidian University, Key Laboratory of Wide Band Gap Semiconductor Materials and Devices, Xi’an 710071 (China); School of Advanced Materials and Nanotechnology, Xidian University, Xi’an 710071 (China); Tang, Xiaoyan, E-mail: xytang@xidian.edu.cn [School of Microelectronics, Xidian University, Key Laboratory of Wide Band Gap Semiconductor Materials and Devices, Xi’an 710071 (China); Xiao, Li; Wang, Liangyong; Tang, Guangming [Zhongxing Telecommunication Equipment Corporation, Shenzhen 518057 (China); Zhang, Yimen; Zhang, Yuming [School of Microelectronics, Xidian University, Key Laboratory of Wide Band Gap Semiconductor Materials and Devices, Xi’an 710071 (China)

    2017-03-01

    Highlights: • Effect of oxidation temperature on interfacial properties of SiO{sub 2}/SiC is investigated. • Raising the oxidation temperature effectively decreases the density of NITs and N{sub eff}. • The higher oxidation temperature reduces the surface RMS roughness of the grow SiO{sub 2}. • SIMS and XPS results reveal the improvement mechanism of high temperature oxidation. - Abstract: The effect of oxidation temperature on interfacial properties of n-type 4H-SiC metal-oxide-semiconductor capacitors has been systematically investigated. Thermal dry oxidation process with three different oxidation temperatures 1200 °C, 1300 °C and 1350 °C were employed to grow SiO{sub 2} dielectric, following by the standard post-oxidation annealing (POA) in NO ambience at 1175 °C for 2 h. The root mean square (RMS) roughness measured by Atomic Force Microscopy for the thermally grown SiO{sub 2} before POA process is reduced with increasing the oxidation temperature, obtaining an atomically flat surface with a RMS of 0.157 nm from the sample oxidized at 1350 °C. Several kinds of electrical measurements were used to evaluate the densities of near interface traps and effective fixed dielectric charge for the samples, exhibiting a trend reduced with increasing the oxidation temperature. The interface state density of 3 × 10{sup 11} cm{sup −2}eV{sup −1} at 0.2 eV from the conduction band edge was achieved from conductance method measurement for the sample oxidized at 1350 °C. The results from Secondary Ion Mass Spectroscopy and X-ray Photoelectron Spectroscopy demonstrate that high oxidation temperature can reduce the width of transition layer, the excess Si and silicon suboxide compositions near the interface, leading to effective improvement of the interfacial properties.

  4. High Temperature Oxidation of Ferritic Steels for Solid Oxide Electrolysis Stacks

    DEFF Research Database (Denmark)

    Molin, Sebastian; Chen, Ming; Bentzen, Janet Jonna

    2013-01-01

    atmospheres at 800°C. Four commercially available alloys: Crofer 22 APU, Crofer 22 H, AL29-4, E-Brite were characterized in humidified hydrogen. One alloy, Crofer 22 APU was also characterized in pure oxygen both in the as-prepared state and after application of a protective coating. Best corrosion resistance......Oxidation rates of ferritic steels used as interconnector plates in Solid Oxide Electrolysis Stacks are of concern as they may be determining for the life time of the technology. In this study oxidation experiments were carried out for up to 1000 hours in hydrogen-side and oxygen-side simulated...... in humidified hydrogen atmosphere was observed for Crofer 22 APU and Crofer 22 H alloys. Corrosion rates for Crofer 22 APU measured in humidified hydrogen are similar to the corrosion rates measured in air. Both coatings of plasma sprayed LSM and dual layer coatings (Co3O4/LSM-Co3O4) applied by wet spraying...

  5. Cesium relocation in mixed-oxide fuel pins resulting from increased temperature reirradiation

    International Nuclear Information System (INIS)

    Lawrence, L.A.; Woodley, R.E.; Weber, E.T.

    1976-06-01

    Mixed-oxide fuel pins from EBR-II test subassemblies PNL-3 and PNL-4 were reirradiated in the GETR to study effects of increased fuel and cladding temperatures on chemical and thermomechanical behavior. Radial and axial distributions of cesium were obtained using postirradiation nondestructive precision gamma-scanning techniques. Data presented relate to the dependence of cesium distribution and transport processes on temperature gradients which were altered after substantial steady-state operation

  6. Models for the Configuration and Integrity of Partially Oxidized Fuel Rod Cladding at High Temperatures

    International Nuclear Information System (INIS)

    Siefken, L.J.

    1999-01-01

    Models were designed to resolve deficiencies in the SCDAP/RELAP5/MOD3.2 calculations of the configuration and integrity of hot, partially oxidized cladding. These models are expected to improve the calculations of several important aspects of fuel rod behavior. First, an improved mapping was established from a compilation of PIE results from severe fuel damage tests of the configuration of melted metallic cladding that is retained by an oxide layer. The improved mapping accounts for the relocation of melted cladding in the circumferential direction. Then, rules based on PIE results were established for calculating the effect of cladding that has relocated from above on the oxidation and integrity of the lower intact cladding upon which it solidifies. Next, three different methods were identified for calculating the extent of dissolution of the oxidic part of the cladding due to its contact with the metallic part. The extent of dissolution effects the stress and thus the integrity of the oxidic part of the cladding. Then, an empirical equation was presented for calculating the stress in the oxidic part of the cladding and evaluating its integrity based on this calculated stress. This empirical equation replaces the current criterion for loss of integrity which is based on temperature and extent of oxidation. Finally, a new rule based on theoretical and experimental results was established for identifying the regions of a fuel rod with oxidation of both the inside and outside surfaces of the cladding. The implementation of these models is expected to eliminate the tendency of the SCDAP/RELAP5 code to overpredict the extent of oxidation of the upper part of fuel rods and to underpredict the extent of oxidation of the lower part of fuel rods and the part with a high concentration of relocated material. This report is a revision and reissue of the report entitled, Improvements in Modeling of Cladding Oxidation and Meltdown

  7. Alloying Au surface with Pd reduces the intrinsic activity in catalyzing CO oxidation

    KAUST Repository

    Qian, Kun; Luo, Liangfeng; Jiang, Zhiquan; Huang, Weixin

    2016-01-01

    were evaluated. The formation of Au-Pd alloy particles was identified. The Au-Pd alloy particles exhibit enhanced dispersions on SiO2 than Au particles. Charge transfer from Pd to Au within Au-Pd alloy particles. Isolated Pd atoms dominate the surface

  8. Oxidation kinetics of some zirconium alloys in flowing carbon dioxide at high temperatures

    International Nuclear Information System (INIS)

    Kohli, R.

    1980-01-01

    The oxidation kinetics of three zirconium alloys (Zr-2.2 wt% Hf, Zr-2.5 wt% Nb, and Zr-3 wt% Nb-1 wt% Sn) have been measured in flowing carbon dioxide in the temperature range from 873 to 1173 K to 120 ks (2000 min). At all oxidation temperatures, Zr-2.5 Nb and Zr-3 Nb-1 Sn showed a transition to rapid linear kinetics after initial parabolic oxidation. The Zr-2.2 Hf showed this transition at temperatures in the range from 973 to 1173 K; at 873 K, no transition was observed within the oxidation times reported. The Zr-2.2 Hf showed the smallest weight gains, followed in order by Zr-2.5 Nb and Zr-3 Nb-1 Sn. Increased oxidation rates and shorter times-to-rate-transition of Zr-2.2 Nb and Zr-1 Sn as compared with Zr-2.2 Hf can be attributed to the presence of niobium, tin, and hafnium in the alloys. This is considered in terms of the Nomura-Akutsu model, according to which hafnium should delay the rate transition, while niobium and tin lead to shorter times-to-rate-transition. The scale on Zr-2.2 Hf was identified as monoclinic zirconia, while the tetragonal phase, 6ZrO 2 .Nb 2 O 5 , was contained in the monoclinic zirconia scales on both other alloys

  9. High temperature oxidation characteristics of developed Ni-Cr-W superalloys in air

    International Nuclear Information System (INIS)

    Suzuki, Tomio; Shindo, Masami

    1996-11-01

    For expanding utilization of the Ni-Cr-W superalloy, which has been developed as one of new high temperature structural materials used in the advanced High Temperature Gas-cooled Reactors (HTGRs), in various engineering fields including the structural material for heat utilization system, the oxidation behavior of this alloy in air as one of high oxidizing environments becomes one of key factors. The oxidation tests for the industrial scale heat of Ni-Cr-W superalloy with the optimized chemical composition and five kinds of experimental Ni-Cr-W alloys with different Cr/W ratio were carried out at high temperatures in the air compared with Hastelloy XR. The conclusions were obtained as follows. (1) The oxidation resistance of the industrial scale heat of Ni-Cr-W superalloy with the optimized chemical composition was superior to that of Hastelloy XR. (2) The most excellent oxidation resistance was obtained in an alloy with 19% Cr of the industrial scale heat of Ni-Cr-W superalloy. (author)

  10. High-Temperature, Dual-Atmosphere Corrosion of Solid-Oxide Fuel Cell Interconnects

    Science.gov (United States)

    Gannon, Paul; Amendola, Roberta

    2012-12-01

    High-temperature corrosion of ferritic stainless steel (FSS) surfaces can be accelerated and anomalous when it is simultaneously subjected to different gaseous environments, e.g., when separating fuel (hydrogen) and oxidant (air) streams, in comparison with single-atmosphere exposures, e.g., air only. This so-called "dual-atmosphere" exposure is realized in many energy-conversion systems including turbines, boilers, gasifiers, heat exchangers, and particularly in intermediate temperature (600-800°C) planar solid-oxide fuel cell (SOFC) stacks. It is generally accepted that hydrogen transport through the FSS (plate or tube) and its subsequent integration into the growing air-side surface oxide layer can promote accelerated and anomalous corrosion—relative to single-atmosphere exposure—via defect chemistry changes, such as increased cation vacancy concentrations, decreased oxygen activity, and steam formation within the growing surface oxide layers. Establishment of a continuous and dense surface oxide layer on the fuel side of the FSS can inhibit hydrogen transport and the associated effects on the air side. Minor differences in FSS composition, microstructure, and surface conditions can all have dramatic influences on dual-atmosphere corrosion behaviors. This article reviews high-temperature, dual-atmosphere corrosion phenomena and discusses implications for SOFC stacks, related applications, and future research.

  11. High-temperature oxidation of Zircaloy in hydrogen-steam mixtures

    International Nuclear Information System (INIS)

    Chung, H.M.; Thomas, G.R.

    1982-09-01

    Oxidation rates of Zircaloy-4 cladding tubes have been measured in hydrogen-steam mixtures at 1200 to 1700 0 C. For a given isothermal oxidation temperature, the oxide layer thicknesses have been measured as a function of time, steam supply rate, and hydrogen overpressure. The oxidation rates in the mixtures were compared with similar data obtained in pure steam and helium-steam environments under otherwise identical conditions. The rates in pure steam and helium-steam mixtures were equivalent and comparable to the parabolic rates obtained under steam-saturated conditions and reported in the literature. However, when the helium was replaced with hydrogen of equivalent partial pressure, a significantly smaller oxidation rate was observed. For high steam-supply rates, the oxidation kinetics in a hydrogen-steam mixture were parabolic, but the rate was smaller than for pure steam or helium-steam mixtures. Under otherwise identical conditions, the ratio of the parabolic rate for hydrogen-steam to that for pure steam decreased with increasing temperature and decreasing steam-supply rate

  12. Manganese oxide phases and morphologies: A study on calcination temperature and atmospheric dependence

    Directory of Open Access Journals (Sweden)

    Matthias Augustin

    2015-01-01

    Full Text Available Manganese oxides are one of the most important groups of materials in energy storage science. In order to fully leverage their application potential, precise control of their properties such as particle size, surface area and Mnx+ oxidation state is required. Here, Mn3O4 and Mn5O8 nanoparticles as well as mesoporous α-Mn2O3 particles were synthesized by calcination of Mn(II glycolate nanoparticles obtained through an economical route based on a polyol synthesis. The preparation of the different manganese oxides via one route facilitates assigning actual structure–property relationships. The oxidation process related to the different MnOx species was observed by in situ X-ray diffraction (XRD measurements showing time- and temperature-dependent phase transformations occurring during oxidation of the Mn(II glycolate precursor to α-Mn2O3 via Mn3O4 and Mn5O8 in O2 atmosphere. Detailed structural and morphological investigations using transmission electron microscopy (TEM and powder XRD revealed the dependence of the lattice constants and particle sizes of the MnOx species on the calcination temperature and the presence of an oxidizing or neutral atmosphere. Furthermore, to demonstrate the application potential of the synthesized MnOx species, we studied their catalytic activity for the oxygen reduction reaction in aprotic media. Linear sweep voltammetry revealed the best performance for the mesoporous α-Mn2O3 species.

  13. Application of flexible micro temperature sensor in oxidative steam reforming by a methanol micro reformer.

    Science.gov (United States)

    Lee, Chi-Yuan; Lee, Shuo-Jen; Shen, Chia-Chieh; Yeh, Chuin-Tih; Chang, Chi-Chung; Lo, Yi-Man

    2011-01-01

    Advances in fuel cell applications reflect the ability of reformers to produce hydrogen. This work presents a flexible micro temperature sensor that is fabricated based on micro-electro-mechanical systems (MEMS) technology and integrated into a flat micro methanol reformer to observe the conditions inside that reformer. The micro temperature sensor has higher accuracy and sensitivity than a conventionally adopted thermocouple. Despite various micro temperature sensor applications, integrated micro reformers are still relatively new. This work proposes a novel method for integrating micro methanol reformers and micro temperature sensors, subsequently increasing the methanol conversion rate and the hydrogen production rate by varying the fuel supply rate and the water/methanol ratio. Importantly, the proposed micro temperature sensor adequately controls the interior temperature during oxidative steam reforming of methanol (OSRM), with the relevant parameters optimized as well.

  14. Application of Flexible Micro Temperature Sensor in Oxidative Steam Reforming by a Methanol Micro Reformer

    Directory of Open Access Journals (Sweden)

    Yi-Man Lo

    2011-02-01

    Full Text Available Advances in fuel cell applications reflect the ability of reformers to produce hydrogen. This work presents a flexible micro temperature sensor that is fabricated based on micro-electro-mechanical systems (MEMS technology and integrated into a flat micro methanol reformer to observe the conditions inside that reformer. The micro temperature sensor has higher accuracy and sensitivity than a conventionally adopted thermocouple. Despite various micro temperature sensor applications, integrated micro reformers are still relatively new. This work proposes a novel method for integrating micro methanol reformers and micro temperature sensors, subsequently increasing the methanol conversion rate and the hydrogen production rate by varying the fuel supply rate and the water/methanol ratio. Importantly, the proposed micro temperature sensor adequately controls the interior temperature during oxidative steam reforming of methanol (OSRM, with the relevant parameters optimized as well.

  15. High temperature oxidation and electrochemical investigations on nickel-base alloys

    International Nuclear Information System (INIS)

    Obigodi-Ndjeng, Georgia

    2011-01-01

    This study examined high-temperature oxidation behavior of different Ni-base alloys. In addition, electrochemical characterization of the alloy's corrosion behavior was carried out, including comparison of the properties of native passive films grown at room temperature and high temperature oxide scales. PWA 1483 (single-crystalline Ni-base superalloy) and model alloys Ni-Cr-X (where X is either Co or Al) were oxidized at 800 and 900 C in air for different time periods. The superalloy showed the best oxidation behavior at both temperatures, which might be due to the fact that the oxidation growth function is subparabolic for the model alloys and parabolic for the superalloy at 800 C. At higher temperatures, changes in the kinetics are induced, as the oxides grow faster, thus only PWA 1483 growth follows the parabolic law. Different scales in a typical sandwich form were detected, with the inner layer comprised of mostly Cr 2 O 3 , the middle layer was mixture of different oxides and spinels, depending on the alloying elements, and the oxide at the interface oxygen/oxide was found to be NiO. The influence of sample preparation could also be shown, as rougher surfaces change the oxidation kinetics from parabolic and subparabolic for polished samples to linear. The influence of moisture on the oxidation behavior of the 2 nd generation single crystal Ni-base superalloys (PWA 1484, PWA 1487, CMSX 4, Rene N5 and Rene N5+) was studied at 1000 C after 100 h oxidation period. It was found that the moisture increased the oxidation rate and mostly the transient oxides growth rate. The water vapor content in air also influenced the behavior of these alloys, as they showed a higher mass gain in air + 30% water vapor than in air + 10% water vapor. The alloys PWA 1484 and CMSX 4 showed respectively the worst and best behavior in all the studied atmospheres. The addition of reactive elements, such as Yttrium, Hafnium and Lanthanum is likely to enhance the oxidation behavior of PWA

  16. New insights into the low-temperature oxidation of 2-methylhexane

    KAUST Repository

    Wang, Zhandong; Mohamed, Samah; Zhang, Lidong; Moshammer, Kai; Popolan-Vaida, Denisia M.; Shankar, Vijai; Lucassen, Arnas; Ruwe, Lena; Hansen, Nils; Dagaut, Philippe; Sarathy, Mani

    2016-01-01

    was composed of 2% 2-methyhexane, 22% O2 and 76% Ar and the pressure of the reactor was kept at 780Torr. Low-temperature oxidation intermediates with two to five oxygen atoms were observed. The detection of C7H14O5 and C7H12O4 species suggests that a third O2

  17. Experimental Consequences of Mottness in High-Temperature Copper-Oxide Superconductors

    Science.gov (United States)

    Chakraborty, Shiladitya

    2009-01-01

    It has been more than two decades since the copper-oxide high temperature superconductors were discovered. However, building a satisfactory theoretical framework to study these compounds still remains one of the major challenges in condensed matter physics. In addition to the mechanism of superconductivity, understanding the properties of the…

  18. Anomalous temperature dependence of the current in a metal-oxide-polymer resistive switching diode

    NARCIS (Netherlands)

    Gomes, H.L.; Rocha, P.R.F.; Kiazadeh, A.; Leeuw, de D.M.; Meskers, S.C.J.

    2011-01-01

    Metal-oxide polymer diodes exhibit non-volatile resistive switching. The current–voltage characteristics have been studied as a function of temperature. The low-conductance state follows a thermally activated behaviour. The high-conductance state shows a multistep-like behaviour and below 300 K an

  19. Oxidation of X20 in Water Vapour: The Effect of Temperature and Oxygen Partial Pressure

    DEFF Research Database (Denmark)

    Hansson, Anette Nørgaard; Montgomery, Melanie; Somers, Marcel A. J.

    2009-01-01

    The oxidation behaviour of X20 in various mixtures of water, oxygen and hydrogen was investigated at temperatures between 500 C and 700 C (time: 336 h). The samples were characterised using reflected light microscopy and scanning electron microscopy equipped with energy dispersive spectroscopy...

  20. Recent Progress in Nanostructured Oxide TE Materials for Power Generation at High Temperatures

    DEFF Research Database (Denmark)

    Van Nong, Ngo; Pryds, Nini; Linderoth, Søren

    Thermoelectric (TE) materials, which can convert waste heat into electricity, could play an important role in a global sustainable energy solution and environmental problems. Metal oxides have been considered as potential TE materials for power generation that can operate at high temperatures...

  1. Low temperature growth of gallium oxide thin films via plasma enhanced atomic layer deposition

    NARCIS (Netherlands)

    O'Donoghue, R.; Rechmann, J.; Aghaee, M.; Rogalla, D.; Becker, H.-W.; Creatore, M.; Wieck, A.D.; Devi, A.P.K.

    2017-01-01

    Herein we describe an efficient low temperature (60–160 °C) plasma enhanced atomic layer deposition (PEALD) process for gallium oxide (Ga2O3) thin films using hexakis(dimethylamido)digallium [Ga(NMe2)3]2 with oxygen (O2) plasma on Si(100). The use of O2 plasma was found to have a significant

  2. Au/iron oxide catalysts: temperature programmed reduction and X-ray diffraction characterization

    International Nuclear Information System (INIS)

    Neri, G.; Visco, A.M.; Galvagno, S.; Donato, A.; Panzalorto, M.

    1999-01-01

    Gold on iron oxides catalysts have been characterized by temperature programmed reduction (TPR) and X-ray diffraction spectroscopy (XRD). The influence of preparation method, gold loading and pretreatment conditions on the reducibility of iron oxides have been investigated. On the impregnated Au/iron oxide catalysts as well as on the support alone the partial reduction of Fe(III) oxy(hydroxides) to Fe 3 O 4 starts in the 550 and 700 K temperature range. On the coprecipitated samples, the temperature of formation of Fe 3 O 4 is strongly dependent on the presence of gold. The reduction temperature is lowered as the gold loading is increased. The reduction of Fe 3 O 4 to FeO occurs at about 900 K and is not dependent on the presence of gold and the preparation method. It is suggested that the effect of gold on the reducibility of the iron oxides is related to an increase of the structural defects and/or of the surface hydroxyl groups. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

  3. Ammonia oxidizer populations vary with nitrogen cycling across a tropical montane mean annual temperature gradient

    Science.gov (United States)

    S. Pierre; I. Hewson; J. P. Sparks; C. M. Litton; C. Giardina; P. M. Groffman; T. J. Fahey

    2017-01-01

    Functional gene approaches have been used to better understand the roles of microbes in driving forest soil nitrogen (N) cycling rates and bioavailability. Ammonia oxidation is a rate limiting step in nitrification, and is a key area for understanding environmental constraints on N availability in forests. We studied how increasing temperature affects the role of...

  4. Reliability of ^1^H NMR analysis for assessment of lipid oxidation at frying temperatures

    Science.gov (United States)

    The reliability of a method using ^1^H NMR analysis for assessment of oil oxidation at a frying temperature was examined. During heating and frying at 180 °C, changes of soybean oil signals in the ^1^H NMR spectrum including olefinic (5.16-5.30 ppm), bisallylic (2.70-2.88 ppm), and allylic (1.94-2.1...

  5. Densification of Highly Defective Ceria by High Temperature Controlled Re-Oxidation

    DEFF Research Database (Denmark)

    Ni, De Wei; Glasscock, Julie; Pons, Aénor

    2014-01-01

    Highly enhanced densification and grain growth of Ce0.9Gd0.1O1.95-δ (CGO, gadolinium-doped ceria, with 10 mol% Gd) is achieved in low oxygen activity atmospheres. However, the material can suffer mechanical failures during cooling when the re-oxidation process is not controlled due to the large...... volume changes. In this work, the redox process of CGO is investigated using dilatometry, microscopy, electrochemical impedance spectroscopy and thermodynamic analysis. In addition, the conditions allowing controlled re-oxidation and cooling in order to preserve the mechanical integrity of the CGO...... component are defined: this can be achieved over a wide temperature range (800−1200◦C) by gradually increasing the oxygen content of the atmosphere. It is found that the electrical conductivity of the CGO, particularly at low temperature (oxidation...

  6. Temperature dependent thermoelectric property of reduced graphene oxide-polyaniline composite

    Energy Technology Data Exchange (ETDEWEB)

    Mitra, Mousumi, E-mail: mousumimitrabesu@gmail.com; Banerjee, Dipali, E-mail: dipalibanerjeebesu@gmail.com [Department of Physics, Indian Institute of Engineering Science and Technology (IIEST), Howrah-711103 (India); Kargupta, Kajari, E-mail: karguptakajari2010@gmail.com [Department of Chemical Engineering, Jadavpur University, Kolkata (India); Ganguly, Saibal, E-mail: gangulysaibal2011@gmail.com [Chemical Engineering department, Universiti Teknologi Petronas, Perak, Tronoh (Malaysia)

    2016-05-06

    A composite material of reduced graphene oxide (rG) nanosheets with polyaniline (PANI) protonated by 5-sulfosalicylic acid has been synthesized via in situ oxidative polymerization method. The morphological and spectral characterizations have been done using FESEM and XRD measurements. The thermoelectric (TE) properties of the reduced graphene oxide-polyaniline composite (rG-P) has been studied in the temperature range from 300-400 K. The electrical conductivity and the Seebeck coefficient of rG-P is higher than the of pure PANI, while the thermal conductivity of the composite still keeps much low value ensuing an increase in the dimensionless figure of merit (ZT) in the whole temperature range.

  7. Oxidation Behavior of Carbon Steel: Effect of Formation Temperature and pH of the Environment

    Science.gov (United States)

    Dubey, Vivekanand; Kain, Vivekanand

    2017-11-01

    The nature of surface oxide formed on carbon steel piping used in nuclear power plants affects flow-accelerated corrosion. In this investigation, carbon steel specimens were oxidized in an autoclave using demineralized water at various temperatures (150-300 °C) and at pH levels (neutral, 9.5). At low temperatures ( 240 °C) as confirmed by scanning electron microscopy. Electrochemical impedance measurement followed by Mott-Schottky analysis indicated an increase in defect density with exposure duration at 150 °C at neutral pH but a low and stable defect density in alkaline environment. The defect density of the oxide formed at neutral pH at 150-300 °C was always higher than that formed in alkaline environment as reported in the literature.

  8. Investigation of the high temperature steam oxidation of Zircaloy 4 cladding tubes

    International Nuclear Information System (INIS)

    Leistikow, S.; Berg, H. v.; Kraft, R.; Pott, E.; Schanz, G.

    1979-01-01

    Also for the ORNL Zircaloy 4 cladding material, an intermediate decrease of the proportion of the ZrO 2 /α-phase layer was found, followed by an drastic increase when the breakaway of the ZrO 2 -scale occurred. Other reasons for small divergencies were evaluated, for instance temperature and time measurements, metallographic evaluation of layer thicknesses, consequences of one-sided (ORNL) and double-sided (KfK) oxidation. The so-called anomalous effect of steam oxidation during temperature transients was reproduced qualitatively and-in case that a reduced gain of oxygen was observed-explained by the predominant existence of the monoclinic oxide phase. The creep-rupture tests below 800 0 C showed a moderate prolongation of time-to-rupture when the tests were performed in steam (or after preoxidation in steam) instead of argon. Also slightly reduced maximum circumferential strain could be measured. (orig./RW) [de

  9. Effects of creep and oxidation on reduced modulus in high-temperature nanoindentation

    International Nuclear Information System (INIS)

    Li, Yan; Fang, Xufei; Lu, Siyuan; Yu, Qingmin; Hou, Guohui; Feng, Xue

    2016-01-01

    Nanoindentation tests were performed on single crystal Ni-based superalloy at temperatures ranging from 20 °C to 800 °C in inert environment. Load-displacement curves at temperatures higher than 500 °C exhibit obvious creep inferred by increasing displacements at load-holding segments. Load-displacement curves obtained at 800 °C also display negative unloading stiffness. Examination of the microstructure beneath the indented area using Transmission Electron Microscope (TEM) reveals abundant dislocation piling up as well as oxide formation on the substrate. A method considering the creep effect is proposed to calculate the reduced modulus. In addition, a dimensionless ratio relating indentation depth and oxide film thickness is introduced to explain the oxidation effect on the mechanical properties derived from the load-displacement curves.

  10. Effect of Ca and Y additions on oxidation behavior of magnesium alloys at high temperatures

    Institute of Scientific and Technical Information of China (English)

    FAN Jianfeng; YANG Changlin; XU Bingshe

    2012-01-01

    Oxidation and ignition of magnesium alloys at elevated temperature were successfully retarded by additions of Y and Ca.which could be melted at 1173 K in air without any protection.Thermogravimetric measurements in dry air revealed that the oxidation dynamics curves of Mg-2.5Ca alloy and Mg-3.5Y-0.79Ca alloy at high temperatures followed the parabolic-line law or the ubic-line law.X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis indicated that the oxide film on the surface of Mg-3.5Y-0.79Ca and Mg-2.5Ca alloys exhibited a duplex structure.which agreed with the results of thermodynamic analysis.By comparison,the ignition-proof effect of the combination addition of Y and Ca was better than that of the single addition of Ca.

  11. Steel billet reheat simulation with growth of oxide layer and investigation on zone temperature sensitivity

    International Nuclear Information System (INIS)

    Dubey, Satish Kumar; Srinivasan, P.

    2014-01-01

    This paper presents a three-dimensional heat conduction numerical model and simulation of steel billet reheating in a reheat furnace. The model considers the growth of oxide scale on the billet surfaces. Control-volume approach and implicit scheme of finite difference method are used to discretize the transient heat conduction equation. The model is validated with analytical results subject to limited conditions. Simulations are carried out for predictions of three-dimensional temperature filed in the billet and oxide scale growth on the billet surfaces. The model predictions are in agreement with expected trends. It was found that the effect of oxide scale on billet heating is considerable. In order to investigate the effect of zone temperatures on the responses, a parametric sensitivity subject to six responses of interest are carried out using analysis of mean approach. The simulation approach and parametric study presented will be useful and applicable to the steel industry.

  12. The oxidation resistance and ignition temperature of AZ31 magnesium alloy with additions of La2O3 and La

    International Nuclear Information System (INIS)

    Zhao, Shizhe; Zhou, Hong; Zhou, Ti; Zhang, Zhihui; Lin, Pengyu; Ren, Luquan

    2013-01-01

    Highlights: ► Using lanthanum and lanthanum oxide (La 2 O 3 ) can improve oxidation resistance of magnesium alloy. ► La 2 O 3 is as effective as La in affecting both alloy microstructure and oxidation resistance. ► The optimum La concentration in alloy is ∼0.7 wt.%. ► We analyzed the oxidation kinetics of AZ31 alloy with both additions. - Abstract: We investigate the oxidation resistance of AZ31 magnesium alloy with additions of La and La oxide (La 2 O 3 ). The contributor is the practical La content in alloy. Both La and La 2 O 3 are effective in improving the oxidation resistance of Mg alloys. The samples with La content of ∼ 0.7 wt.% possess the best resistance to oxidation of all. Oxide scale, ignition temperature and oxidation kinetics are analyzed. However, higher La content is detrimental to the oxidation resistance.

  13. Low temperature incineration of mixed wastes using bulk metal oxide catalysts

    International Nuclear Information System (INIS)

    Gordon, M.J.; Gaur, S.; Kelkar, S.; Baldwin, R.M.

    1996-01-01

    Volume reduction of low-level mixed wastes from former nuclear weapons facilities is a significant environmental problem. Processing of these materials presents unique scientific and engineering problems due to the presence of minute quantities of radionuclides which must be contained and concentrated for later safe disposal. Low-temperature catalytic incineration is one option that has been utilized at the Rocky Flats facility for this purpose. This paper presents results of research regarding evaluation of bulk metal oxides as catalysts for low-temperature incineration of carbonaceous residues which are typical by-products of fluidized bed combustion of mixed wastes under oxygen-lean conditions. A series of 14 metal oxides were screened in a thermogravimetric analyzer, using on-line mass spectrometry for speciation of reaction product gases. Catalyst evaluation criteria focused on the thermal-redox activity of the metals using both carbon black and PVC char as surrogate waste materials. Results indicated that metal oxides which were P-type semiconductor materials were suitable as catalysts for this application. Oxides of cobalt, molybdenum, vanadium, and manganese were found to be particularly stable and active catalysts under conditions specific to this process (T<650C, low oxygen partial pressures). Bench-scale evaluation of these metal oxides with respect to stability to chlorine (HCl) attack was carried out at 550C using a TG/MS system. Cobalt oxide was found to be resistant to metal loss in a HCl/He gaseous environment while metal loss from Mo, Mn, and V-based catalysts was moderate to severe. XRD and SEM/EDX analysis of spent Co catalysts indicated the formation of non-stoichiometric cobalt chlorides. Regeneration of chlorinated cobalt was found to successfully restore the low-temperature combustion activity to that of the fresh metal oxide

  14. Rapidly reversible redox transformation in nanophase manganese oxides at room temperature triggered by changes in hydration.

    Science.gov (United States)

    Birkner, Nancy; Navrotsky, Alexandra

    2014-04-29

    Chemisorption of water onto anhydrous nanophase manganese oxide surfaces promotes rapidly reversible redox phase changes as confirmed by calorimetry, X-ray diffraction, and titration for manganese average oxidation state. Surface reduction of bixbyite (Mn2O3) to hausmannite (Mn3O4) occurs in nanoparticles under conditions where no such reactions are seen or expected on grounds of bulk thermodynamics in coarse-grained materials. Additionally, transformation does not occur on nanosurfaces passivated by at least 2% coverage of what is likely an amorphous manganese oxide layer. The transformation is due to thermodynamic control arising from differences in surface energies of the two phases (Mn2O3 and Mn3O4) under wet and dry conditions. Such reversible and rapid transformation near room temperature may affect the behavior of manganese oxides in technological applications and in geologic and environmental settings.

  15. Raman and XPS characterization of vanadium oxide thin films with temperature

    Energy Technology Data Exchange (ETDEWEB)

    Ureña-Begara, Ferran, E-mail: ferran.urena@uclouvain.be [Université catholique de Louvain, Institute of Information and Communication Technologies, Electronics and Applied Mathematics (ICTEAM), Louvain-la-Neuve (Belgium); Crunteanu, Aurelian [XLIM Research Institute, UMR 7252, CNRS/Université de Limoges, Limoges (France); Raskin, Jean-Pierre [Université catholique de Louvain, Institute of Information and Communication Technologies, Electronics and Applied Mathematics (ICTEAM), Louvain-la-Neuve (Belgium)

    2017-05-01

    Highlights: • Comprehensive study of the oxidation of VO{sub 2} thin films from R.T. up to 550 °C. • Phase changes and mixed-valence vanadium oxides formed during the oxidation process. • Reported Raman and XPS signatures for each vanadium oxide. • Monitoring of the current and resistance evolution at the surface of the films. • Oxidation model describing the evolution of the vanadium oxides and phase changes. - Abstract: The oxidation mechanisms and the numerous phase transitions undergone by VO{sub 2} thin films deposited on SiO{sub 2}/Si and Al{sub 2}O{sub 3} substrates when heated from room temperature (R.T.) up to 550 °C in air are investigated by Raman and X-ray photoelectron spectroscopy. The results show that the films undergo several intermediate phase transitions between the initial VO{sub 2} monoclinic phase at R.T. and the final V{sub 2}O{sub 5} phase at 550 °C. The information about these intermediate phase transitions is scarce and their identification is important since they are often found during the synthesis of vanadium dioxide films. Significant changes in the film conductivity have also been observed to occur associated to the phase transitions. In this work, current and resistance measurements performed on the surface of the films are implemented in parallel with the Raman measurements to correlate the different phases with the conductivity of the films. A model to explain the oxidation mechanisms and phenomena occurring during the oxidation of the films is proposed. Peak frequencies, full-width half-maxima, binding energies and oxidation states from the Raman and X-ray photoelectron spectroscopy experiments are reported and analyzed for all the phases encountered in VO{sub 2} films prepared on SiO{sub 2}/Si and Al{sub 2}O{sub 3} substrates.

  16. Green synthesis of Ni-Nb oxide catalysts for low-temperature oxidative dehydrogenation of ethane.

    Science.gov (United States)

    Zhu, Haibo; Rosenfeld, Devon C; Anjum, Dalaver H; Caps, Valérie; Basset, Jean-Marie

    2015-04-13

    The straightforward solid-state grinding of a mixture of Ni nitrate and Nb oxalate crystals led to, after mild calcination (Tethane to ethylene at a relatively low temperature (Tethane. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. High temperature oxidation and electrochemical studies on novel co-base superalloys

    Energy Technology Data Exchange (ETDEWEB)

    Klein, Leonhard

    2013-02-27

    Isothermal oxidation in air was carried out on novel γ'-strengthened Cobalt-base superalloys of the system Co-Al-W-B. After fast initial oxide formation, a multi-layered structure establishes, consisting of an outer cobalt oxide layer, a middle spinel-containing layer, and an inner Al{sub 2}O{sub 3}-rich region. Ion diffusion in outward direction is hindered by the development of Al{sub 2}O{sub 3}, that can be either present as a continuous and protective layer or as a discontinuous Al{sub 2}O{sub 3}-rich area without comparable protective effect. Furthermore, high temperature oxidation leads to phase transformation (from γ/γ' into γ/Co{sub 3}W) at the alloy/oxide layer interface due to aluminium depletion. Pure cobalt and ternary Co-Al-W alloys exhibit parabolic oxide growth due to the lack or insufficient amounts of protective oxides, whereas quaternary Co-Al-W-B alloys possess sub-parabolic oxidation behaviour (at 900 C). At lower temperatures (800 C), even a blockage of further oxidation can be observed. High amounts of B (0.12 at%) significantly improve oxidation resistance mainly due to its beneficial effect on inner Al{sub 2}O{sub 3}-formation at the alloy/oxide interface. Furthermore, B prevents decohesion of high temperature scales due to the formation of B-rich phases (presumably tungsten borides) in the middle oxide layer. Appropriate amounts of chromium (8 at%) as additional alloying element to Co-Al-W-B alloys lead to the formation of an inner duplex layer composed of protective Cr{sub 2}O{sub 3} and Al{sub 2}O{sub 3} phases. In this respect, chromium also benefits selective oxidation of aluminium, which results in higher Al{sub 2}O{sub 3}-contents compared to chromium-free alloys. Major drawbacks of chromium additions are, on the one hand, the formation of volatile chromium-containing species at temperatures exceeding 1000 C and on the other hand, the instability of the γ/γ'-microstructure. Titanium and silicon additions lead to

  18. Behaviour of aqueous sulfamethizole solution and temperature effects in cold plasma oxidation treatment.

    Science.gov (United States)

    Sokolov, Alexander; Louhi-Kultanen, Marjatta

    2018-06-07

    The increase in volume and variety of pharmaceuticals found in natural water bodies has become an increasingly serious environmental problem. The implementation of cold plasma technology, specifically gas-phase pulsed corona discharge (PCD), for sulfamethizole abatement was studied in the present work. It was observed that sulfamethizole is easily oxidized by PCD. The flow rate and pH of the solution have no significant effect on the oxidation. Treatment at low pulse repetition frequency is preferable from the energy efficiency point of view but is more time-consuming. The maximum energy efficiency was around 120 g/kWh at half-life and around 50 g/kWh at the end of the treatment. Increasing the solution temperature from room temperature to 50 °C led to a significant reaction retardation of the process and decrease in energy efficiency. The pseudo-first order reaction rate constant (k 1 ) grows with increase in pulse repetition frequency and does not depend on pH. By contrast, decreasing frequency leads to a reduction of the second order reaction rate constant (k 2 ). At elevated temperature of 50 °C, the k 1 , k 2 values decrease 2 and 2.9 times at 50 pps and 500 pps respectively. Lower temperature of 10 °C had no effect on oxidation efficiency compared with room temperature.

  19. Structural and dielectric characterization of sputtered Tantalum Titanium Oxide thin films for high temperature capacitor applications

    Energy Technology Data Exchange (ETDEWEB)

    Rouahi, A., E-mail: rouahi_ahlem@yahoo.fr [Univ. Grenoble Alpes, G2Elab, F-38000 (France); Laboratoire Matériaux Organisation et Propriétés (LMOP), Université de Tunis El Manar, 2092 Tunis (Tunisia); Challali, F. [Laboratoire des Sciences des Procédés et des Matériaux (LSPM)-CNRS-UPR3407, Université Paris13, 99 Avenue Jean-Baptiste Clément, 93430, Villetaneuse (France); Dakhlaoui, I. [Laboratoire Matériaux Organisation et Propriétés (LMOP), Université de Tunis El Manar, 2092 Tunis (Tunisia); Vallée, C. [CNRS, LTM, CEA-LETI, F-38000 Grenoble (France); Salimy, S. [Institut des Matériaux Jean Rouxel (IMN) UMR CNRS 6502, Université de Nantes, 2, rue de la Houssinière, B.P. 32229, 44322, Nantes, Cedex 3 (France); Jomni, F.; Yangui, B. [Laboratoire Matériaux Organisation et Propriétés (LMOP), Université de Tunis El Manar, 2092 Tunis (Tunisia); Besland, M.P.; Goullet, A. [Institut des Matériaux Jean Rouxel (IMN) UMR CNRS 6502, Université de Nantes, 2, rue de la Houssinière, B.P. 32229, 44322, Nantes, Cedex 3 (France); Sylvestre, A. [Univ. Grenoble Alpes, G2Elab, F-38000 (France)

    2016-05-01

    In this study, the dielectric properties of metal-oxide-metal capacitors based on Tantalum Titanium Oxide (TiTaO) thin films deposited by reactive magnetron sputtering on aluminum bottom electrode are investigated. The structure of the films was characterized by Atomic Force Microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The dielectric properties of TiTaO thin films were studied by complex impedance spectroscopy over a wide frequency range (10{sup -2} - to 10{sup 5} Hz) and temperatures in -50 °C to 325 °C range. The contributions of different phases, phases’ boundaries and conductivity effect were highlighted by Cole – Cole diagram (ε” versus ε’). Two relaxation processes have been identified in the electric modulus plot. A first relaxation process appears at low temperature with activation energy of 0.37 eV and it is related to the motion of Ti{sup 4+} (Skanavi’s model). A second relaxation process at high temperature is related to Maxwell-Wagner-Sillars relaxation with activation energy of 0.41 eV. - Highlights: • Titanium Tantalum Oxide thin films are grown on Aluminum substrate. • The existence of phases was confirmed by X-ray photoelectron spectroscopy. • Conductivity effect appears in Cole-Cole plot. • At low temperatures, a relaxation phenomenon obeys to Skanavi’s model. • Maxwell-Wagner-Sillars polarization is processed at high temperatures.

  20. High-temperature Raman spectroscopy of solid oxide fuel cell materials and processes.

    Science.gov (United States)

    Pomfret, Michael B; Owrutsky, Jeffrey C; Walker, Robert A

    2006-09-07

    Chemical and material processes occurring in high temperature environments are difficult to quantify due to a lack of experimental methods that can probe directly the species present. In this letter, Raman spectroscopy is shown to be capable of identifying in-situ and noninvasively changes in material properties as well as the formation and disappearance of molecular species on surfaces at temperatures of 715 degrees C. The material, yttria-stabilized zirconia or YSZ, and the molecular species, Ni/NiO and nanocrystalline graphite, factor prominently in the chemistry of solid oxide fuel cells (SOFCs). Experiments demonstrate the ability of Raman spectroscopy to follow reversible oxidation/reduction kinetics of Ni/NiO as well as the rate of carbon disappearance when graphite, formed in-situ, is exposed to a weakly oxidizing atmosphere. In addition, the Raman active phonon mode of YSZ shows a temperature dependent shift that correlates closely with the expansion of the lattice parameter, thus providing a convenient internal diagnostic for identifying thermal gradients in high temperature systems. These findings provide direct insight into processes likely to occur in operational SOFCs and motivate the use of in-situ Raman spectroscopy to follow chemical processes in these high-temperature, electrochemically active environments.

  1. The effects of annealing temperature on the permittivity and electromagnetic attenuation performance of reduced graphene oxide

    Science.gov (United States)

    Wu, Fan; Zeng, Qiao; Xia, Yilu; Sun, Mengxiao; Xie, Aming

    2018-05-01

    Reduced graphene oxide (RGO) has been prepared through the thermal reduction method with different annealing temperatures to explore the effects of temperature on the permittivity and electromagnetic attenuation performance. The real and imaginary parts of permittivity increase along with the decrease in the oxygen functional group and the increase in the filler loading ratio. A composite only loaded with 1 wt. % of RGO can possess an effective electromagnetic absorption bandwidth of 7.60 GHz, when graphene oxide was reduced under 300 °C for 2 h. With the annealing temperature increased to 700 °C and the well reduced RGO loaded 7 wt. % in the composite, the electromagnetic interference shielding efficiency can get higher than 35 dB from 2 to 18 GHz. This study shows that controlling the oxygen functional groups on the RGO surface can also obtain an ideal electromagnetic attenuation performance without any other decorated nanomaterials.

  2. Oxidative Stress at High Temperatures in Lactococcus lactis Due to an Insufficient Supply of Riboflavin

    DEFF Research Database (Denmark)

    Chen, Jun; Shen, Jing; Solem, Christian

    2013-01-01

    Lactococcus lactis MG1363 was found to be unable to grow at temperatures above 37°C in a defined medium without riboflavin, and the cause was identified to be dissolved oxygen introduced during preparation of the medium. At 30°C, growth was unaffected by dissolved oxygen and oxygen was consumed...... riboflavin to the medium, it was possible to improve growth and oxygen consumption at 37°C, and this also normalized the [ATP]-to-[ADP] ratio. A codon-optimized redox-sensitive green fluorescent protein (GFP) was introduced into L. lactis and revealed a more oxidized cytoplasm at 37°C than at 30°C....... These results indicate that L. lactis suffers from heat-induced oxidative stress at increased temperatures. A decrease in intracellular flavin adenine dinucleotide (FAD), which is derived from riboflavin, was observed with increasing growth temperature, but the presence of riboflavin made the decrease smaller...

  3. Correlation between Low Temperature Adaptation and Oxidative Stress in Saccharomyces cerevisiae

    Directory of Open Access Journals (Sweden)

    Estéfani García-Rios

    2016-08-01

    Full Text Available Many factors, such as must composition, juice clarification, fermentation temperature or inoculated yeast strain, strongly affect the alcoholic fermentation and aromatic profile of wine. As fermentation temperature is effectively controlled by the wine industry, low-temperature fermentation (10-15 ºC is becoming more prevalent in order to produce white and rosé wines with more pronounced aromatic profiles. Elucidating the response to cold in Saccharomyces cerevisiae is of paramount importance for the selection or genetic improvement of wine strains. Previous research has shown the strong implication of oxidative stress response in adaptation to low temperature during the fermentation process. Here we aimed first to quantify the correlation between recovery after shock with different oxidants and cold, and then to detect the key genes involved in cold adaptation that belong to sulfur assimilation, peroxiredoxins, glutathione-glutaredoxins and thioredoxins pathways. To do so, we analyzed the growth of knockouts from the EUROSCARF collection S. cerevisiae BY4743 strain at low and optimal temperatures. The growth rate of these knockouts, compared with the control, enabled us to identify the genes involved, which were also deleted and validated as key genes in the background of two commercial wine strains with a divergent phenotype in their low-temperature growth. We identified three genes, AHP1, MUP1 and URM1, whose deletion strongly impaired low-temperature growth.

  4. Role of oxides and porosity on high temperature oxidation of liquid fuelled HVOF thermal sprayed Ni50Cr coatings

    OpenAIRE

    Song, B.; Bai, M.; Voisey, K.T.; Hussain, Tanvir

    2017-01-01

    High chromium content in Ni50Cr thermally sprayed coatings can generate a dense and protective scale at the surface of coating. Thus, the Ni50Cr coating is widely used in high temperature oxidation and corrosion applications. A commercially available gas atomized Ni50Cr powder was sprayed onto a power plant steel (ASME P92) using a liquid fuelled high velocity oxy-fuel (HVOF) thermal spray with three processing parameters in this study. Microstructure of as-sprayed coatings was examined using...

  5. The surface oxide as a source of oxygen on Rh(1 1 1)

    Energy Technology Data Exchange (ETDEWEB)

    Lundgren, E. [Department of Synchrotron Radiation Research, Institute of Physics, Lund University, Box 118, S-221 00 Lund (Sweden)]. E-mail: edvin.lundgren@sljus.lu.se; Gustafson, J. [Department of Synchrotron Radiation Research, Institute of Physics, Lund University, Box 118, S-221 00 Lund (Sweden); Resta, A. [Department of Synchrotron Radiation Research, Institute of Physics, Lund University, Box 118, S-221 00 Lund (Sweden); Weissenrieder, J. [Department of Synchrotron Radiation Research, Institute of Physics, Lund University, Box 118, S-221 00 Lund (Sweden); Mikkelsen, A. [Department of Synchrotron Radiation Research, Institute of Physics, Lund University, Box 118, S-221 00 Lund (Sweden); Andersen, J.N. [Department of Synchrotron Radiation Research, Institute of Physics, Lund University, Box 118, S-221 00 Lund (Sweden); Koehler, L. [Institut fuer Materialphysik and Centre for Computational Materials Science, Universitaet Wien, A-1090 Vienna (Austria); Kresse, G. [Institut fuer Materialphysik and Centre for Computational Materials Science, Universitaet Wien, A-1090 Vienna (Austria); Klikovits, J. [Institut fuer Allgemeine Physik, Technische Universitaet Wien, A-1040 Vienna (Austria); Biederman, A. [Institut fuer Allgemeine Physik, Technische Universitaet Wien, A-1040 Vienna (Austria); Schmid, M. [Institut fuer Allgemeine Physik, Technische Universitaet Wien, A-1040 Vienna (Austria); Varga, P. [Institut fuer Allgemeine Physik, Technische Universitaet Wien, A-1040 Vienna (Austria)

    2005-06-15

    The reduction of a thin surface oxide on the Rh(1 1 1) surface by CO is studied in situ by photoemission spectroscopy, scanning tunneling microscopy, and density functional theory. CO molecules are found not to adsorb on the surface oxide at a sample temperature of 100 K, in contrast to on the clean and chemisorbed oxygen covered surface. Despite this behavior, the surface oxide may still be reduced by CO, albeit in a significantly different fashion as compared to the reduction of a phase containing only chemisorbed on surface oxygen. The experimental observations combined with theoretical considerations concerning the stability of the surface oxide, result in a model of the reduction process at these pressures suggesting that the surface oxide behaves as a source of oxygen for the CO-oxidation reaction.

  6. Effects of copper, hypoxia and acute temperature shifts on mitochondrial oxidation in rainbow trout (Oncorhynchus mykiss) acclimated to warm temperature

    International Nuclear Information System (INIS)

    Sappal, Ravinder; Fast, Mark; Stevens, Don; Kibenge, Fred; Siah, Ahmed; Kamunde, Collins

    2015-01-01

    Highlights: • Warm acclimation reduced the electron transport system (ETS) efficiency. • Warm acclimation altered the effects of acute temperature shift, hypoxia and Cu on ETS. • Warm acclimation increased thermal sensitivity of state 3 and reduced that of state 4. • Cu stimulated while hypoxia inhibited ETS respiratory activity. • Interactions of Cu and hypoxia on the ETS and plasma metabolites were antagonistic. - Abstract: Temperature fluctuations, hypoxia and metals pollution frequently occur simultaneously or sequentially in aquatic systems and their interactions may confound interpretation of their biological impacts. With a focus on energy homeostasis, the present study examined how warm acclimation influences the responses and interactions of acute temperature shift, hypoxia and copper (Cu) exposure in fish. Rainbow trout (Oncorhynchus mykiss) were acclimated to cold (11 °C; control) and warm (20 °C) temperature for 3 weeks followed by exposure to environmentally realistic levels of Cu and hypoxia for 24 h. Subsequently, mitochondrial electron transport system (ETS) respiratory activity supported by complexes I–IV (CI–IV), plasma metabolites and condition indices were measured. Warm acclimation reduced fish condition, induced aerobic metabolism and altered the responses of fish to acute temperature shift, hypoxia and Cu. Whereas warm acclimation decelerated the ETS and increased the sensitivity of maximal oxidation rates of the proximal (CI and II) complexes to acute temperature shift, it reduced the thermal sensitivity of state 4 (proton leak). Effects of Cu with and without hypoxia were variable depending on the acclimation status and functional index. Notably, Cu stimulated respiratory activity in the proximal ETS segments, while hypoxia was mostly inhibitory and minimized the stimulatory effect of Cu. The effects of Cu and hypoxia were modified by temperature and showed reciprocal antagonistic interaction on the ETS and plasma

  7. Effects of copper, hypoxia and acute temperature shifts on mitochondrial oxidation in rainbow trout (Oncorhynchus mykiss) acclimated to warm temperature

    Energy Technology Data Exchange (ETDEWEB)

    Sappal, Ravinder [Department of Pathology and Microbiology, Atlantic Veterinary College, University of Prince Edward Island, Charlottetown, Prince Edward Island C1A 4P3 (Canada); Department of Biomedical Sciences, Atlantic Veterinary College, University of Prince Edward Island, Charlottetown, Prince Edward Island C1A 4P3 (Canada); Fast, Mark [Department of Pathology and Microbiology, Atlantic Veterinary College, University of Prince Edward Island, Charlottetown, Prince Edward Island C1A 4P3 (Canada); Stevens, Don [Department of Biomedical Sciences, Atlantic Veterinary College, University of Prince Edward Island, Charlottetown, Prince Edward Island C1A 4P3 (Canada); Kibenge, Fred [Department of Pathology and Microbiology, Atlantic Veterinary College, University of Prince Edward Island, Charlottetown, Prince Edward Island C1A 4P3 (Canada); Siah, Ahmed [British Columbia Centre for Aquatic Health Sciences, 871A Island Highway, Campbell River, British Columbia V9W 2C2 (Canada); Kamunde, Collins, E-mail: ckamunde@upei.ca [Department of Biomedical Sciences, Atlantic Veterinary College, University of Prince Edward Island, Charlottetown, Prince Edward Island C1A 4P3 (Canada)

    2015-12-15

    Highlights: • Warm acclimation reduced the electron transport system (ETS) efficiency. • Warm acclimation altered the effects of acute temperature shift, hypoxia and Cu on ETS. • Warm acclimation increased thermal sensitivity of state 3 and reduced that of state 4. • Cu stimulated while hypoxia inhibited ETS respiratory activity. • Interactions of Cu and hypoxia on the ETS and plasma metabolites were antagonistic. - Abstract: Temperature fluctuations, hypoxia and metals pollution frequently occur simultaneously or sequentially in aquatic systems and their interactions may confound interpretation of their biological impacts. With a focus on energy homeostasis, the present study examined how warm acclimation influences the responses and interactions of acute temperature shift, hypoxia and copper (Cu) exposure in fish. Rainbow trout (Oncorhynchus mykiss) were acclimated to cold (11 °C; control) and warm (20 °C) temperature for 3 weeks followed by exposure to environmentally realistic levels of Cu and hypoxia for 24 h. Subsequently, mitochondrial electron transport system (ETS) respiratory activity supported by complexes I–IV (CI–IV), plasma metabolites and condition indices were measured. Warm acclimation reduced fish condition, induced aerobic metabolism and altered the responses of fish to acute temperature shift, hypoxia and Cu. Whereas warm acclimation decelerated the ETS and increased the sensitivity of maximal oxidation rates of the proximal (CI and II) complexes to acute temperature shift, it reduced the thermal sensitivity of state 4 (proton leak). Effects of Cu with and without hypoxia were variable depending on the acclimation status and functional index. Notably, Cu stimulated respiratory activity in the proximal ETS segments, while hypoxia was mostly inhibitory and minimized the stimulatory effect of Cu. The effects of Cu and hypoxia were modified by temperature and showed reciprocal antagonistic interaction on the ETS and plasma

  8. Load-partitioning in an oxide dispersion-strengthened 310 steel at elevated temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Miao, Yinbin; Mo, Kun; Zhou, Zhangjian; Liu, Xiang; Lan, Kuan-Che; Zhang, Guangming; Park, Jun-Sang; Almer, Jonathan; Stubbins, James F.

    2016-12-01

    Here the high temperature tensile performance of an oxide dispersion-strengthened (ODS) 310 steel is reported upon. The microstructure of the steel was examined through both transmission electron microscopy (TEM) and synchrotron scattering. In situ synchrotron tensile investigation was performed at a variety of temperatures, from room temperature up to 800°C. Pyrochlore structure yttrium titanate and sodium chloride structure titanium nitride phases were identified in the steel along with an austenite matrix and marginal residual α’-martensite. The inclusion phases strengthen the steel by taking extra load through particle-dislocation interaction during plastic deformation or dislocation creep procedures. As temperature rises, the load partitioning effect of conventional precipitate phases starts to diminish, whereas those ultra-fine oxygen-enriched nanoparticles continue to bear a considerable amount of extra load. Introduction of oxygen-enriched nanoparticles in austenitic steel proves to improve the high temperature performance, making austenitic ODS steels promising for advanced nuclear applications.

  9. Role of high-temperature creep stress in thermally grown oxide growth of thermal barrier coatings

    Energy Technology Data Exchange (ETDEWEB)

    Ogawa, K.; Nakao, Y.; Seo, D.; Miura, H.; Shoji, T. [Tohoku Univ., Sendai (Japan)

    2008-07-01

    Thermally grown oxide (TGO) grows at the top / bond coating interface of the thermal barrier coating (TBC) in service. It is supposed that the failures of the TBC occur due to thermal stress and the decrease of adhesive strength caused by the TGO growth. Recently, large local stress has been found to change both the diffusion constant of oxygen through an existing oxide and the rate of chemical reaction at the oxide / oxidized material interface. Since high thermal stress occurs in the TBC, the volume expansion of the newly grown oxide, and centrifugal force, the growth rate of the TGO may change depending on not only temperature but also the stress. The aim of this study is to make clear the influence of stress on the growth rate of the TGO quantitatively. As a result, the thickness of the TGO clearly increases with increase of the amplitude of the applied stress and temperature. The increase rate of the TGO thickness is approximately 23% when the applied stress is increased from 0 to 205 MPa at 900 C, and approximately 29% when the stress is increased from 0 to 150 MPa at 950 C. (orig.)

  10. A method of eliminating the surface defect in low-temperature oxidation powder added UO2 pellet

    International Nuclear Information System (INIS)

    Yoo, H. S.; Lee, S. J.; Kim, J. I.; Jeon, K. R.; Kim, J. W.

    2002-01-01

    A study on methods to eliminate surface defect shown in low-temperature oxidation powder added UO 2 pellet has been performed. Powders oxidized at 350 .deg. C for 4 hrs were prepared and mixed with UO 2 powder after crushing them. After being sintered, surfaces of the pellet were inspected both visually and optically. A large number of defects were observed on the surface of the specimens in which low-temperature oxidation powders were directly mixed or master mixed with UO 2 powder while both specimens produced from mixed powders including milled oxidation powders and powders that were milled totally after mixing had clean surfaces. However, optical examination showed considerably large defected pores in the milled oxidation powder added pellet and it was confirmed that the inner defects can be eliminated completely only when milling the entire mixture on UO 2 and low-temperature oxidation powder, but not by crushing only oxidation powder

  11. Improving superconducting properties of YBCO high temperature superconductor by Graphene Oxide doping

    Energy Technology Data Exchange (ETDEWEB)

    Dadras, S., E-mail: dadras@alzahra.ac.ir; Dehghani, S.; Davoudiniya, M.; Falahati, S.

    2017-06-01

    In this research, we report the synthesis and characterization of YBa{sub 2}Cu{sub 3}O{sub 7-δ} (YBCO) high temperature superconductor prepared by sol-gel method and doped with Graphene Oxide (GO) in different weight percentages, 0, 0.1, 0.7 and 1 % wt. The x-ray diffraction (XRD) analysis confirms the formation of orthorhombic phase of superconductivity for all the prepared samples. We found that GO doping reduces the crystalline size of the samples. We evaluated the effects of GO doping on the normal state resistivity (ρ), superconducting transition temperature (T{sub c}) and critical current density (J{sub c}). The results show that the GO doping has a positive effect on these properties. Also, the highest J{sub c} is obtained for the 0.7 %wt GO doped YBCO compound that its critical current density is about 15 times more than the J{sub c} of pure one in 0.4 T magnetic field. The scanning electron microscope (SEM) analysis shows that there are better connections between the grains of GO doped samples. - Highlights: • Graphene Oxide doping increased the YBCO critical current density. • Graphene Oxide creates a better connection between the YBCO grains. • The normal resistivity of samples were decreased by GO doping to YBCO compounds. • Graphene Oxide doping has a positive effect on the critical transition temperature.

  12. Bipolar resistive switching in room temperature grown disordered vanadium oxide thin-film devices

    Science.gov (United States)

    Wong, Franklin J.; Sriram, Tirunelveli S.; Smith, Brian R.; Ramanathan, Shriram

    2013-09-01

    We demonstrate bipolar switching with high OFF/ON resistance ratios (>104) in Pt/vanadium oxide/Cu structures deposited entirely at room temperature. The SET (RESET) process occurs when negative (positive) bias is applied to the top Cu electrode. The vanadium oxide (VOx) films are amorphous and close to the vanadium pentoxide stoichiometry. We also investigated Cu/VOx/W structures, reversing the position of the Cu electrode, and found the same polarity dependence with respect to the top and bottom electrodes, which suggests that the bipolar nature is linked to the VOx layer itself. Bipolar switching can be observed at 100 °C, indicating that it not due to a temperature-induced metal-insulator transition of a vanadium dioxide second phase. We discuss how ionic drift can lead to the bipolar electrical behavior of our junctions, similar to those observed in devices based on several other defective oxides. Such low-temperature processed oxide switches could be of relevance to back-end or package integration processing schemes.

  13. Investigation of a new methodology in high temperature oxidation application to commercial austenitic steels

    Energy Technology Data Exchange (ETDEWEB)

    Vangeli, P.; Ivarsson, B. [Avesta Sheffield, R and D (Sweden)

    2001-07-01

    Avesta Sheffield R and D has evaluated a scaling temperature for heat resistant steels from laboratory gravimetric measurements of cyclic exposures. In this paper, this old method is described. A new methodology, based on the results of isothermal and cyclic tests, is proposed and discussed. It includes isothermal and cyclic oxidation kinetics of different commercial austenitic steels. Oxidation of Avesta Sheffield 153MA, 253MA and 353MA and standard commercial heat resistant steels 309S, 310S and A800 have been investigated under isothermal and cyclic conditions, in air, in the temperature range 800-1200 C. For all alloys, oxidation rates obey a parabolic law below a critical temperature. The activation energies have been calculated. Kinetics of the cyclic tests show that a critical mass change corresponding to a critical thickness of the oxide scale is responsible for the spallation start. This thickness depends on the composition of the alloys, and is very much increased by alloying minor elements like Ce. (orig.)

  14. High temperature oxidation behavior of austenitic stainless steel AISI 304 in steam of nanofluids contain nanoparticle ZrO2

    International Nuclear Information System (INIS)

    Prajitno, Djoko Hadi; Syarif, Dani Gustaman

    2014-01-01

    The objective of this study is to evaluate high temperature oxidation behavior of austenitic stainless steel SS 304 in steam of nanofluids contain nanoparticle ZrO 2 . The oxidation was performed at high temperatures ranging from 600 to 800°C. The oxidation time was 60 minutes. After oxidation the surface of the samples was analyzed by different methods including, optical microscope, scanning electron microscope (SEM) and X-ray diffraction (XRD). X-ray diffraction examination show that the oxide scale formed during oxidation of stainless steel AISI 304 alloys is dominated by iron oxide, Fe 2 O 3 . Minor element such as Cr 2 O 3 is also appeared in the diffraction pattern. Characterization by optical microscope showed that cross section microstructure of stainless steel changed after oxidized with the oxide scale on the surface stainless steels. SEM and x-ray diffraction examination show that the oxide of ZrO 2 appeared on the surface of stainless steel. Kinetic rate of oxidation of austenite stainless steel AISI 304 showed that increasing oxidation temperature and time will increase oxidation rate

  15. High temperature oxidation behavior of austenitic stainless steel AISI 304 in steam of nanofluids contain nanoparticle ZrO2

    Energy Technology Data Exchange (ETDEWEB)

    Prajitno, Djoko Hadi, E-mail: djokohp@batan.go.id; Syarif, Dani Gustaman, E-mail: djokohp@batan.go.id [Research Center for Nuclear Materials and Radiometry, Jl. Tamansari 71, Bandung 40132 (Indonesia)

    2014-03-24

    The objective of this study is to evaluate high temperature oxidation behavior of austenitic stainless steel SS 304 in steam of nanofluids contain nanoparticle ZrO{sub 2}. The oxidation was performed at high temperatures ranging from 600 to 800°C. The oxidation time was 60 minutes. After oxidation the surface of the samples was analyzed by different methods including, optical microscope, scanning electron microscope (SEM) and X-ray diffraction (XRD). X-ray diffraction examination show that the oxide scale formed during oxidation of stainless steel AISI 304 alloys is dominated by iron oxide, Fe{sub 2}O{sub 3}. Minor element such as Cr{sub 2}O{sub 3} is also appeared in the diffraction pattern. Characterization by optical microscope showed that cross section microstructure of stainless steel changed after oxidized with the oxide scale on the surface stainless steels. SEM and x-ray diffraction examination show that the oxide of ZrO{sub 2} appeared on the surface of stainless steel. Kinetic rate of oxidation of austenite stainless steel AISI 304 showed that increasing oxidation temperature and time will increase oxidation rate.

  16. CHALLENGES IN GENERATING HYDROGEN BY HIGH TEMPERATURE ELECTROLYSIS USING SOLID OXIDE CELLS

    Energy Technology Data Exchange (ETDEWEB)

    M. S. Sohal; J. E. O' Brien; C. M. Stoots; M. G. McKellar; J. S. Herring; E. A. Harvego

    2008-03-01

    Idaho National Laboratory’s (INL) high temperature electrolysis research to generate hydrogen using solid oxide electrolysis cells is presented in this paper. The research results reported here have been obtained in a laboratory-scale apparatus. These results and common scale-up issues also indicate that for the technology to be successful in a large industrial setting, several technical, economical, and manufacturing issues have to be resolved. Some of the issues related to solid oxide cells are stack design and performance optimization, identification and evaluation of cell performance degradation parameters and processes, integrity and reliability of the solid oxide electrolysis (SOEC) stacks, life-time prediction and extension of the SOEC stack, and cost reduction and economic manufacturing of the SOEC stacks. Besides the solid oxide cells, balance of the hydrogen generating plant also needs significant development. These issues are process and ohmic heat source needed for maintaining the reaction temperature (~830°C), high temperature heat exchangers and recuperators, equal distribution of the reactants into each cell, system analysis of hydrogen and associated energy generating plant, and cost optimization. An economic analysis of this plant was performed using the standardized H2A Analysis Methodology developed by the Department of Energy (DOE) Hydrogen Program, and using realistic financial and cost estimating assumptions. The results of the economic analysis demonstrated that the HTE hydrogen production plant driven by a high-temperature helium-cooled nuclear power plant can deliver hydrogen at a cost of $3.23/kg of hydrogen assuming an internal rate of return of 10%. These issues need interdisciplinary research effort of federal laboratories, solid oxide cell manufacturers, hydrogen consumers, and other such stakeholders. This paper discusses research and development accomplished by INL on such issues and highlights associated challenges that need to

  17. Identification of the Products of Oxidation of Quercetin by Air Oxygenat Ambient Temperature

    Directory of Open Access Journals (Sweden)

    Viktor A Utsal

    2007-03-01

    Full Text Available Oxidation of quercetin by air oxygen takes place in water and aqueous ethanol solutions under mild conditions, namely in moderately-basic media (pH ∼ 8-10 at ambient temperature and in the absence of any radical initiators, without enzymatic catalysis or irradiation of the reaction media by light. The principal reaction products are typical of other oxidative degradation processes of quercetin, namely 3,4-dihydroxy-benzoic (proto-catechuic and 2,4,6-trihydroxybenzoic (phloroglucinic acids, as well as the decarboxylation product of the latter – 1,3,5-trihydroxybenzene (phloroglucinol. In accordance with the literature data, this process involves the cleavage of the γ-pyrone fragment (ring C of the quercetin molecule by oxygen, with primary formation of 4,6-dihydroxy-2-(3,4-dihydroxybenzoyloxybenzoic acid (depside. However under such mild conditions the accepted mechanism of this reaction (oxidative decarbonylation with formation of carbon monoxide, CO should be reconsidered as preferably an oxidative decarboxylation with formation of carbon dioxide, CO2. Direct head-space analysis of the gaseous components formed during quercetin oxidation in aqueous solution at ambient temperature indicates that the ratio of carbon dioxide/carbon monoxide in the gas phase after acidification of the reaction media is ca. 96:4 %. Oxidation under these mild conditions is typical for other flavonols having OH groups at C3 (e.g., kaempferol, but it is completely suppressed if this hydroxyl group is substituted by a glycoside fragment (as in rutin, or a methyl substituent. An alternative oxidation mechanism involving the direct cleavage of the C2-C3 bond in the diketo-tautomer of quercetin is proposed.

  18. Diffusional aspects of the high-temperature oxidation of protective coatings

    Science.gov (United States)

    Nesbitt, J. A.

    1989-01-01

    The role of diffusional transport associated with the high-temperature oxidation of coatings is examined, with special attention given to the low-pressure plasma spraying MCrAl-type overlay coatings and similar Ni-base alloys which form protective AlO3 scales. The use of diffusional analysis to predict the minimum solute concentration necessary to form and grow a solute oxide scale is illustrated. Modeling procedures designed to simulate the diffusional transport in coatings and substrates are presented to show their use in understanding coating degradation, predicting the protective life of a coating, and evaluating various coating parameters to guide coating development.

  19. Cu/Nitroxyl Catalyzed Aerobic Oxidation of Primary Amines into Nitriles at Room Temperature.

    Science.gov (United States)

    Kim, Jinho; Stahl, Shannon S

    2013-07-05

    An efficient catalytic method has been developed for aerobic oxidation of primary amines to the corresponding nitriles. The reactions proceed at room temperature and employ a catalyst consisting of (4,4'- t Bu 2 bpy)CuI/ABNO (ABNO = 9-azabicyclo[3.3.1]nonan-3-one N -oxyl). The reactions exhibit excellent functional group compatibility and substrate scope, and are effective with benzylic, allylic and aliphatic amines. Preliminary mechanistic studies suggest that aerobic oxidation of the Cu catalyst is the turnover-limiting step of the reaction.

  20. Cu/Nitroxyl Catalyzed Aerobic Oxidation of Primary Amines into Nitriles at Room Temperature

    OpenAIRE

    Kim, Jinho; Stahl, Shannon S.

    2013-01-01

    An efficient catalytic method has been developed for aerobic oxidation of primary amines to the corresponding nitriles. The reactions proceed at room temperature and employ a catalyst consisting of (4,4′-tBu2bpy)CuI/ABNO (ABNO = 9-azabicyclo[3.3.1]nonan-3-one N-oxyl). The reactions exhibit excellent functional group compatibility and substrate scope, and are effective with benzylic, allylic and aliphatic amines. Preliminary mechanistic studies suggest that aerobic oxidation of the Cu catalyst...

  1. Irradiation temperature dependence of production efficiency of lattice defects in some neutron-irradiated oxides

    International Nuclear Information System (INIS)

    Okada, Moritami; Atobe, Kozo; Nakagawa, Masuo

    2004-01-01

    Temperature dependence of production efficiency of irradiation-induced defects in neutron-irradiated oxides has been investigated. Some oxide single crystals, MgO, α-Al 2 O 3 (sapphire) and TiO 2 (rutile), were irradiated at several controlled temperatures, 10, 20, 50, 100, 150 and 200 K, using the low-temperature irradiation facility of Kyoto University Reactor (KUR-LTL), and at ambient temperature (∼370 K) in the same facility. Irradiation temperature dependence of production efficiency of a 1 μm band in TiO 2 differs greatly from that of anion vacancy (F-type centers) in MgO and α-Al 2 O 3 . Results for MgO and α-Al 2 O 3 show steep negative gradients from 10 to 370 K, whereas that for TiO 2 includes a valley between 40 and 60 K and a hump at about 130 K, and then disappear at about 200 K. In MgO and α-Al 2 O 3 , this behavior can be explained by the recombination of Frenkel pairs, which is activated at higher temperature. In TiO 2 , in addition to the recombination mechanism, a covalent bonding property is thought to be exerted strong influence, and it is suggested that a disappearance of the 1 μm band at above 200 K is due to the recombination process of Frenkel pairs which is caused by the irradiation-induced crystallization

  2. Oxidation of mine tailings from Rankin Inlet, Nunavut, at subzero temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Meldrum, J. L.; Jamieson, H. E.; Dyke, L. D.

    2001-10-01

    An experiment was undertaken to determine if encapsulation in permafrost of acid-generating sulphidic tailings from a Ni-Cu mine on the shores of Hudson Bay in Nunavut will maintain the tailings and their saline pore water in a chemically inert state. The experiment involved collection of tailings material and pore water samples three years after burial, followed by long-term thermal monitoring. Tailings were studied at temperatures between +30 degrees C and -10 degrees C. Oxygen consumption was measured directly to determine the effect of low temperatures on oxidation rate. Significant oxidation was observed at +30 degrees C, which was substantially reduced at lower temperatures. At -10 degrees C oxygen consumption was below the detection limit. The highest measured oxygen flux correlated with a temperature increase of one degree C, which is consistent with exothermic sulphide oxidation reactions. The experiment showed that freezing in Rankin Inlet is progressing and tailings will be ice-bonded approximately 15 years after burial. 30 refs., 3 tabs. 6 figs.

  3. Room temperature NO2-sensing properties of porous silicon/tungsten oxide nanorods composite

    International Nuclear Information System (INIS)

    Wei, Yulong; Hu, Ming; Wang, Dengfeng; Zhang, Weiyi; Qin, Yuxiang

    2015-01-01

    Highlights: • Porous silicon/WO 3 nanorods composite is synthesized via hydrothermal method. • The morphology of WO 3 nanorods depends on the amount of oxalic acid (pH value). • The sensor can detect ppb level NO 2 at room temperature. - Abstract: One-dimensional single crystalline WO 3 nanorods have been successfully synthesized onto the porous silicon substrates by a seed-induced hydrothermal method. The controlled morphology of porous silicon/tungsten oxide nanorods composite was obtained by using oxalic acid as an organic inducer. The reaction was carried out at 180 °C for 2 h. The influence of oxalic acid (pH value) on the morphology of porous silicon/tungsten oxide nanorods composite was investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM). The NO 2 -sensing properties of the sensor based on porous silicon/tungsten oxide nanorods composite were investigated at different temperatures ranging from room temperature (∼25 °C) to 300 °C. At room temperature, the sensor behaved as a typical p-type semiconductor and exhibited high gas response, good repeatability and excellent selectivity characteristics toward NO 2 gas due to its high specific surface area, special structure, and large amounts of oxygen vacancies

  4. New insights into the low-temperature oxidation of 2-methylhexane

    KAUST Repository

    Wang, Zhandong

    2016-09-24

    In this work, we studied the low-temperature oxidation of a stoichiometric 2-methylhexane/O2/Ar mixture in a jet-stirred reactor coupled with synchrotron vacuum ultraviolet photoionization molecular-beam mass spectrometry. The initial gas mixture was composed of 2% 2-methyhexane, 22% O2 and 76% Ar and the pressure of the reactor was kept at 780Torr. Low-temperature oxidation intermediates with two to five oxygen atoms were observed. The detection of C7H14O5 and C7H12O4 species suggests that a third O2 addition process occurs in 2-methylhexane low-temperature oxidation. A detailed kinetic model was developed that describes the third O2 addition and subsequent reactions leading to C7H14O5 (keto-dihydroperoxide and dihydroperoxy cyclic ether) and C7H12O4 (diketo-hydroperoxide and keto-hydroperoxy cyclic ether) species. The kinetics of the third O2 addition reactions are discussed and model calculations were performed that reveal that third O2 addition reactions promote 2-methylhexane auto-ignition at low temperatures. © 2016 The Combustion Institute.

  5. Effect of ion irradiation on the optical properties and room temperature oxidation of copper surface

    Energy Technology Data Exchange (ETDEWEB)

    Poperenko, L.V.; Ramadan Shaaban, Essam; Khanh, N.Q.; Stashchuk, V.S.; Vinnichenko, M.V.; Yurgelevich, I.V.; Nosach, D.V.; Lohner, T

    2004-05-01

    Ex situ and in situ spectroellipsometric investigation of room temperature oxidation of ion-implanted copper surface was performed. The ellipsometer is capable to measure simultaneously the ellipsometric parameters {psi} and {delta} at 88 different wavelength values in the range of 280-760 nm within a few minutes in the high precision operation mode using two zone averaging and within a fraction of a second in the one zone operation mode. The native oxide layer formed earlier on the surface of the copper was sputtered off during the aluminum ion implantation. In situ study of the growth of the newly formed native oxide layer on the ion implanted surface was carried out. Ion beam analytical measurements were performed to gain further information on the native oxide layer. The absolute number of the oxygen atoms in the native copper oxide layer was determined. The depth distribution of the implanted aluminum was extracted from Rutherford backscattering spectra. It is found that Al implantation enhanced the oxidation resistance.

  6. Effect of ion irradiation on the optical properties and room temperature oxidation of copper surface

    International Nuclear Information System (INIS)

    Poperenko, L.V.; Ramadan Shaaban, Essam; Khanh, N.Q.; Stashchuk, V.S.; Vinnichenko, M.V.; Yurgelevich, I.V.; Nosach, D.V.; Lohner, T.

    2004-01-01

    Ex situ and in situ spectroellipsometric investigation of room temperature oxidation of ion-implanted copper surface was performed. The ellipsometer is capable to measure simultaneously the ellipsometric parameters Ψ and Δ at 88 different wavelength values in the range of 280-760 nm within a few minutes in the high precision operation mode using two zone averaging and within a fraction of a second in the one zone operation mode. The native oxide layer formed earlier on the surface of the copper was sputtered off during the aluminum ion implantation. In situ study of the growth of the newly formed native oxide layer on the ion implanted surface was carried out. Ion beam analytical measurements were performed to gain further information on the native oxide layer. The absolute number of the oxygen atoms in the native copper oxide layer was determined. The depth distribution of the implanted aluminum was extracted from Rutherford backscattering spectra. It is found that Al implantation enhanced the oxidation resistance

  7. Oxidation of methane on nanoparticulate Au/TiO2 at low temperature: A combined microreactor and DFT study

    DEFF Research Database (Denmark)

    Walther, Guido; Jones, Glenn; Jensen, Søren

    2009-01-01

    Herein we present results from experimental and theoretical studies concerning low temperature oxidation of CH4 over TiO2 supported Au nanoparticles. Our findings suggest that partial oxidation cannot be achieved under these conditions (1 bar, 30–250 °C). In order to understand this further, resu......-calculations investigating the thermodynamics of CH4 oxidation on a stepped Au(2 1 1) surface. Keywords: Gold; Titanium dioxide; Catalysis; Microreactor; Methane; Oxidation; Particle size...

  8. Influence of heat treatment on the high temperature oxidation mechanisms of an Fe-TiCN cermet

    OpenAIRE

    Alvaredo Olmos, Paula; Abajo Clemente, Carolina; Tsipas, Sophia Alexandra; Gordo Odériz, Elena

    2014-01-01

    In this study, the oxidation behaviour of an iron matrix cermet containing 50 % vol. Ti(C,N) was investigated before and after heat treatment by oxidation tests performed in static air at temperatures between 500 °C and 1000 °C. The oxidation mechanism for this type of composite materials was established and it was found that the heat treated material presents lower mass gain than the as-sintered material at the early stages of the oxidation, due to the volatilization of oxides. The oxidation...

  9. The effect of substrate temperature on atomic layer deposited zinc tin oxide

    Energy Technology Data Exchange (ETDEWEB)

    Lindahl, Johan, E-mail: johan.lindahl@angstrom.uu.se; Hägglund, Carl, E-mail: carl.hagglund@angstrom.uu.se; Wätjen, J. Timo, E-mail: timo.watjen@angstrom.uu.se; Edoff, Marika, E-mail: marika.edoff@angstrom.uu.se; Törndahl, Tobias, E-mail: tobias.torndahl@angstrom.uu.se

    2015-07-01

    Zinc tin oxide (ZTO) thin films were deposited on glass substrates by atomic layer deposition (ALD), and the film properties were investigated for varying deposition temperatures in the range of 90 to 180 °C. It was found that the [Sn]/([Sn] + [Zn]) composition is only slightly temperature dependent, while properties such as growth rate, film density, material structure and band gap are more strongly affected. The growth rate dependence on deposition temperature varies with the relative number of zinc or tin containing precursor pulses and it correlates with the growth rate behavior of pure ZnO and SnO{sub x} ALD. In contrast to the pure ZnO phase, the density of the mixed ZTO films is found to depend on the deposition temperature and it increases linearly with about 1 g/cm{sup 3} in total over the investigated range. Characterization by transmission electron microscopy suggests that zinc rich ZTO films contain small (~ 10 nm) ZnO or ZnO(Sn) crystallites embedded in an amorphous matrix, and that these crystallites increase in size with increasing zinc content and deposition temperature. These crystallites are small enough for quantum confinement effects to reduce the optical band gap of the ZTO films as they grow in size with increasing deposition temperature. - Highlights: • Zinc tin oxide thin films were deposited by atomic layer deposition. • The structure and optical properties were studied at different growth temperatures. • The growth temperature had only a small effect on the composition of the films. • Small ZnO or ZnO(Sn) crystallites were observed by TEM in zinc rich ZTO films. • The growth temperature affects the crystallite size, which influences the band gap.

  10. The effect of substrate temperature on atomic layer deposited zinc tin oxide

    International Nuclear Information System (INIS)

    Lindahl, Johan; Hägglund, Carl; Wätjen, J. Timo; Edoff, Marika; Törndahl, Tobias

    2015-01-01

    Zinc tin oxide (ZTO) thin films were deposited on glass substrates by atomic layer deposition (ALD), and the film properties were investigated for varying deposition temperatures in the range of 90 to 180 °C. It was found that the [Sn]/([Sn] + [Zn]) composition is only slightly temperature dependent, while properties such as growth rate, film density, material structure and band gap are more strongly affected. The growth rate dependence on deposition temperature varies with the relative number of zinc or tin containing precursor pulses and it correlates with the growth rate behavior of pure ZnO and SnO x ALD. In contrast to the pure ZnO phase, the density of the mixed ZTO films is found to depend on the deposition temperature and it increases linearly with about 1 g/cm 3 in total over the investigated range. Characterization by transmission electron microscopy suggests that zinc rich ZTO films contain small (~ 10 nm) ZnO or ZnO(Sn) crystallites embedded in an amorphous matrix, and that these crystallites increase in size with increasing zinc content and deposition temperature. These crystallites are small enough for quantum confinement effects to reduce the optical band gap of the ZTO films as they grow in size with increasing deposition temperature. - Highlights: • Zinc tin oxide thin films were deposited by atomic layer deposition. • The structure and optical properties were studied at different growth temperatures. • The growth temperature had only a small effect on the composition of the films. • Small ZnO or ZnO(Sn) crystallites were observed by TEM in zinc rich ZTO films. • The growth temperature affects the crystallite size, which influences the band gap

  11. PHASE CHANGES ON 4H AND 6H SIC AT HIGH TEMPERATURE OXIDATION

    Directory of Open Access Journals (Sweden)

    Jan Setiawan

    2016-10-01

    Full Text Available ABSTRACT PHASE CHANGES ON 4H AND 6H SIC AT HIGH TEMPERATURE OXIDATION. The oxidation on two silicon carbide contain 6H phase and contains 6H and 4H phases has been done.  Silicon carbide is ceramic non-oxide with excellent properties that potentially used in industry.  Silicon carbide is used in nuclear industry as structure material that developed as light water reactor (LWR fuel cladding and as a coating layer in the high temperature gas-cooled reactor (HTGR fuel.  In this study silicon carbide oxidation simulation take place in case the accident in primary cooling pipe is ruptured.  Sample silicon carbide made of powder that pressed into pellet with diameter 12.7 mm and thickness 1.0 mm, then oxidized at temperature 1000 oC, 1200 oC dan 1400 oC for 1 hour.  The samples were weighted before and after oxidized.  X-ray diffraction con-ducted to the samples using Panalytical Empyrean diffractometer with Cu as X-ray source.  Diffraction pattern analysis has been done using General Structure Analysis System (GSAS software. This software was resulting the lattice parameter changes and content of SiC phases.  The result showed all of the oxidation samples undergoes weight gain.  The 6S samples showed the highest weight change at oxidation temperature 1200 oC, for the 46S samples showed increasing tendency with the oxidation temperature.  X-ray diffraction pattern analysis showed the 6S samples contain dominan phase 6H-SiC that matched to ICSD 98-001-5325 card.  Diffraction pattern on 6S showed lattice parameter, composition and crystallite size changes.  Lattice parameters changes had smaller tendency from the model and before oxidation.  However, the lowest silicon carbide composition or the highest converted into other phases up to 66.85 %, occurred at oxidation temperature 1200 oC.  The 46S samples contains two polytypes silicon car-bide.  The 6H-SiC phases matched by ICSD 98-016-4972 card and 4H-SiC phase matched by ICSD 98

  12. Hydrogen production through high-temperature electrolysis in a solid oxide cell

    International Nuclear Information System (INIS)

    Herring, J.St.; Lessing, P.; O'Brien, J.E.; Stoots, C.; Hartvigsen, J.; Elangovan, S.

    2004-01-01

    An experimental research programme is being conducted by the INEEL and Ceramatec, Inc., to test the high-temperature, electrolytic production of hydrogen from steam using a solid oxide cell. The research team is designing and testing solid oxide cells for operation in the electrolysis mode, producing hydrogen rising a high-temperature heat and electrical energy. The high-temperature heat and the electrical power would be supplied simultaneously by a high-temperature nuclear reactor. Operation at high temperature reduces the electrical energy requirement for electrolysis and also increases the thermal efficiency of the power-generating cycle. The high-temperature electrolysis process will utilize heat from a specialized secondary loop carrying a steam/hydrogen mixture. It is expected that, through the combination of a high-temperature reactor and high-temperature electrolysis, the process will achieve an overall thermal conversion efficiency of 40 to 50%o while avoiding the challenging chemistry and corrosion issues associated with the thermochemical processes. Planar solid oxide cell technology is being utilised because it has the best potential for high efficiency due to minimized voltage and current losses. These losses also decrease with increasing temperature. Initial testing has determined the performance of single 'button' cells. Subsequent testing will investigate the performance of multiple-cell stacks operating in the electrolysis mode. Testing is being performed both at Ceramatec and at INEEL. The first cells to be tested were single cells based on existing materials and fabrication technology developed at Ceramatec for production of solid oxide fuel cells. These cells use a relatively thick (∼ 175 μm) electrolyte of yttria- or scandia-stabilised zirconia, with nickel-zirconia cermet anodes and strontium-doped lanthanum manganite cathodes. Additional custom cells with lanthanum gallate electrolyte have been developed and tested. Results to date have

  13. Room temperature transparent conducting magnetic oxide (TCMO properties in heavy ion doped oxide semiconductor

    Directory of Open Access Journals (Sweden)

    Juwon Lee

    2017-08-01

    Full Text Available Bismuth doped ZnO (ZnBi0.03O0.97 thin films are grown using pulsed laser deposition. The existence of positively charged Bi, absence of metallic zinc and the Zn-O bond formation in Bi doped ZnO are confirmed using X-ray Photoelectron Spectroscopy (XPS. Temperature dependent resistivity and UV-visible absorption spectra show lowest resistivity with 8.44 × 10-4 Ω cm at 300 K and average transmittance of 93 % in the visible region respectively. The robust ferromagnetic signature is observed at 350 K (7.156 × 10-4 emu/g. This study suggests that Bi doped ZnO films should be a potential candidate for spin based optoelectronic applications.

  14. High-temperature steam-oxidation behavior of Zr-1Nb-1Sn-0.1Fe cladding tube at temperatures of 800-1000

    International Nuclear Information System (INIS)

    Lee, Cheol Min; Cho, Tae Won; Jeong, Gwan Yoon; Kim, Mi Jin; Kim, Ji Hyeon; Lee, Hee Jae; Sohn, Dong Seong; Mok, Yong Kyoon

    2016-01-01

    To prevent cladding failure, NRC issued a regulation Title 10 § 50.46, which specifies cladding temperature of 1204 .deg. C and 17% ECR should not be exceeded. The fundamental reason of the mechanical degradation of cladding is the formation of the oxide which is brittle. Theoretically, the oxide layer is formed following parabolic rate. However, from many experiments, sub-parabolic rates are often observed. There have been many suggestions so far; chemical and stress gradient across the oxide layer could initiate the sub-parabolic rate, the phase transformation of Zirconium dioxide from tetragonal to monoclinic could be the reason, change of the grain size of Zirconium dioxide could cause the cubic oxidation rate, and there is a suggestion that if electron migration is the major mechanism of the oxide growth, then the subparabolic rate can show up. However, the reason why the sub-parabolic rate appears is still not certain. Another important degradation mechanism is breakaway oxidation. A clear explanation that why the breakaway oxidation appears is still not clear. Most of the people believe the phase transformation of Zirconium dioxide cause instability within the oxide, which causes breakaway oxidation to appear. However, how much effect is caused from the phase transformation is not so sure. In this study, detailed analysis about the oxidation kinetics and the breakaway oxidation of Zr-1Nb-1Sn- 0.1Fe were carried out at temperatures between 800 - 1000 .deg. C.

  15. Creep performance of oxide ceramic fiber materials at elevated temperature in air and in steam

    Science.gov (United States)

    Armani, Clinton J.

    Structural aerospace components that operate in severe conditions, such as extreme temperatures and detrimental environments, require structural materials that have superior long-term mechanical properties and that are thermochemically stable over a broad range of service temperatures and environments. Ceramic matrix composites (CMCs) capable of excellent mechanical performance in harsh environments are prime candidates for such applications. Oxide ceramic materials have been used as constituents in CMCs. However, recent studies have shown that high-temperature mechanical performance of oxide-oxide CMCs deteriorate in a steam-rich environment. The degradation of strength at elevated temperature in steam has been attributed to the environmentally assisted subcritical crack growth in the oxide fibers. Furthermore, oxide-oxide CMCs have shown significant increases in steady-state creep rates in steam. The present research investigated the effects of steam on the high-temperature creep and monotonic tension performance of several oxide ceramic materials. Experimental facilities were designed and configured, and experimental methods were developed to explore the influence of steam on the mechanical behaviors of ceramic fiber tows and of ceramic bulk materials under temperatures in the 1100--1300°C range. The effects of steam on creep behavior of Nextel(TM)610 and Nextel(TM)720 fiber tows were examined. Creep rates at elevated temperatures in air and in steam were obtained for both types of fibers. Relationships between creep rates and applied stresses were modeled and underlying creep mechanisms were identified. For both types of fiber tows, a creep life prediction analysis was performed using linear elastic fracture mechanics and a power-law crack velocity model. These results have not been previously reported and have critical design implications for CMC components operating in steam or near the recommended design limits. Predictions were assessed and validated via

  16. A study of the relationship between microstructure and oxidation effects in nuclear graphite at very high temperatures

    Science.gov (United States)

    Lo, I.-Hsuan; Tzelepi, Athanasia; Patterson, Eann A.; Yeh, Tsung-Kuang

    2018-04-01

    Graphite is used in the cores of gas-cooled reactors as both the neutron moderator and a structural material, and traditional and novel graphite materials are being studied worldwide for applications in Generation IV reactors. In this study, the oxidation characteristics of petroleum-based IG-110 and pitch-based IG-430 graphite pellets in helium and air environments at temperatures ranging from 700 to 1600 °C were investigated. The oxidation rates and activation energies were determined based on mass loss measurements in a series of oxidation tests. The surface morphology was characterized by scanning electron microscopy. Although the thermal oxidation mechanism was previously considered to be the same for all temperatures higher than 1000 °C, the significant increases in oxidation rate observed at very high temperatures suggest that the oxidation behavior of the selected graphite materials at temperatures higher than 1200 °C is different. This work demonstrates that changes in surface morphology and in oxidation rate of the filler particles in the graphite materials are more prominent at temperatures above 1200 °C. Furthermore, possible intrinsic factors contributing to the oxidation of the two graphite materials at different temperature ranges are discussed taking account of the dominant role played by temperature.

  17. Fabrication processes of C/Sic composites for high temperature components in energy systems and investigation of their oxidation behavior

    International Nuclear Information System (INIS)

    El-Hakim, E.

    2004-01-01

    Carbon fibre-reinforced ceramic matrix composite are promising candidate materials for high temperature applications such as structural components in energy systems, fusion reactors and advanced gas turbine engines. C/C composites has low oxidation resistance at temperatures above 500degree. To overcome this low oxidation resistance a coating should be applied. Tenax HTA 5131 carbon fibres impregnated with phenolic resin and reinforced silicon carbide were modified by the addition of a coating layer of boron oxide, (suspended in Dyansil-40) for improving anti-oxidation properties of the composites.The oxidation behavior of carbon-silicon carbide composites coated with B 2 O 3 , as an protective layer former, in dry air has been studied in the temperature range 800- 1000 degree for 8 hrs and 16 hrs. The results show that the oxidation rates of the uncoated composites samples are higher than those of the coated composites. The uncoated samples exhibit the highest oxidation rate during the initial stages of oxidation. The composite coated with B 2 O 3 had a significantly improved oxidation resistance due to the formation of a barrier layer for oxygen diffusion. This improvement in the oxidation resistance is attributed to the blocking of the active sites for oxygen diffusion. The oxidation resistance of the coated composite is highly improved; the weight loss percentage of casted samples is 4.5-16% after 16-hrs oxidation in air while the weight loss of uncoated samples is about 60%. The results are supported by scanning electron microscopy

  18. Enhanced and selective ammonia sensing of reduced graphene oxide based chemo resistive sensor at room temperature

    Science.gov (United States)

    Kumar, Ramesh; Kaur, Amarjeet

    2016-05-01

    The reduced graphene oxide thin films were fabricated by using the spin coating method. The reduced graphene oxide samples were characterised by Raman studies to obtain corresponding D and G bands at 1360 and 1590 cm-1 respectively. Fourier transform infra-red (FTIR) spectra consists of peak corresponds to sp2 hybridisation of carbon atoms at 1560 cm-1. The reduced graphene oxide based chemoresistive sensor exhibited a p-type semiconductor behaviour in ambient conditions and showed good sensitivity to different concentration of ammonia from 25 ppm to 500 ppm and excellent selectivity at room temperature. The sensor displays selectivity to several hazardous vapours such as methanol, ethanol, acetone and hydrazine hydrate. The sensor demonstrated a sensitivity of 9.8 at 25 ppm concentration of ammonia with response time of 163 seconds.

  19. Flow-Tube Reactor Experiments on the High Temperature Oxidation of Carbon Weaves

    Science.gov (United States)

    Panerai, Francesco; White, Jason D.; Robertson, Robert; Borner, Arnaud; Ferguson, Joseph C.; Mansour, Nagi N.

    2017-01-01

    Under entry conditions carbon weaves used in thermal protection systems (TPS) decompose via oxidation. Modeling this phenomenon is challenging due to the different regimes encountered along a flight trajectory. Approaches using equilibrium chemistry may lead to over-estimated mass loss and recession at certain conditions. Concurrently, there is a shortcoming of experimental data on carbon weaves to enable development of improved models. In this work, a flow-tube test facility was used to measure the oxidation of carbon weaves at temperatures up to 1500 K. The material tested was the 3D carbon weave used for the heat shield of the NASA Adaptive Deployable Entry and Placement Technology, ADEPT. Oxidation was characterized by quantifying decomposition gases (CO and CO2), by mass measurements, and by microscale surface analysis. The current set of measurements contributes to the development of finite rate chemistry models for carbon fabrics used in woven TPS materials.

  20. Composition and corrosion properties of high-temperature oxide films on steel type 18-10

    International Nuclear Information System (INIS)

    Vakulenko, B.F.; Morozov, O.N.; Chernysheva, M.V.

    1985-01-01

    The composition and propeties of oxide films, formed in the process of tube production of steel type 18-10, as well as the behaviour of the steels coated with oxide films under operating conditions of NPP heat-exchange equipment at the 20-300 deg C temperatures are determined. It is found, that the films have a good adhesion to the steel surface and repeat the metal structure without interfering with, the surface defect determination. Introduction of the NaNO 2 corrosion inhibitor decreases the film destruction rate to the level of the base metal corrosion. It is found acceptable to use tubes of steel 18-10 coated with dense oxide films in the heat-exchange and water supply systems of NPP