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2009


Rare-earth disilicate formation under Deep Geological Repository approach conditions


Alba, MD; Chain, P; Orta, MM
Applied Clay Science, 46 (2009) 63-68

ABSTRACT

The Deep Geological Repository (DGR) concept involves the placement of long-lived radioactive waste in rooms excavated deep. The major responsibility of the disposal safety falls on the Engineered Barrier System (EBS). The main constituent of EBS is bentonite that prevents the release of radiactive nuclei by physical and chemical mechanisms. The physical mechanism is expected to fault with the weathering of the bentonite while the chemical mechanisms have been only proved at 300 °C. It is the aim of this paper to explore the feasibility of the chemical mechanism at temperatures closer to the DGP conditions and to shed light on the mechanism of transformation of the argillaceous materials of the EBS in rare-earth disilicate phases. Saponite was submitted to hydrothermal reaction at 175 °C and 150 °C with different solutions of REE3+ cations (REE = Sc, Lu, Y, Sm, Nd and La). The products were analyzed by XRD, NMR and electron microscopy. At conditions close to the DGP, the saponite was able to form rare-earth silicates. The formation of the disilicate phase, as final product, needs a set of stages and oxyorthosilicate as precursor.


Septiembre, 2009 | DOI: 10.1016/j.clay.2009.07.012

Influence of sulfur on the structural, surface properties and photocatalytic activity of sulfated TiO2


Colon, G; Hidalgo, MC; Navio, JA; Kubacka, A; Fernandez-Garcia, M
Applied Catalysis B-Environmental, 90 (2009) 633-641

ABSTRACT

TiO2 materials were prepared by sol–gel method and then impregnated with sulfuric acid and calcined using different temperatures and atmosphere (air and nitrogen). Systematic variation of these two experimental parameters makes possible to modulate the amount of surface sulfur from the impregnation procedure. The best photocatalyst for liquid phenol degradation was obtained after calcination at 700 °C in air, while gas toluene degradation optimum performance is obtained by calcination at 700 °C in nitrogen from 500 °C. Structural analysis of these materials by XRD, micro-Raman spectroscopy and FE-SEM shows that once calcined at 700 °C the material was a well-crystallized, high surface area anatase structure in all cases. The surface characterization by FTIR and XPS confirms the presence of a higher amount of sulfur species and acidic OH groups in samples partially calcined in nitrogen, and a low XPS O/Ti-atomic ratio with the O 1s peak shifted to higher binding energies (1.8 vs. 2 ± 0.1 and 530.4 eV vs. 529.8 eV, respectively, against the reference materials) for samples calcined at 700 °C, temperature at which most of sulfate species have been evolved. The paper presents an attempt to correlate the contribution of the observed structural defects within the anatase sub-surface layers and surface acidity to the different photoactivity behaviour exhibited for phenol liquid phase and toluene gas phase photodegradation.


Agosto, 2009 | DOI: 10.1016/j.apcatb.2009.04.026

Incorporation and Thermal Evolution of Rhodamine 6G Dye Molecules Adsorbed in Porous Columnar Optical SiO2 Thin Films


Sanchez-Valencia, JR; Blaszczyk-Lezak, I; Espinos, JP; Hamad, S; Gonzalez-Elipe, AR; Barranco, A
Langmuir, 25 (2009) 6869-6874

ABSTRACT

Rhodamine 6G (Rh6G) dye molecules have been incorporated into transparent and porous SiO2 thin films prepared by evaporation at glancing angles. The porosity of these films has been assessed by analyzing their water adsorption isotherms measured for the films deposited on a quartz crystal monitor. Composite Rh6G/SiO2 thin films were prepared by immersion of a SiO2 thin film into a solution of the dye at a given pH. It is found that the amount of Rh6G molecules incorporated into the film is directly dependent on the pH of the solution and can be accounted for by a model based on the point of zero charge (PZC) concepts originally developed for colloidal oxides. At low pHs, the dye molecules incorporate in the form of monomers, while dimers or higher aggregates are formed if the pH increases. Depending on the actual preparation and treatment conditions, they also exhibit high relative fluorescence efficiency. The thermal stability of the composite films has been also investigated by characterizing their optical behavior after heating in an Ar atmosphere at increasing temperatures up to 275 °C. Heating induces a progressive loss of active dye molecules, a change in their agglomeration state, and an increment in their relative fluorescence efficiency. The obtained Rh6G/SiO2 composite thin films did not disperse the light and therefore can be used for integration into optical and photonic devices.


Agosto, 2009 | DOI: 10.1021/la900695t

Chemical and electronic interface structure of spray pyrolysis deposited undoped and Al-doped ZnO thin films on a commercial Cz-Si solar cell substrate


Gabas, M; Barrett, NT; Ramos-Barrado, JR; Gota, S; Rojas, TC; Lopez-Escalante, MC
Solar Energy Materials and Solar Cells, 93 (2009) 1356-1365

ABSTRACT

We have studied differences in the interface between undoped and Al-doped ZnO thin films deposited on commercial Si solar cell substrates. The undoped ZnO film is significantly thicker than the Al-doped film for the same deposition time. An extended silicate-like interface is present in both samples. Transmission electron microscopy (TEM) and photoelectron spectroscopy (PES) probe the presence of a zinc silicate and several Si oxides in both cases. Although Al doping improves the conductivity of ZnO, we present evidence for Al segregation at the interface during deposition on the Si substrate and suggest the presence of considerable fixed charge near the oxidized Si interface layer. The induced distortion in the valence band, compared to that of undoped ZnO, could be responsible for considerable reduction in the solar cell performance.


Agosto, 2009 | DOI: 10.1016/j.solmat.2009.02.018

Identification of hydrogen and deuterium at the surface of water ice by reflection electron energy loss spectroscopy


Yubero, F; Tokesi, K
Applied Physics Letters, 95 (2009) 084101

ABSTRACT

A nondestructive method to distinguish between hydrogen (H) and deuterium (D) at surfaces by reflection electron energy loss spectroscopy is presented. It is based on the analysis of the energy distributions of electrons elastically backscattered from surfaces containing H or D. We consider standard and deuterated water ices as test surfaces. The recoil energy of the backscattered electrons depends on the atomic mass of the targets, and the contributions of H, D, and O to the measured spectra can be easily separated. The results of Monte Carlo simulations corroborate the experimental findings.


Agosto, 2009 | DOI: 10.1063/1.3202402

Near-ambient X-ray photoemission spectroscopy and kinetic approach to the mechanism of carbon monoxide oxidation over lanthanum substituted cobaltites


Hueso, JL; Martinez-Martinez, D; Caballero, A; Gonzalez-Elipe, AR; Mun, BS; Salmeron, M
Catalysis Communications, 10 (2009) 1898-1902

ABSTRACT

We have studied the oxidation of carbon monoxide over a lanthanum substituted perovskite (La0.5Sr0.5CoO3−d) catalyst prepared by spray pyrolysis. Under the assumption of a first-order kinetics mechanism for CO, it has been found that the activation energy barrier of the reaction changes from ∼80 to ∼40 kJ mol−1 at a threshold temperature of ca. 320 °C. In situ XPS near-ambient pressure (∼0.2 torr) shows that the gas phase oxygen concentration over the sample decreases sharply at ca. 300 °C. These two observations suggest that the oxidation of CO undergoes a change of mechanism at temperatures higher than 300 °C.


Agosto, 2009 | DOI: 10.1016/j.catcom.2009.06.022

Aluminium anodisation for Au-CeO2/Al2O3-Al monoliths preparation


Sanz, O; Martinez, LM; Echave, FJ; Dominguez, MI; Centeno, MA; Odriozola, JA; Montes, M
Chemical Engineering Journal, 151 (2009) 324-332

ABSTRACT

The anodisation of aluminium monoliths was performed in order to generate an alumina layer that ensures a good adherence of the catalysts. In this study, it is demonstrated that the morphology of the produced alumina layer depends on time, temperature, current density and concentration of the selected electrolyte. When anodisation process with the extreme conditions was applied (30 °C, 50 min, 2 A dm−2 and 2.6 M of sulphuric acid) a significant cracks were obtained and used to fix the subsequent catalytic coatings. The washcoating method was used to cover the monoliths with colloidal solutions of CeO2 and/or Au-CeO2 catalysts. The resulting monolithic catalysts were tested in the CO oxidation reaction being 1%Au-CeO2 containing system the most active. The structured catalyst prepared this way changed neither the textural nor the catalytic properties of the deposited catalytic powders.


Agosto, 2009 | DOI: 10.1016/j.cej.2009.03.062

Synthesis of complex carbonitride powders TiyMT1−yCxN1−x (MT: Zr, V, Ta, Hf) via a mechanically induced self-sustaining reaction


Cordoba, JM; Aviles, MA; Sayagues, MJ; Alcala, MD; Gotor, FJ
Journal of Alloys and Compounds, 482 (2012) 349-355

ABSTRACT

The machinability of materials is a dynamic field with enormous implications in different industrial sectors because manufacturers are constantly looking for improvements that can increase the overall productivity. Manufacturers of cutting tool inserts need to develop products that can perform at higher speeds and last longer under increasingly rigorous operating conditions. It has been revealed that cermets may exhibit better properties and performances when solid solution of multiple hard compounds is added instead of a mixture of several binary ones. In this work, a mechanically induced self-sustaining reaction (MSR) is described as a suitable synthesis method to obtain a wide range of different new quaternary carbonitride systems by milling mixtures of elemental powders of transition metals and graphite in a nitrogen atmosphere. Characterization was carried out using X-ray powder diffraction, elemental analysis, energy dispersive X-ray analysis (EDX), scanning and transmission electron microscopy and electron diffraction (ED).


Agosto, 2009 | DOI: 10.1016/j.jallcom.2009.04.012

Synthesis by pyrolysis of aerosols and ceramic application of Cr-doped CaYAlO4 red–orange pigments


Lyubenova, TS; Carda, JB; Ocana, M
Journal of the European Ceramic Society, 29 (2009) 2193-2198

ABSTRACT

The synthesis of red–orange Cr-doped YCaAlO4 pigments has been improved (softer thermal conditions and lower environmental impact) and optimised by using the pyrolysis of aerosols method. We also study the crystallochemical features of the Cr chromophore with special emphasis on its oxidation state which has not been yet clarified, finding that Cr(III) and Cr(IV) species are present in the octahedral and interstitial tetrahedral sites of the YCaAlO4 lattice, respectively. Finally, the applicability of this system as ceramic pigment was tested using conventional industrial glazes. A change from orange to pink shades was detected after glaze firing, which is mainly attributed to the Cr3+ to Cr4+ oxidation.


Agosto, 2009 | DOI: 10.1016/j.jeurceramsoc.2009.01.020

Reactivity of LaNi1−y Co y O3−δ Perovskite Systems in the Deep Oxidation of Toluene


Pereniguez, R; Hueso, JL; Holgado, JP; Gaillard, F; Caballero, A
Catalysis Letters, 131 (2009) 164-169

ABSTRACT

In the present work we have evaluated the oxidation of toluene over different lanthanum perovskites with a general composition of LaNi1−y Co y O3−δ. These catalysts, prepared by a spray pyrolysis method, have been characterised by XRD, BET and FE-SEM techniques. Additional experiments of temperature programmed desorption of O2, reduction in H2 and X-ray absorption spectroscopy were also performed in order to identify the main surface oxygen species and the reducibility of the different perovskites. The catalytic behaviour toward the oxidation of toluene (as a model for VOCs compounds) was evaluated in the range 100–600 °C, detecting a total conversion for all the samples below 400 °C and higher activities for the cobalt-containing perovskites. The catalytic behaviour of these samples is consistent with a suprafacial mechanism, with the α-type oxygen playing an active role in the oxidation reaction.


Agosto, 2009 | DOI: 10.1007/s10562-009-9968-0

Mineralogical stability of phyllosilicates in hyperalkaline fluids: Influence of layer nature, octahedral occupation and presence of tetrahedral Al


Becerro, AI; Mantovani, M; Escudero, A
American Mineralogist, 94 (2009) 1187-1197

ABSTRACT

Mineralogical changes in a set of phyllosilicates, differing in their layer nature, chemical composition, octahedral character, and Al content of the tetrahedral sheet, were analyzed after hydrothermal reaction in an alkaline solution. The composition of the alkaline solution was selected to simulate the first stage of cement degradation [NaOH-KOH-Ca(OH)2]. The reaction products have been analyzed by XRD, 29Si and 27Al MAS NMR spectroscopy, SEM/EDX, and TEM. The results indicate that the main factor influencing the stability of the clays is the occupation of the octahedral sheet such that all trioctahedral members withstand the alkaline attack, whereas most of the dioctahedral clays suffer a complete dissolution and crystallization of new phases. Second, clays with Al in the tetrahedral sheet of their layers are shown to be less stable than those with a pure Si tetrahedral sheet.


Agosto, 2009 | DOI: 10.2138/am.2009.3164

Comparative investigation of TiAlC(N), TiCrAlC(N), and CrAlC(N) coatings deposited by sputtering of МАХ-phase Ti2 − хCrхAlC targets


Shtansky, DV; Kiryukhantsev-Korneev, PV; Sheveyko, AN; Mavrin, BN; Rojas, C; Fernandez, A; Levashov, EA
Surface and Coatings Technology, 203 (2009) 3595-3609

ABSTRACT

A comparative investigation of the structure and properties of TiAlC(N), TiCrAlC(N), and CrAlC(N) coatings deposited by sputtering of МАХ-phase Ti2 − хCrхAlC targets (where x = 0, 0.5, 1.5, and 2) in an Ar atmosphere or in a gaseous mixture of Ar + N2 is presented. The coatings were characterized in terms of their structure, elemental and phase composition, hardness, elastic modulus, elastic recovery, thermal stability, friction coefficient, wear rate, corrosion, and high-temperature oxidation resistance. The structure of the coatings was studied by means of X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, glow discharge optical emission spectroscopy, electron energy loss spectroscopy, and Raman spectroscopy. To evaluate the thermal stability and oxidation resistance, the coatings were annealed either in vacuum or in air at temperatures 600–1200 °C. The results obtained show that the TiAlCN coatings possess high hardness of 32–35 GPa, low friction coefficient against WC–Co well below 0.25, high thermal stability up to 1200 °C, and superior performance in dry milling tests against high Cr steel. Meanwhile, the coatings with high Cr content demonstrated improved oxidation resistance up to 1000 °C and superior electrochemical behavior, but their mechanical and tribological properties were deteriorated.


Agosto, 2009 | DOI: 10.1016/j.surfcoat.2009.05.036

High surface area α-alumina preparation by using urban waste


Martin-Ruiz, MM; Perez-Maqueda, LA; Cordero, T; Balek, V; Subrt, J; Murafa, N; Pascual-Cosp, J
Ceramics International, 35 (2009) 2111-2117

ABSTRACT

A new method for preparing high surface area α-alumina from urban waste is proposed. The method consists of the precipitation of a precursor that contains bohemite mixed with a linear polymer and subsequently the thermal decomposition of the precursor by heating in nitrogen and air to 1200 °C. The resulting α-alumina consists of nanocrystals of about 100 nm aggregated into larger particles with relatively high surface area (12 m2 g−1) and a significant macropore volume of 0.545 cm3 g. Methods of X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) were used to characterize microstructure of prepared materials. Results of differential thermal analysis, thermogravimetry and emanation thermal analysis characterized the thermal behaviour of α-alumina precursors.


Agosto, 2009 | DOI: 10.1016/j.ceramint.2008.11.011

Structural characteristics and morphology of SmxCe1−xO2−x/2 thin films


Hartmanova, M; Jergel, M; Mansilla, C; Holgado, JP; Zemek, J; Jurek, K; Kundracik, F
Applied Surface Science, 255 (2009) 9085-9091

ABSTRACT

Effect of the deposition temperature (200 and 500 °C) and composition of SmxCe1−xO2−x/2 (x = 0, 10.9–15.9 mol%) thin films prepared by electron beam physical vapor deposition (EB-PVD) and Ar+ ion beam assisted deposition (IBAD) combined with EB-PVD on structural characteristics and morphology/microstructure was investigated. The X-ray photoelectron spectroscopy (XPS) of the surface and electron probe microanalysis (EPMA) of the bulk of the film revealed the dominant occurrence of Ce4+ oxidation state, suggesting the presence of CeO2 phase, which was confirmed by X-ray diffraction (XRD). The Ce3+ oxidation states corresponding to Ce2O3 phase were in minority. The XRD and scanning electron microscopy (SEM) showed the polycrystalline columnar structure and a rooftop morphology of the surface. Effects of the preparation conditions (temperature, composition, IBAD) on the lattice parameter, grain size, perfection of the columnar growth and its impact on the surface morphology are analyzed and discussed.


Agosto, 2009 | DOI: 10.1016/j.apsusc.2009.06.108

Kinetics of the thermal decomposition of anhydrous cobalt nitrate by SCRT method


Ortega, A; Macias, M; Gotor, FJ
Journal of Thermal Analysis and Calorimetry, 98 (2009) 441-448

ABSTRACT

It has been shown the ability of the Sample Controlled Reaction Temperature (SCRT) method for both discriminate the kinetic law and calculate the activation energy of the reaction. This thermal decomposition is best described by a Johnson–Mehl–Avrami kinetic model (with n = 2) with an activation energy of nuclei growth which fall in the range 52–59 kJ mol−1. The process is not a single-step because the initial rate of decomposition is likely to be limited by nucleation. The results reported here constitute the first attempt to use the new SCRT method to study the kinetic of the thermal decomposition of cobalt nitrate.


Agosto, 2009 | DOI: 10.1007/s10973-009-0322-y

Chemical State of Nitrogen and Visible Surface and Schottky Barrier Driven Photoactivities of N-Doped TiO2 Thin Films


Romero-Gomez, P; Rico, V; Borras, A; Barranco, A; Espinos, JP; Cotrino, J; Gonzalez-Elipe, AR
Journal of Physical Chemistry C, 113 (2009) 13341-13351

ABSTRACT

N-doped TiO2 thin films have been prepared by plasma enhanced chemical vapor deposition and by physical vapor deposition by adding nitrogen or ammonia to the gas phase. Different sets of N-doped TiO2 thin films have been obtained by changing the preparation conditions during the deposition. The samples have been characterized by X-ray diffraction, Raman, UV−vis spectroscopy, and X-ray photoemission spectroscopy (XPS). By changing the preparation conditions, different structures, microstructures, and degrees and types of doping have been obtained and some relationships have been established between these film properties and their visible light photoactivity. The N1s XP spectra of the samples are characterized by three main features, one tentatively attributed to Ti−N (i.e., nitride with a binding energy (BE) of 396.1 eV) and two others with BEs of 399.3 and 400.7 eV, tentatively attributed to nitrogen bonded simultaneously to titanium and oxygen atoms (i.e., Ti−N−O like species). By controlling the deposition conditions it is possible to prepare samples with only one of these species as majority component. It has been shown that only the samples with Ti−N−O like species show surface photoactivity being able to change their wetting angle when they are illuminated with visible light. The presence of these species and an additional complex structure formed by a mixture of anatase and rutile phases is an additional condition that is fulfilled by the thin films that also present photocatalytic activity with visible light (i.e., surface and Schottky barrier driven photoactivities). The relationships existing between the reduction state of the samples and the formation of Ti−N or Ti−N−O like species are also discussed.


Julio, 2009 | DOI: 10.1021/jp9024816

FTIR study of photocatalytic degradation of 2-propanol in gas phase with different TiO2 catalysts


Arana, J; Alonso, AP; Rodriguez, JMD; Colon, G; Navio, JA; Pena, JP
Applied Catalysis B-Environmental, 89 (2009) 204-213

ABSTRACT

The photocatalytic efficiency of different TiO 2 catalysts in the degradation of 2-propanol in gas phase has been studied. The obtained efficiencies have been compared considering the distribution of rutile-anatase phases, surface area, particle size, distribution of surface hydroxyl groups and Brönsted or Lewis acid centres. The catalysts used were Degussa-P25 (TiO 2-P25), Hombikat, Millennium, Kemira and s/g-TiO 2, a catalyst prepared by a sol-gel method. The best photocatalytic behaviours have been obtained with those catalysts with higher surface area and the presence of only anatase phase (Hombikat and Millennium). A progressive deactivation of TiO 2-P25 and s/g-TiO 2 has been observed during the photocatalytic process. FTIR studies indicated that degradation mechanisms depended on the catalyst employed. Deactivation processes observed in TiO 2-P25 have been correlated with the formation of carboxylates.


Julio, 2009 | DOI: 10.1016/j.apcatb.2008.11.027

Effect of Sulfate Pretreatment on Gold-Modified TiO2 for Photocatalytic Applications


Hidalgo, MC; Maicu, M; Navio, JA; Colon, G
Journal of Physical Chemistry C, 113 (2009) 12840-12847

ABSTRACT

The influence of sulfated pretreatment of TiO2 on the structure, morphology, and dispersion of gold and photocatalytic properties of Au/TiO2 were studied. Notable enhancements in the photocatalytic activity of TiO2 were achieved by deposition of gold onto samples that had previously undergone sulfate treatment followed by high temperature calcination. The enhancement in activity can be attributed to the stronger bonding and improved electronic communication between gold particles and TiO2 on defect rich surfaces as are found on sulfated samples after calcination at 700 °C. Two different methods for gold deposition were evaluated: chemical reduction by citrate and photodeposition. The citrate method produced more homogeneous and smaller gold particles with a better dispersion than photodeposition, which lead to greater increases in activity in the photocatalytic degradation of phenol when the former method was used for deposition on both sulfated and nonsulfated TiO2. The combination of sulfate pretreatment and gold deposition by chemical reduction was shown to be a good strategy to obtain gold/titania catalysts possessing homogeneous particle size and dispersion of the metal and a strong bonding between the Au and the TiO2 surface.


Julio, 2009 | DOI: 10.1021/jp903432p

ZnO activation by using activated carbon as a support: Characterisation and photoreactivity


Melian, EP; Diaz, OG; Rodriguez, JMD; Colon, G; Arana, J; Melian, JH; Navio, JA; Pena, JP
Applied Catalysis A-General, 364 (2009) 176-181

ABSTRACT

The effect of the mixing ZnO with different portions of activated carbon (AC) has been studied. The resulting catalysts were characterised and evaluated in the photocatalytic decomposition of aqueous pollutants. Changes in the catalyst colour and in the FTIR vibration bands of the surface hydroxyl groups were recorded. νOH vibrations were shifted to lower wavenumbers as AC loading increased, demonstrating modification of the acid-base character of the catalysts. Laser scattering studies showed that AC loading leads to smaller ZnO particles. BET surface area measurements and scanning electron micrograph (SEM) analysis showed agglomeration of ZnO particle pores in the AC structure.

Results showed that in addition to a synergistic effect of the AC-ZnO combination, AC content modifies the ZnO particle properties and consequently photocatalytic behaviour. This was evident in phenol degradation experiments where changes in the concentration profiles of the catechol and hydroquinone degradation intermediates, were observed. However, the AC-ZnO catalysts were less efficient than pure ZnO in the degradation of 2,4-dichlorophenol (DCP). This seems to be due to the strong adsorption of the DCP molecule on AC, resulting in lower diffusion to the catalytic ZnO and thus a lower rate of photocatalysis.


Julio, 2009 | DOI: 10.1016/j.apcata.2009.05.042

Deposition of Al-Fe pillared bentonites and gold supported Al-Fe pillared bentonites on metallic monoliths for catalytic oxidation reactions


Martinez, LM; Dominguez, MI; Sanabria, N; Hernandez, WY; Moreno, S; Molina, R; Odriozola, JA; Centeno, MA
Applied Catalysis A-General, 364 (2009) 166-173

ABSTRACT

Al-Fe pillared bentonite and gold supported on Al-Fe pillared bentonite catalysts deposed on Fecralloy monoliths have been prepared, characterized and tested in two oxidation reactions: gaseous oxidation of CO and phenol oxidation in aqueous medium. The deposition of the solid on the metallic substrate does not alter its structural characteristics. The use of monoliths improves the activity in both reactions and offers the additional advantage to facilitate the separation of the catalyst from the reaction medium.


Julio, 2009 | DOI: 10.1016/j.apcata.2009.05.046

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