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Effect of Nb Doping on Hydration and Conductivity of La27W5O55.5−δ

ID=362
Authors Cao, Y., Duan, N., Jian, L., Evans, A. and Haugsrud, R.
Source
J. Am. Ceram. Soc.
Time of Publication: 2016
Abstract Hydration properties and electrical characteristics of the high-temperature proton conductor La27(W0.85Nb0.15)5O55.5−δ are investigated by means of thermogravimetry, impedance spectroscopy, and the electromotive force (EMF) method as a function of temperature, water vapor, and oxygen partial pressures, as well as isotope exchange measurements in order to elucidate the mechanism and thermodynamics of protons formation and transport. The highest proton conductivity, 1.3 × 10-3 S/cm, is achieved at 700°C in wet O2. Proton self-diffusion coefficients are estimated from thermogravimetric measurements of hydration and conductivity data. Comparison of the conductivity characteristics between nominally pure and Nb-substituted materials reveals that the ionic conductivity increases and the activation energy decreases with Nb doping. These differences are discussed to reflect changes in the structure promoting ionic transport rather than changing the concentration of defects to any large extent.
Keywords Lanthanum tungstate; proton concentration; proton conductivity; H/D isotope effect
Remark doi:10.1111/jace.14346
Link

Synthesis, characterization and performance of robust poison-resistant ultrathin film yttria stabilized zirconia – nickel anodes for application in solid electrolyte fuel cells

ID=361
Authors F.J. Garcia-Garcia, F. Yubero, J.P. Espinós, A.R. González-Elipe, R.M. Lambert
Source
Journal of Power Sources
Volume: 324, Pages: 679–686
Time of Publication: 2016
Abstract We report on the synthesis of undoped ∼5 μm YSZ-Ni porous thin films prepared by reactive pulsed DC magnetron sputtering at an oblique angle of incidence. Pre-calcination of the amorphous unmodified precursor layers followed by reduction produces a film consisting of uniformly distributed tilted columnar aggregates having extensive three-phase boundaries and favorable gas diffusion characteristics. Similarly prepared films doped with 1.2 at.% Au are also porous and contain highly dispersed gold present as Ni-Au alloy particles whose surfaces are strongly enriched with Au. With hydrogen as fuel, the performance of the undoped thin film anodes is comparable to that of 10–20 times thicker typical commercial anodes. With a 1:1 steam/carbon feed, the un-doped anode cell current rapidly falls to zero after 60 h. In striking contrast, the initial performance of the Au-doped anode is much higher and remains unaffected after 170 h. Under deliberately harsh conditions the performance of the Au-doped anodes decreases progressively, almost certainly due to carbon deposition. Even so, the cell maintains some activity after 3 days operation in dramatic contrast with the un-doped anode, which stops working after only three hours of use. The implications and possible practical application of these findings are discussed.
Keywords Magnetron sputtering; Oblique angle deposition; Thin film anodes; Carbon-tolerant; SOFC
Remark doi:10.1016/j.jpowsour.2016.05.124
Link

Electrical characterization of amorphous LiAlO2 thin films deposited by atomic layer deposition

ID=360
Authors Yang Hu, Amund Ruud, Ville Miikkulainen, Truls Norby, Ola Nilsen and Helmer Fjellvåg
Source
RSC Advances
Volume: 6, Issue: 65, Pages: 60479-60486
Time of Publication: 2016
Abstract LiAlO2 thin films deposited by atomic layer deposition (ALD) have a potential application as an electrolyte in three-dimensional (3D) all-solid-state microbatteries. In this study, Li-ion conductivity of such films is investigated by both in-plane and cross-plane methods. LiAlO2 thin films with a Li composition of [Li]/([Li] + [Al]) = 0.46 and an amorphous structure were grown by ALD with thicknesses of 90, 160 and 235 nm on different substrates. The electrical characterization was conducted by impedance spectroscopy using inert electrodes over a temperature range of 25–200 °C in an inert atmosphere. In-plane conductivities were obtained from films on insulating sapphire substrates, whereas cross-plane conductivities were measured from films on conducting titanium substrates. For the first time, comparison of the in-plane and cross-plane conductivities in these ALD LiAlO2 films has been achieved. More comparable results are obtained using a cross-plane method, whereas in-plane conductivity measurements demonstrate a considerable thickness-dependence with thinner film thickness. The room-temperature conductivity of the LiAlO2 films has been determined to be in the order of 10−10 S cm−1 with an activation energy of ca. 0.8 eV.
Remark DOI: 10.1039/C6RA03137D
Link

Thin film YSZ-based limiting current-type oxygen and humidity sensor on thermally oxidized silicon substrates

ID=359
Author Shunsuke Akasaka
Source
Sensors and Actuators B: Chemical
Volume: 236, Pages: 499–505
Time of Publication: 2016
Abstract In this paper, we propose a thin film yttria-stabilized-zirconia (YSZ)-based limiting current-type oxygen and humidity sensor. These sensors were fabricated from layers of thin films on thermally oxidized silicon substrates, with the intention of installing such sensors onto microheaters. Sputtered porous Pt cathode are situated beneath the YSZ films, and are designed to provide a gas diffusion layer as well as function as electrodes. The porous Pt layer exhibits good performance as a gas diffusion layer because of its small pore size. Optimized YSZ sputtering growth conditions result in in-plane densification without the presence of cracks. The temperature dependence of the oxygen sensor’s level of limiting current was T −0.5. This result was attributed to the shrinkage of the extremely small pores in the gas diffusion layer. Between 450 and 550 °C, following the application of a voltage of 1.1 V, the time response measurements show a rapid response of a few seconds. The oxygen concentration and water vapor pressure correspond to the level of the limiting current at 1.1 V and 1.8 V, respectively.
Keywords Yttria-stabilized-zirconia; Limiting current; Oxygen sensor; Humidity sensor; Thin film; Silicon substrate
Remark doi:10.1016/j.snb.2016.06.025
Link

Conduction Mechanisms in BaTiO3–Bi(Zn1/2Ti1/2)O3 Ceramics

ID=358
Authors Kumar, N., Patterson, E. A., Frömling, T. and Cann, D. P.
Source
J. Am. Ceram. Soc.
Time of Publication: 2016
Abstract Polycrystalline BaTiO3–Bi(Zn1/2Ti1/2)O3 (BT–BZT) ceramics have superior dielectric properties for high-temperature and high-energy density applications as compared to the existing materials. While it has been shown that the addition of BZT to BT leads to an improvement in resistivity by two orders of magnitude, in this study impedance spectroscopy is used to demonstrate a novel change in conduction mechanism. While nominally undoped BT exhibits extrinsic-like p-type conduction, it is reported that BT–BZT ceramics exhibit intrinsic n-type conduction using atmosphere-dependent conductivity measurements. Annealing studies and Seebeck measurements were performed and confirmed this result. For BT, resistivity values were higher for samples annealed in nitrogen as compared to oxygen, whereas the opposite responses were observed for BZT-containing solid solutions. This suggests a fundamental change in the defect equilibrium conditions upon the addition of BZT to the solid solution that lowered the carrier concentration and changed the sign of the majority charge carrier. This is then also linked to the observed improvement in resistivity in BT–BZT ceramics as compared to undoped BT.
Remark doi:10.1111/jace.14313
Link

Effect of Nd-deficiency on electrochemical properties of NdBaCo2O6−δ cathode for intermediate-temperature solid oxide fuel cells

ID=357
Authors Kaihua Yia,Liping Sun, Qiang Li, Tian Xia, Lihua Huo, Hui Zhao, Jingwei Li, Zhe Lü, Jean-Marc Bassat, Aline Rougier, Sébastien Fourcade, Jean-Claude Grenier
Source
International Journal of Hydrogen Energy
Volume: 41, Issue: 24, Pages: 10228–10238
Time of Publication: 2016
Abstract Nd1−xBaCo2O6−δ (N1−xBCO) is evaluated as cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The effects of Nd-deficiency on the crystal structure, thermal expansion behavior, electrical conductivity and electrochemical performance are studied. N1−xBCO oxides crystallize in the orthorhombic symmetry with Pmmm space group. A good chemical compatibility between N1−xBCO and CGO electrolyte is found at 1100 °C in air. Introducing Nd-deficiency promotes the formation of oxygen vacancy, and significantly improves the electrochemical performance of N1−xBCO cathodes. The lowest area specific resistance (ASR) value of 0.043 Ω cm2 is obtained on the N0.96BCO cathode at 700 °C in air. The rate limiting step for electrochemical oxygen reduction reaction (ORR) is charge transfer process at the interface. The power output of the electrolyte supported cell Ni-CGO/CGO/N0.96BCO reaches 0.6 W cm−2 at 700 °C.
Keywords Solid oxide fuel cell; Double perovskite; Nd-deficiency; Cathode; Electrode reaction
Remark doi:10.1016/j.ijhydene.2016.04.248
Link

Controlling mixed conductivity in Na1/2Bi1/2TiO3 using A-site non-stoichiometry and Nb-donor doping

ID=356
Authors Linhao Li, Ming Li, Huairuo Zhang, Ian M. Reaney and Derek C. Sinclair
Source
J. Mater. Chem. C
Volume: 4, Pages: 5779-5786
Time of Publication: 2016
Abstract Precise control of electronic and/or ionic conductivity in electroceramics is crucial to achieve the desired functional properties as well as to improve manufacturing practices. We recently reported the conventional piezoelectric material Na1/2Bi1/2TiO3 (NBT) can be tuned into a novel oxide-ion conductor with an oxide-ion transport number (tion) > 0.9 by creating bismuth and oxygen vacancies. A small Bi-excess in the nominal starting composition (Na0.50Bi0.50+xTiO3+3x/2, x = 0.01) or Nb-donor doping (Na0.50Bi0.50Ti1−yNbyO3+y/2, 0.005 ≤ y ≤ 0.030) can reduce significantly the electrical conductivity to create dielectric behaviour by filling oxygen vacancies and suppressing oxide ion conduction (tion ≤ 0.10). Here we show a further increase in the starting Bi-excess content (0.02 ≤ x ≤ 0.10) reintroduces significant levels of oxide-ion conductivity and increases tion ∼ 0.4–0.6 to create mixed ionic/electronic behaviour. The switch from insulating to mixed conducting behaviour for x > 0.01 is linked to the presence of Bi-rich secondary phases and we discuss possible explanations for this effect. Mixed conducting behaviour with tion ∼ 0.5–0.6 can also be achieved with lower levels of Nb-doping (y ∼ 0.003) due to incomplete filling of oxygen vacancies without the presence of secondary phases. NBT can now be compositionally tailored to exhibit three types of electrical behaviour; Type I (oxide-ion conductor); Type II (mixed ionic-electronic conductor); Type III (insulator) and these results reveal an approach to fine-tune tion in NBT from near unity to zero. In addition to developing new oxide-ion and now mixed ionic/electronic NBT-based conductors, this flexibility in control of oxygen vacancies allows fine-tuning of both the dielectric/piezoelectric properties and design manufacturing practices for NBT-based multilayer piezoelectric devices.
Remark DOI: 10.1039/C6TC01719C
Link

Influence of cathode functional layer composition on electrochemical performance of solid oxide fuel cells

ID=355
Authors Antônio de Pádua Lima Fernandes, Eric Marsalha Garcia, Rubens Moreira de Almeida, Hosane Aparecida Taroco, Edyth Priscilla Campos Silva, Rosana Zacarias Domingues, Tulio Matencio
Source
Journal of Solid State Electrochemistry
Time of Publication: 2016
Abstract In this work, anode-supported solid oxide fuel cells (SOFC) were tested with a yttria-stabilized zirconia (YSZ) (8 mol% Y2O3-ZrO2)/gadolinium-doped ceria (GDC) (Ce0.9Gd 0.1O1.95) bilayer electrolyte and two lanthanum strontium cobalt ferrite (LSCF) composition as functional cathode layer: La0.6Sr0.4Co0.8Fe0.2O3-δ (LSCF 1) and La0.60Sr0.40Co0.2Fe0.8O3-δ (LSCF 2). The functional cathode layers were made of 50 % (w/w) LSCF and 50 % (w/w) GDC. Microstructural characterization was performed by scanning electron microscopy and X-ray diffraction. Electrochemical impedance spectroscopy (EIS) and power measurements were performed under oxygen and hydrogen atmospheres. The microscopy studies showed that the LSCF 2 functional layer is more uniform and adherent to the electrolyte and the cathode collector than the LSCF 1 functional layer, which has cracks, chips, and lower adhesion. The use of the LSCF 2 layer allowed an approximately 25-fold reduction in ohmic resistance (0.06 Ω cm−2) compared with the LSCF 1 layer (1.5 Ω cm−2). The power measurements showed a considerable increase in the power cell using LSCF 2 (approximately 420 mW cm−2) compared with the power cell using LSCF 1 (approximately 180 mW cm−2).
Keywords SOFC, LSCF, Interface, Electrochemical performance, Cathode, Functional layer
Remark First Online: 20 May 2016. DOI: 10.1007/s10008-016-3241-4
Link

Mechanical degradation under hydrogen of yttrium doped barium zirconate electrolyte material prepared with NiO additive

ID=354
Authors D. Ciria, M. Ben Hassine, M. Jiménez-Melendo, A. Iakovleva, P. Haghi-Ashtiani, V. Aubin, G. Dezanneau
Source
Journal of Power Sources
Volume: 321, Pages: 226–232
Time of Publication: 2016
Abstract Recently, a novel process was presented to fabricate dense yttrium-doped barium zirconate electrolytes with high proton conductivity. This process was based on the use of a NiO additive during reactive sintering. We show here that materials made from this process present a fast degradation of mechanical properties when put in hydrogen-rich conditions, while material made from conventional sintering without NiO aid remains intact in the same conditions. The fast degradation of samples made from reactive sintering, leading to sample failure under highly compressive conditions, is due to the reduction of NiO nanoparticles at grain boundaries as shown from structural and chemical analyses using Transmission Electron Microscopy. By the present study, we alert about the potential risk of cell failure due to this mechanical degradation.
Keywords PCFCs; Mechanical properties; BZY; Solid state reactive sintering
Remark doi:10.1016/j.jpowsour.2016.05.001
Link

Electrochemical Property Assessment of Pr2CuO4 Submicrofiber Cathode for Intermediate-Temperature Solid Oxide Fuel Cells

ID=353
Authors Ting Zhao, Li-Ping Sun, Qiang Li, Li-Hua Huo, Hui Zhao, Jean-Marc Bassat, Aline Rougier, Sébastien Fourcade and Jean-Claude Grenier
Source
Journal of Electrochemical Energy Conversion and Storage
Volume: 13, Issue: 1, Pages: 011006
Time of Publication: 2016
Abstract The Pr2CuO4 (PCO) submicrofiber precursors are prepared by electrospinning technique and the thermo-decomposition procedures are characterized by thermal gravity (TG), X-ray diffraction (XRD), Fourier transform infrared spectoscopy (FT-IR), and scanning electron microscopy (SEM), respectively. The fibrous PCO material was formed by sintering the precursors at 900 °C for 5 hrs. The highly porous PCO submicrofiber cathode forms good contact with the Ce0.9Gd0.1O1.95 (CGO) electrolyte after heat-treated at 900 °C for 2 hrs. The performance of PCO submicrofiber cathode is comparably studied with the powder counterpart at various temperatures. The porous microstructure of the submicrofiber cathode effectively increases the three-phase boundary (TPB), which promotes the surface oxygen diffusion and/or adsorption process on the cathode. The PCO submicrofiber cathode exhibits an area specific resistance (ASR) of 0.38 Ω cm2 at 700 °C in air, which is 30% less than the PCO powder cathode. The charge transfer process is the rate limiting step of the oxygen reduction reaction (ORR) on the submicrofiber cathode. The maximum power densities of the electrolyte-support single cell PCO|CGO|NiO-CGO reach 149 and 74.5 mW cm−2 at 800 and 700 °C, respectively. The preliminary results indicate that the PCO submicrofiber can be considered as potential cathode for intermediate temperature solid fuel cells (IT-SOFCs).
Remark doi: 10.1115/1.4033526
Link

Direct conversion of methane to aromatics in a catalytic co-ionic membrane reactor

ID=352
Authors S.H.Morejudo, R.Zanon, S.escolastico, I. Yuste-Tirados, H. Malerød-Fjeld, P.K. Vestre, W.G.Coors, A.Martinez, T.Norby, J.M.Serra, C.Kjølseth
Source
Science
Volume: 353, Issue: 6299, Pages: 563-566
Publisher: American Association for the Advancement of Science (AAAS), ISBN: Print ISSN:0036-8075 Online ISSN:1095-9203, Time of Publication: 2016-08
Abstract Nonoxidative methane dehydroaromatization (MDA: 6CH4 ↔ C6H6 + 9H2) using shape-selective Mo/zeolite catalysts is a key technology for exploitation of stranded natural gas reserves by direct conversion into transportable liquids. However, this reaction faces two major issues: The one-pass conversion is limited by thermodynamics, and the catalyst deactivates quickly through kinetically favored formation of coke. We show that integration of an electrochemical BaZrO3-based membrane exhibiting both proton and oxide ion conductivity into an MDA reactor gives rise to high aromatic yields and improved catalyst stability. These effects originate from the simultaneous extraction of hydrogen and distributed injection of oxide ions along the reactor length. Further, we demonstrate that the electrochemical co-ionic membrane reactor enables high carbon efficiencies (up to 80%) that improve the technoeconomic process viability. Methane gas is expensive to ship. It is usually converted into carbon monoxide and hydrogen and then liquefied. This is economically feasible only on very large scales. Hence, methane produced in small amounts at remote locations is either burned or not extracted. A promising alternative is conversion to benzene and hydrogen with molybdenumzeolite catalysts. Unfortunately, these catalysts deactivate because of carbon buildup; plus, hydrogen has to be removed to drive the reaction forward. Morejudo et al. address both of these problems with a solid-state BaZrO3 membrane reactor that electrochemically removes hydrogen and supplies oxygen to suppress carbon buildup.
Keywords CMR, MDA, catalytic membrane reactor, ZSM-5, MCM-22, FBR, FBR-PolyM, Pd-CMR, Co-ionic CMR, FT, ProboStat CMR base unit (NORECS)
Remark http://science.sciencemag.org/highwire/filestream/682540/field_highwire_adjunct_files/0/Morejudo.SM.pdf
BaZrO3
BaZrO3
Link

Magnetron-Sputtered YSZ and CGO Electrolytes for SOFC

ID=351
Authors A. A. Solovyev , A. V. Shipilova, I. V. Ionov, A. N. Kovalchuk, S. V. Rabotkin, V. O. Oskirko
Source
Journal of Electronic Materials
Time of Publication: 2016
Abstract Reactive magnetron sputtering has been used for deposition of yttria-stabilized ZrO2 (YSZ) and gadolinium-doped CeO2 (CGO) layers on NiO-YSZ commercial anodes for solid oxide fuel cells. To increase the deposition rate and improve the quality of the sputtered thin oxide films, asymmetric bipolar pulse magnetron sputtering was applied. Three types of anode-supported cells, with single-layer YSZ or CGO and YSZ/CGO bilayer electrolyte, were prepared and investigated. Optimal thickness of oxide layers was determined experimentally. Based on the electrochemical characteristics of the cells, it is shown that, at lower operating temperatures of 650°C to 700°C, the cells with single-layer CGO electrolyte are most effective. The power density of these fuel cells exceeds that of the cell based on YSZ single-layer electrolyte at the same temperature. Power densities of 650 mW cm−2 and 500 mW cm−2 at 700°C were demonstrated by cells with single-layer YSZ and CGO electrolyte, respectively. Significantly enhanced maximum power density was achieved in a bilayer-electrolyte single cell, as compared with cells with a single electrolyte layer. Maximum power density of 1.25 W cm−2 at 800°C and 1 W cm−2 at 750°C under voltage of 0.7 V were achieved for the YSZ/CGO bilayer electrolyte cell with YSZ and CGO thickness of about 4 μm and 1.5 μm, respectively. This signifies that the YSZ thin film serves as a blocking layer to prevent electrical current leakage in the CGO layer, leading to the overall enhanced performance. This performance is comparable to the state of the art for cells based on YSZ/CGO bilayer electrolyte.
Keywords Solid oxide fuel cell CGO YSZ bilayer electrolyte magnetron sputtering pulse electron-beam treatment
Remark Link

Characteristics of Cu and Mo-doped Ca3Co4O9−δ cathode materials for use in solid oxide fuel cells

ID=350
Authors Sea-Fue Wang, Yung-Fu Hsu, Jing-Han Chang, Soofin Cheng, Hsi-Chuan Lu
Source
Ceramics International
Time of Publication: 2016
Abstract In this study, Cu and Mo ions were doped in Ca3Co4O9−δ to improve the electrical conductivity and electrochemical behavior of Ca3Co4O9−δ ceramic and the performance of a solid oxide fuel cell (SOFC) single cell based on NiO-SDC/SDC/doped Ca3Co4O9−δ-SDC were examined. Cu substitution in the monoclinic Ca3Co4O9−δ ceramic effectively enhanced the densification, slightly increased the grain size, and triggered the formation of some Ca3Co2O6; however, no second phase was found in porous Mo-doped Ca3Co4O9−δ ceramics even when the sintering temperature reached 1050 °C. Substitution of Cu ions caused slight increase in the Co3+ and Co4+ contents and decrease in the Co2+ content; however, doping with Mo ions showed the opposite trend. Doping the Ca3Co4O9−δ ceramic with a small amount of Cu or Mo increased its electrical conductivity. The maximum electrical conductivity measured was 218.8 S cm−1 for the Ca3Co3.9Cu0.1O9−δ ceramic at 800 °C. The Ca3Co3.9Cu0.1O9−δ ceramic with a coefficient of thermal expansion coefficient of 12.1×10−6 K−1 was chosen as the cathode to build SOFC single cells consisting of a 20 μm SDC electrolyte layer. Without optimizing the microstructure of the cathode or hermetically sealing the cell against the gas, a power density of 0.367 Wcm−2 at 750 °C was achieved, demonstrating that Cu-doped Ca3Co4O9−δ can be used as a potential cathode material for IT-SOFCs.
Keywords Solid oxide fuel cell; Cathode; Impedance; Cell performance
Remark In Press, doi:10.1016/j.ceramint.2016.04.037
Link

Synthesis and characterization of robust, mesoporous electrodes for solid oxide fuel cells

ID=349
Authors Laura Almar, Alex Morata, Marc Torrell, Mingyang Gong, Meilin Liu, Teresa Andreu and Albert Tarancón
Source
Journal of Materials Chemistry A
Time of Publication: 2016
Abstract The use of mesoporous electrodes in solid oxide cells would lead to a significant enhancement of the performance due to their high surface area and large number of active sites for electrochemical reactions. However, their application in real devices is still hindered by the potential instability of the mesostructure and morphology at high temperatures required for device fabrication and under severe conditions for high-current, long-term operation. Here we report our findings on the preparation and characterization of mesoporous electrodes based on ceria infiltrated with catalysts: an anode consisting of a Ce0.8Sm0.2O1.9 (SDC) scaffold infiltrated with Ni and a cathode consisting of an SDC scaffold infiltrated with Sm0.5Sr0.5CoO3−δ (SSC). In particular, a doped-zirconia electrolyte supported cell with a mesoporous Ni–SDC anode and a mesoporous SSC–SDC cathode demonstrates an excellent peak power density of 565 mW cm−2 at 750 °C (using humidified hydrogen as the fuel). More importantly, both mesoporous electrodes display remarkable stability, yielding a combined electrode virtual non-degradation for the last 500 hours of the test at a constant current density of 635 mA cm−2 at 750 °C, demonstrating the potential of these mesoporous materials as robust electrodes for solid oxide fuel cells or other high-temperature electrochemical energy storage and conversion devices.
Remark DOI: 10.1039/C6TA00321D
Link

Fluorite-like compounds with high anionic conductivity in Nd2MoO6 – Bi2O3 system

ID=348
Authors E.P. Kharitonova, V.I. Voronkova, D.A. Belov, E.I. Orlova
Source
International Journal of Hydrogen Energy
Time of Publication: 2016
Abstract A wide range of (Bi2O3)x(Nd2O3)(1−x)/2(MoO3)(1−x)/2 solid solutions with the structure of the anion-conducting bismuth oxide was found in the Bi2O3–Nd2MoO6 join of ternary Bi2O3–MoO3–Nd2O3 system at 0.5 ≤ x ≤ 1. In said concentration range the compounds with large (0.92 ≤ x ≤ 0.98) and small (0.5 ≤ x < 0.6) bismuth content are tetragonal at room temperature. In the intermediate concentration range (0.67 ≤ x ≤ 0.9) cubic δ-Bi2O3 structure is stabilized at room temperature. It is shown that two tetragonal phases observed at different bismuth concentrations differ from each other in their polymorphism and behavior of the unit cell parameters. All the obtained compounds show high conductivity that reaches 0.1 S/cm (for a cubic sample with x = 0.8 at 800 °C).
Keywords Bi2O3; Nd2O3; MoO3; Polymorphism; Oxygen conductivity
Remark In press, doi:10.1016/j.ijhydene.2016.03.046
Link

Structural study and proton conductivity in BaCe0.7Zr0.25−xYxZn0.05O3 (x = 0.05, 0.1, 0.15, 0.2 & 0.25)

ID=347
Authors Ahmed Afif, Nikdalila Radenahmad, Chee Ming Lim, Mohamad Iskandar Petra, Md. Aminul Islam, Seikh Mohammad Habibur Rahman, Sten Eriksson, Abul Kalam Azad
Source
International Journal of Hydrogen Energy
Time of Publication: 2016
Abstract Solid oxide fuel cell (SOFC) has been considered to generate power represented by conductivity. Zinc doped Barium Cerium Zirconium Yttrium oxide (BCZYZn) has been found to offer high protonic conductivity and high stability as being electrolyte for proton-conducting SOFCs. In this study, we report a new series of proton conducting materials, BaCe0.7Zr0.25−xYxZn0.05O3 (x = 0.05, 0.1, 0.15, 0.2 and 0.25). The materials were synthesized by solid state reaction route and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), thermal expansion, particle size and impedance spectroscopy (IS). Rietveld analysis of the XRD data reveal a cubic perovskite structure with Pm-3m space group up to composition x = 0.15. For x = 0.15 and 0.20, the materials have structural phase change to orthorhombic in the Pbnm space group. Scanning electron microscopy images show high density materials. Thermal expansion measurements show that the thermal expansion coefficient is in the range 10.0–11.0 × 10−6/°C. Impedance spectroscopy shows higher ionic conduction under wet condition compared to dry condition. Y content of 25% (BCZYZn25) exhibits highest conductivity of 1.84 × 10−2 S/cm in wet Argon. This study indicated that perovskite electrolyte BCZYZn is promising material for the next generation of intermediate temperature solid oxide fuel cells (IT-SOFCs).
Keywords Proton conductor; Sinterability; Rietveld refinement; Conductivity; SOFC electrolyte
Remark In Press, doi:10.1016/j.ijhydene.2016.02.135
Link

Ca-doped fluorite-like compounds based on Nd5Mo3O16

ID=346
Authors V.I. Voronkova, E.P. Kharitonova, E.I. Orlova, A.V. Levchenko, A.M. Antipin, N.I. Sorokina, D.A. Belov
Source
Journal of Alloys and Compounds
Time of Publication: 2016
Abstract We have studied phase relations in a molybdenum oxide-rich region of the ternary system CaO–Nd2O3–MoO3. Using polycrystalline samples prepared by solid-state reactions in air, the system has been shown to contain a rather broad region of cubic fluorite-like phases isostructural with Nd5Mo3O16. The atomic structure of a calcium-doped fluorite-like Nd5Mo3O16+δ single crystal grown from an off-stoichiometric melt has been studied by X-ray diffraction. The peculiarities of the structure of calcium-doped fluorite-related compounds were revealed. Experimental structural data demonstrate partial mutual substitutions of Nd and Mo cations, splitting of the O2 position into several additional positions, and the presence of excess oxygen, which occupies octahedral sites in the voids of the structure. Some of the fluorite-like samples have high electrical conductivity, on the order of 10−2 S/cm at 800 °C.
Keywords Ceramics; Oxides; Crystal growth; Crystal structure; Ionic conductivity
Remark doi:10.1016/j.jallcom.2016.03.013
Link

Crystal structure and proton conductivity of BaSn0.6Sc0.4O3-δ: Insights from neutron powder diffraction and solid state NMR

ID=345
Authors Francis Gachau Kinyanjui, Stefan Tommy Norberg, Christopher Knee, Istaq Ahmed, Stephen Hull, Lucienne Buannic, Ivan Hung, Zhehong Gan, Frédéric Blanc, Clare P. Grey and Sten Eriksson
Source
Journal of Materials Chemistry A
Time of Publication: 2016
Remark DOI: 10.1039/C5TA09744D
Link

Optically-transparent and electrically-conductive AgI–AgPO3–WO3 glass fibers

ID=344
Authors Maxime Rioux, Yannick Ledemi, Jeff Viens, Steeve Morency, Seyed Alireza Ghaffari and Younès Messaddeq
Source
RSC Advances
Volume: 5, Pages: 40236-40248
Time of Publication: 2015
Abstract In this study, we report to our knowledge the first optically-transparent and electrically-conductive optical glass fiber belonging to the system AgI–AgPO3–WO3. The addition of tungsten oxide (WO3) into the phosphate glassy network allowed the adjustment of the glass transition temperature, thermal expansion coefficient, refractive index, optical band edge, and electrical conductivity, which are all very important parameters in view of drawing glass fibers with a desired set of electrical and optical properties. Furthermore, the addition of WO3 can improve considerably glass stability against water and humidity in the environment. AgI–AgPO3–WO3 glass fibers with 15 mol% WO3 showed 2 dB m−1 optical propagation loss from 800 to 950 nm wavelength range, and 10−3 S cm−1 electrical conductivity at 1 MHz AC frequency. Complex impedance spectra and thermal activation energies ranging from 0.15 to 0.30 eV are indicative of a dominant conductivity mechanism being ionic in nature within the range of AC frequencies from 1 Hz to 1 MHz. Fibers exhibited higher electrical conductivities than the bulk glasses. Glasses in the AgI–AgPO3–WO3 system can be used for fibers that require a set of adjustable properties pertaining to electrical conductivity, optical transparency, and environmental stability.
Remark DOI: 10.1039/C5RA00681C
Link

Phase Relations and Physical Properties of Layered Pb-Containing Nd2MoO6 Compounds

ID=343
Authors Valentina Voronkova, Ekaterina Orlova, Sergey Kazakov, Elena Kharitonova and Dmitry Belov
Source
European Journal of Inorganic Chemistry
Volume: 2016, Issue: 7, Pages: 1022-1029
Time of Publication: 2016
Abstract The phase relations along the Nd2MoO6–PbO join of the ternary Nd2O3–MoO3–PbO system have been studied by means of solid-state synthesis in air. The samples with high Pb content underwent a reversible first-order phase transition near 820 °C. XRD analysis revealed two tetragonal phases, the high-temperature centric phase (I41/acd) and the low-temperature acentric phase (Iequation image2m). In the region of the phase transition, the permittivity of the Pb-containing samples show a strong lambda-type anomaly and electrical conductivity increases sharply by one and half orders of magnitude. The conductivities of the Pb-containing samples reach 10–2 S/cm at 850 °C, which is two orders of magnitude greater than the conductivity of pure Nd2MoO6. The conductivity in such compounds may be due to oxygen ions. A permittivity anomaly, existence of a piezoelectric effect, and the symmetry change from acentric Iequation image2m to centric I41/acd may indicate an antiferroelectric nature of the phase transition.
Keywords Conducting materials;Layered compounds;Lead;Rare earths;Solid-phase synthesis
Remark DOI: 10.1002/ejic.201501167
Link

Phase stability and thermoelectric properties of Cu10.5Zn1.5Sb4S13 tetrahedrite

ID=342
Authors Subramaniam Harish, Duraisamy Sivaprahasama, Manjusha Battabyal, Raghavan Gopalan
Source
Journal of Alloys and Compounds
Volume: 667, Pages: 323–328
Time of Publication: 2016
Abstract Cu10.5Zn1.5Sb4S13 tetrahedrite compound was prepared by mechanical milling of Cu2S, ZnS and Sb2S3 powders and spark plasma sintered (SPS) to dense samples. The phase formation, chemical homogeneity, thermal stability of the compound and the thermoelectric properties of the sintered samples were evaluated. Single phase tetrahedrite with the crystallite size of 40 nm was obtained after 30 h of milling followed by annealing at 573 K for 6 h in an argon atmosphere. In-situ high-temperature X-ray diffraction studies revealed that the phase is stable up to 773 K. The Seebeck coefficient of the sintered samples of density >98% shows p-type behavior with maximum thermopower of 170 μV/K at 573 K. The electrical resistivity (ρ) decreases with temperature up to 475 K and then increases. A low thermal conductivity of 0.5 W/(m⋅K), in combination with moderate power factor gave a maximum ZT of ∼0.038 at 573 K in Cu10.5Zn1.5Sb4S13 sample having a grain size of ∼200 nm.
Keywords Thermoelectric; Tetrahedrite; Solid state reactions; Spark plasma sintering; Figure of merit
Remark doi:10.1016/j.jallcom.2016.01.094
Link

New ferroelastic K2Sr(MoO4)2: Synthesis, phase transitions, crystal and domain structures, ionic conductivity

ID=341
Authors Galina D. Tsyrenova, Erzhena Т. Pavlova, Sergey F. Solodovnikov, Nadezhda N. Popova, Tatyana Yu. Kardash, Sergey Yu. Stefanovich, Irina А. Gudkova, Zoya A. Solodovnikova, Bogdan I. Lazoryak
Source
Journal of Solid State Chemistry
Volume: 237, Pages: 64–71
Time of Publication: 2016
Abstract K2Sr(MoO4)2 crystals were synthesized and their properties examined. The distortive polymorphic transformations at 421 K (α (LT)→ β(MT)) and 744 K (β(MT)→γ (HT)) of K2Sr(MoO4)2 were studied. It has been shown that the transitions go in sequence from the high-temperature palmierite K2Pb(SO4)2-type γ-phase (R View the MathML source3¯m) to an intermediate β-phase with a probable incommensurate structure and then to a low-temperature α-phase. Domain structures peculiarities in ferroelastic α-K2Sr(MoO4)2 have been investigated. The electrical conductivity of K2Sr(MoO4)2 rises tenfold in the vicinity of the phase transition at 744 K that may be associated with a change conductivity path from quasi-one-dimensional to two-dimensional. The crystal structure of the α-phase (sp. gr. С2/c, а=14.318(3) Å, b=5.9337(12) Å, с=10.422(2) Å, β=105.83(3)°, Z=4, R=0.0219) is similar to that of α-Pb3(PO4)2. Sr-atoms are mainly located at site with the coordination number CN=8 (a tetragonal antiprism with bond lengths of 2.578(2)–2.789(2) Å) and K atoms are located at site with CN=9+1.
Keywords Potassium; Strontium; molybdates; Phase transitions; Ferroelastics; Crystal structure; Crystal optics analysis; Domain structure; Ionic conductivity
Remark doi:10.1016/j.jssc.2016.01.011
Link

New methods for the preparation and dielectric properties of Lа2 − xSrxNiO4 (х = 1/8) ceramic

ID=340
Authors T.I. Chupakhina, N.I. Kadyrova, N.V. Melnikova, O.I. Gyrdasova, E.A. Yakovleva, Yu.G. Zainulin
Source
Materials Research Bulletin
Volume: 77, Pages: 190–198
Time of Publication: 2016
Abstract The perovskite-type oxide La2−xSrxNiO4 (x = 1/8) was prepared by a new precursor route. The reaction proceeds in the self-ignition mode. Single-phase powder and gas-tight ceramic samples can be produced by single annealing of decomposition products. It was shown that as a result of thermobaric treatment of La2−xSrxNiO4 (x = 1/8) the solid solution La2−xSrxNiO4 with a higher concentration of strontium and the second phase La3Ni2O7 are formed. Short-term (5 min) thermobaric treatment (P = 2.5 GPa) at t° = 900 °С changes the unit cell parameters, but is not accompanied by structural transitions. At the same time, morphological restructuring of the sample occurs—the agglomerates delaminate into thin plates crystals. It was established that the permittivity of the material exposed to thermobaric treatment is much higher compared to that of the sample annealed at atmospheric pressure and virtually does not depend on frequency in a wide temperature range.
Keywords Oxides; X-ray diffraction; High pressure; Impedance spectroscopy; Dielectric properties
Remark doi:10.1016/j.materresbull.2016.01.023
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Chemical stability and H2 flux degradation of cercer membranes based on lanthanum tungstate and lanthanum chromite

ID=339
Authors Jonathan M. Polfus, , Zuoan Li, Wen Xing, Martin F. Sunding, John C. Walmsley, Marie-Laure Fontaine, Partow P. Henriksen, Rune Bredesen
Source
Journal of Membrane Science
Volume: 503, Pages: 42–47
Time of Publication: 2016
Abstract Ceramic–ceramic composite (cercer) membranes of (Mo-doped) lanthanum tungstate, La27(W,Mo)5O55.5−δ, and lanthanum chromite, La0.87Sr0.13CrO3−δ, have recently been shown to exhibit H2 permeabilities among state-of-the-art. The present work deals with the long-term stability of these cercer membranes in line with concern of flux degradation and phase instability observed in previous studies. The H2 permeability of disc shaped membranes with varying La/W ratio in the lanthanum tungstate phase (5.35≤La/W≤5.50) was measured at 900 and 1000 °C with a feed gas containing 49% H2 and 2.5% H2O for up to 1500 h. It was observed that the H2 permeability decreased by a factor of up to 5.3 over 1500 h at 1000 °C. Post-characterization of the membranes and similarly annealed samples was performed by SEM, STEM and XRD, and segregation of La2O3 was observed. The decrease in H2 permeability was ascribed to the compositional instability of the cation-disordered lanthanum tungstate under the measurement conditions. Equilibration of the La/W ratio by segregation of La2O3 leads to a lower ionic conductivity according to the materials inherent defect chemistry. Partial decomposition and reduction of the lanthanum tungstate phase, presumably to metallic tungsten, was also observed after exposure to nominally dry hydrogen.
Keywords Hydrogen separation; Dense ceramic membrane; Ceramic–ceramic composite; Lanthanum tungstate; Lanthanum chromite
Remark doi:10.1016/j.memsci.2015.12.054
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Nb-doped TiO2 sol–gel films for CO sensing applications

ID=338
Authors M. Duta, L. Predoana, J.M. Calderon-Moreno, S. Preda, M. Anastasescu, A. Marin, I. Dascalu, P. Chesler, C. Hornoiu, M. Zaharescu, P. Osiceanu, M. Gartner
Source
Materials Science in Semiconductor Processing
Volume: 42, Issue: 3, Pages: 397–404
Time of Publication: 2016
Abstract Nb doped titania (TiO2:Nb) multilayered films (1–10 layers) with anatase structure were obtained by the low-cost sol–gel and dipping method on microscope glass substrates, followed by thermal treatment at 450 °C for 1 h. After each layer deposition, an intermediate annealing step was performed at 300 °C for 30 min. Doping TiO2 sol–gel films with a low amount of Nb (0.8 at%) allows obtaining an improved CO sensor able to operate under environmental atmosphere (air). It was found that the sensor sensitivity is less dependent on the film thickness but is significantly influenced by Nb doping at the optimal working temperature of 400 °C. Good recovery characteristics were obtained for a wide CO detection range, between 0 and 2000 ppm. The gas-sensing behavior of the films was correlated with the structural, chemical and morphological properties of the multi-layered structures.
Keywords Sol–gel method; Nb-doped TiO2 films; Microstructure; CO sensor
Remark doi:10.1016/j.mssp.2015.11.004
Link
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