Characteristics of ZnO-B2O3-SiO2-CaO glass frits prepared by spray pyrolysis as inorganic binder for Cu electrode

ZnO-B₂O₃-SiO₂-CaO glass frits were directly prepared by high temperature spray pyrolysis for use in Cu electrodes. The frits prepared at temperatures above 1400 °C were spherical, amorphous, of fine size and dense structure. The mean particle size and geometric standard deviation of the frits prepared at 1400 °C were 0.87 μm and 1.37, respectively. The temperatures of glass transition, crystallization and melting were 454, 534 and 800 °C, respectively. The glass layer fired at 800 °C had a dense structure due to the material's complete melting, despite some crystals being observed by SEM. A copper electrode formed from copper paste with glass frits had a dense structure when fired at 800 °C. The specific resistances of electrodes formed from copper paste with and without glass frits were 2.5 and 8.5 μΩ cm, respectively.     

Elaboration and characterization of Al doped ZnO nanorod thin films annealed in hydrogen

ZnO thin films doped with Al concentrations of 1.0, 2.0, 3.0, 4.0, 5.0 at% were prepared by a sol-gel spin-coating method on glass substrates and respectively annealed at 550 °C for 2 h in hydrogen and air. The X-ray diffraction and selected-area electron diffraction results confirm that the Al doped ZnO thin films are of wurtzite hexagonal ZnO. The scanning electron microscope results indicate that the Al doped ZnO nanorod thin films can be got by annealing in hydrogen rather than in air. The optical properties reveal that the Al doped ZnO thin films have obviously enhanced transmittance in the visible region. The electrical properties show that the resistivity of 1.0 at% Al doped ZnO thin films has been remarkably reduced from 0.73 Ω m by annealing in air to 3.2 × 10⁻⁵ Ω m by annealing in hydrogen. It is originated that the Al doped ZnO nanorod thin films annealed in hydrogen increased in electron concentration and mobility due to the elimination of adsorbed oxygen species, and multicoordinated hydrogen.     

New process for synthesis of ZnO thin films: Microstructural, optical and electrical characterization

Nanocrystalline ZnO thin films were prepared on glass substrates by using spin coating technique. The effect of annealing temperature (400-700 °C) on structural, compositional, microstructural, morphological, electrical and optical properties of ZnO thin films were studied by X-ray diffraction (XRD), Energy dispersive Spectroscopy (EDS), Atomic Force Microscopy (AFM), High Resolution Transmission Microscopy (HRTEM), Scanning Electron Microscopy (SEM), Electrical conductivity and UV-visible Spectroscopy (UV-vis). XRD measurements show that all the films are nanocrystallized in the hexagonal wurtzite structure and present a random orientation. The crystallite size increases with increasing annealing temperature. These modifications influence the optical properties. The AFM analysis revealed that the surface morphology is smooth. The HRTEM analysis of ZnO thin film annealed at 700 °C confirms nanocrystalline nature of film. The SEM results shows that a uniform surface morphology and the nanoparticles are fine with an average grain size of about 40-60 nm. The dc room temperature electrical conductivity of ZnO thin films were increased from 10⁻⁶ to 10⁻⁵ (Ω cm)⁻¹ with increase in annealing temperature. The electron carrier concentration (n) and mobility (μ) of ZnO films annealed at 400-700 °C were estimated to be of the order of 4.75-7.10 × 10¹⁹ cm⁻³ and 2.98-5.20 × 10⁻⁵ cm² V⁻¹ S⁻¹.The optical band gap has been determined from the absorption coefficient. We found that the optical band gap energy decreases from 3.32 eV to 3.18 eV with increasing annealing temperature between 400 and 700 °C. This means that the optical quality of ZnO films is improved by annealing.It is observed that the ZnO thin film annealing at 700 °C has a smooth and flat texture suited for different optoelectronic applications.     

Effects of the nickel-coated ferritic stainless steel for solid oxide fuel cells interconnects

In this study, a protective nickel layer was prepared on the SUS430 alloy substrate by the atmospheric plasma spraying technology (APS). Oxidation kinetics, area specific resistance (ASR) and interfacial microstructure of the SUS430 alloy with nickel layers as well as its elemental composition were studied under the flowing humidified hydrogen atmosphere at 800 °C to evaluate the effectiveness of the protective nickel layer. The current collector between the interconnect and the anode was optimized in this paper. Results showed that the oxide growth rate constant of the SUS430 alloy with the APS nickel layer was 1.99 × 10⁻¹⁴ g² cm⁻⁴ s⁻¹, which was only one fiftieth of that of the alloy without a protective layer. The ASR of the SUS430 alloy with the APS nickel layer was 12 mΩ cm² after being oxidized under the simulated SOFC anode operating atmosphere at 800 °C for 250 h. With the optimized structure of current collector, the contact ASR between the nickel-coated interconnect and the Ni-YSZ anode was only 3 mΩ cm² after being oxidized at 800 °C for 100 h.     

Study of post annealing influence on structural, chemical and electrical properties of ZTO thin films

Zinc-Tin-Oxide (ZTO) thin films were deposited on glass substrate with varying concentrations (ZnO:SnO₂; 100:0, 90:10, 70:30 and 50:50 wt.%) at room temperature by flash evaporation technique. These deposited ZTO films were annealed at 450 °C in vacuum. These films were characterized to study the effect of annealing and addition of SnO₂ concentration on the structural, chemical and electrical properties. The XRD analysis indicates that crystallization of the ZTO films strongly depends on the concentration of SnO₂ and post annealing where annealed films showed polycrystalline nature. Atomic force microscopy (AFM) images manifest the surface morphology of these ZTO thin films. The XPS core level spectra of Zn(2p), O(1s) and Sn(3d) have been deconvoluted into their Gaussian component to evaluate the chemical changes, while valence band spectra reveal the electronic structures of these films. A small shift in Zn(2p) and Sn(3d) core level towards higher binding energy and O(1s) core level towards lower binding energy have been observed. The minimum electrical resistivity (ρ ≈ 3.69 × 10⁻² Ω-cm), maximum carrier concentration (n ≈ 3.26 × 10¹⁹ cm⁻³) and Hall mobility (μ ≈ 5.2 cm² v⁻¹ s⁻¹) were obtained for as-prepared ZTO (50:50) film thereafter move towards lowest resistivity (ρ ≈ 1.12 × 10⁻³ Ω-cm), highest carrier concentration (n ≈ 2.96 × 10²⁰ cm⁻³) and mobility (μ ≈ 18.8 cm² v⁻¹ s⁻¹) for annealed ZTO (50:50) thin film.     

The corrosion of Fe3Al alloy in liquid zinc

A systematic study of the isothermal corrosion testing and microscopic examination of Fe₃Al alloy in liquid zinc containing small amounts of aluminum (less than 0.2 wt.%) at 450 °C was carried out in this work. The results showed the corrosion of Fe₃Al alloy in molten zinc was controlled by the dissolution mechanism. The alloy exhibited a regular corrosion layer, constituted of small metallic particles (diameter: 2-5 μm) separated by channels filled with liquid zinc, which represented a porosity of about 29%. The XRD result of the corrosion layer formed at the interface confirmed the presence of Zn and FeZn_6.67. The corrosion rate of Fe₃Al alloy in molten zinc was calculated to be approximately 1.5 × 10⁻⁷ g cm⁻² s⁻¹. Three steps could occur in the whole process: the superficial dissolution of metallic Cr in the corrosion layer, the new phase formation of FeZn_6.67 and the diffusion of the dissolved species in the channels of the corrosion layer.     

High strain rate superplasticity at intermediate temperatures of the Al 7075 alloy severely processed by equal channel angular pressing

The mechanical properties of an overaged Al 7075-O alloy processed by ECAP were examined by tensile tests at intermediate-high temperatures ranging from 250 to 400 °C and strain rates from 10⁻⁵ to 10⁻¹ s⁻¹. The influence of the number of ECAP passes on the ductility enhancement was evaluated. Elongation to failure, e_F, significantly increased with increasing the number of ECAP passes up to 8 at 130 °C. The alloy processed under these conditions exhibited a maximum value of 322% at 300 °C and an initial strain rate of 10⁻³ s⁻¹. High strain rate, e_F = 210%, at a strain rate as high as 10⁻² s⁻¹. The large elongations together with lower stresses and lower stress exponents than those for the start material confirm that grain boundary sliding (GBS) is the operative deformation mechanism. A loss of superplastic behaviour at temperatures above 350 °C is related to abnormal grain growth and a change of deformation mechanism.     

Y2O3-BaO-SiO2-B2O3-Al2O3 glass sealant for solid oxide fuel cells

A glass based on Y₂O₃-BaO-SiO₂-B₂O₃-Al₂O₃ (named YBA) has been investigated as sealant for planar solid oxide fuel cells (SOFCs). The YBA glass has been systematically characterized by differential thermal analysis, dilatometer, scanning electron microscopy, impedance analysis, and open circuit voltage to examine their suitability as sealant. The coefficient of thermal expansion of YBA is 11.64 × 10⁻⁶ K⁻¹ between 323 and 873 K. The resistivity is 9.1 × 10⁴ Ω cm at 800 °C. The glass sealant is found to be well adhered with other cell components, such as electrolytes and stainless steels, at an optimum sealing temperature of 800 °C. All measured results showed that the YBA glass appears to be a promising sealant for SOFCs.     

Electrical and thermal characterization of Sm doped ceria electrolytes synthesized by combustion technique

Nanocrystalline samarium doped ceria electrolyte [Ce_0.9Sm_0.1O_1.95] was synthesized by citrate gel combustion technique involving mixtures of cerium nitrate oxidizer (O) and citric acid fuel (F) taken in the ratio of O/F = 1. The as-combusted precursors were calcined at 700 °C/2 h to obtain fully crystalline ceria nano particles. It was further made into cylindrical pellets by compaction and sintered at 1200 °C with different soaking periods of 2, 4 and 6 h. The sintered ceria was characterized for the microstructures, electrical conductivity, thermal conductivity and thermal diffusivity properties. In addition, the combustion derived ceria powder was also analysed for the crystallinity, BET surface area, particle size and powder morphology. Sintered ceria samples attained nearly 98% of the theoretical density at 1200 °C/6 h. The sintered microstructures exhibit dense ceria grains of size less than 500 nm. The electrical conductivity measurements showed the conductivity value of the order of 10⁻² S cm⁻¹ at 600 °C with activation energy of 0.84 eV between the temperatures 100 and 650 °C for ceria samples sintered at 1200 °C for 6 h. The room temperature thermal diffusivity and thermal conductivity values were determined as 0.5 × 10⁻⁶ m² s⁻¹ and 1.2 W m⁻¹ K⁻¹, respectively.     

Transparent conducting oxide films of heavily Nb-doped titania by reactive co-sputtering

Niobium-doped titania (TNO) films of various Nb content were deposited on glass and silicon substrates by reactive co-sputtering of Ti and Nb metal targets. Nb content in the TNO films was varied from 0 to ∼13 at.% (atomic percent), corresponding to Ti_1−xNb_xO₂ with x = 0-0.52, by modulating the Nb target power from 0 to 150 W (Watts). The influence of ion bombardment on the TNO films was investigated by applying an RF substrate bias from 0 to 25 W. The as-deposited TNO films were all amorphous and insulating, but after annealing at 600 °C for 1 h in hydrogen, they became crystalline and conductive. The annealed films crystallized into either pure anatase or mixed anatase and rutile structures. The as-deposited and the annealed films were transparent, with an average transmittance above 70%. Anatase TNO film (Ti_1−0.39Nb_0.39O₂) with Nb 9.7 at.% exhibited a dramatically reduced resistivity of 9.2 × 10⁻⁴ Ω cm, a carrier density of 6.6 × 10²¹ cm⁻³ and a carrier mobility around 1.0 cm² V⁻¹ s⁻¹. In contrast, the mixed-phase Ti_1−0.39Nb_0.39O₂ showed a higher resistivity of 1.2 × 10⁻¹ Ω cm. This work demonstrates that the anatase phase, oxygen vacancies, and Nb dopants are all important factors in achieving high conductivities in TNO films.     

In situ diffraction study of thermal decomposition in Maxthal Ti2AlC

The thermal stability of Ti₂AlC at elevated temperature (1000-1550 °C) in vacuum has been investigated using in situ neutron diffraction. At temperatures above 1400 °C, Ti₂AlC became unstable and began to decompose via sublimation of Al, resulting in a porous surface layer of TiC_x being formed. The apparent activation energy for Ti₂AlC decomposition was determined to be 85.7 ± 2.6 kJ mol⁻¹. The kinetics of isothermal phase decomposition was modelled using least-squares linear regression fitting and the Avrami equation. The corresponding least-squares regression exponent (R²) and Avrami constants (k and n) for isothermal decomposition were determined to be 0.89, 0.268 min⁻ⁿ and 0.1, respectively.     

Effect of Cr7C3 on the mechanical, thermal, and electrical properties of Cr2AlC

In this work, phase pure Cr₂AlC and impure Cr₂AlC with Cr₇C₃ have been fabricated to investigate the mechanical, thermal, and electrical properties. The thermal expansion coefficient is determined as 1.25 × 10⁻⁵ K⁻¹ in the temperature range of 25-1200 °C. The thermal conductivity of the Cr₂AlC is 15.73 W/m K when it is measured at 200 °C. With increasing temperature from 25 °C to 900 °C, the electrical conductivity of Cr₂AlC decreases from 1.8 × 10⁶ Ω⁻¹ m⁻¹ to 5.6 × 10⁵ Ω⁻¹ m⁻¹. For the impure phase of Cr₇C₃, it has a strengthening and embrittlement effect on the bulk Cr₂AlC. And the Cr₂AlC with Cr₇C₃ would result in a lower high-temperature thermal expansion coefficient, thermal conductivity, specific heat capacity and electrical conductivity.     

Studies on the power factor of (Ba,Sr)Co2+xRu4−xO11 compounds

We have prepared polycrystalline single-phase ACo_2+xRu_4−xO₁₁ (A = Sr, Ba; 0 ≤ x ≤ 0.5) using the ceramic method and we have studied their structure, electrical resistivity and Seebeck coefficient, in order to estimate their power factor (P.F.). These layered compounds show values of electrical resistivity of the order of 10⁻⁵ Ωm and their Seebeck coefficients are positive and range from 1 μV K⁻¹ (T = 100 K) to 20 μV K⁻¹ (T = 450 K). The maximum power factor at room temperature is displayed by BaCo₂Ru₄O₁₁ (P.F.: 0.20 μW K⁻² cm⁻¹), value that is comparable to that shown by compounds such as SrRuO₃ and Sr₆Co₅O₁₅.     

SmBaCoCuO5+x as cathode material based on GDC electrolyte for intermediate-temperature solid oxide fuel cells

The performance of SmBaCoCuO_5+x (SBCCO) cathode has been investigated for their potential utilization in intermediate-temperature solid oxide fuel cells (IT-SOFCs). The powder X-ray diffraction (XRD), thermal expansion and electrochemical performance on Ce_0.9Gd_0.1O_1.95 (GDC) electrolyte are evaluated. XRD results show that there is no chemical reaction between SBCCO cathode and GDC electrolyte when the temperature is below 950 °C. The thermal expansion coefficient (TEC) value of SBCCO is 15.53 × 10⁻⁶ K⁻¹, which is ∼23% lower than the TEC of the SmBaCo₂O_5+x (SBCO) sample. The electrochemical impedance spectra reveals that SBCCO symmetrical half-cells by sintering at 950 °C has the best electrochemical performance and the area specific resistance (ASR) of SBCCO cathode is as low as 0.086 Ω cm² at 800 °C. An electrolyte-supported fuel cell generates good performance with the maximum power density of 517 mW cm⁻² at 800 °C in H₂. Preliminary results indicate that SBCCO is promising as a cathode for IT-SOFCs.     

Processing map for hot working of Inconel 718 alloy

Cylindrical specimens of Inconel 718 alloy with grain size of 90 μm were used in the compression tests and processing maps at the strains of 0.1, 0.3, 0.5 and 0.7 were developed at 950-1150 °C in the strain rate range 0.001-100 s⁻¹. Only one unstable region for adiabatic shear bands and one small dynamic recrystallization zone in the stable region are exhibited in the processing map at 0.1 strain. As the strain is beyond 0.3, there exist three unstable regions in the processing maps where one is for adiabatic shear bands and the other two are for intergranular cracking. At the same time, the zone of dynamic recrystallization with a peak efficiency of 0.39 at about 950 °C and 0.001 s⁻¹ in the stable region is enlarged and the distribution of which is from lower temperature and lower strain rate to higher ones. Optical micrographs of the specimens compressed to 0.7 strain show good agreement with the processing maps and main hot working schedules have been designed. Influence of initial grain size from 10 μm to 90 μm on the occurrence temperature of adiabatic shear bands and intergranular cracking has been analyzed at a strain rate of 100 s⁻¹ and in the temperature range 900-1200 °C.     

A facile and environment-friendly method to fabricate thin electrolyte films for solid oxide fuel cells

A facile and environment-friendly method, the so-called vertical deposition (abbreviated as VD) method, is used to prepare thin yttria-stabilized zirconia (YSZ) films (≤5 μm) for solid oxide fuel cells (SOFCs). The YSZ films are self-assembled by VD process based on capillary force. The influence of experimental conditions (e.g. concentration of YSZ dispersion, deposition times, and sintering procedure) on the morphology of the films produced and thereby on the performance of SOFC devices is investigated. The single cell utilizing a 5 μm dense YSZ film as solid electrolyte achieves a high open circuit voltage of 1.05 V which remains stable at 700 °C for 4 h. The peak power density is 0.4 W cm⁻² at 800 °C for the phase inversion anode-supported fuel cell composed of an YSZ electrolyte film of 5 μm thick. The VD method developed herein is promising for preparing ultra-thin electrolyte films for SOFCs.     

Growth of ZnO nanorods by air annealing of ZnO films with an applied electric field

A novel method of ZnO nanorods growth is presented based on low temperature (300 °C) air annealing of ZnO film while applying an electric field (∼ 10 V/cm) parallel to the film. The films were deposited on glass substrates using a filtered vacuum arc deposition system equipped with a Zn cathode, at an arc current of 160 A, oxygen pressure of 3.2 mTorr, and deposition time of 30 s. Cu tape electrodes were applied on each end of the coated sample, and used to apply the electric field. The samples were annealed in a quartz furnace at 200, 300, 400 °C for 20 or 60 min. Each sample surface was examined using a Scanning Electron Microscope (SEM) and a High Resolution SEM (HRSEM) to study its micro- and nano-structure. The film crystallographic structure was studied using X-ray diffractometry (XRD). ZnO rods with lengths of ∼ 3 μm were observed on the samples annealed at 300 °C for 20 min with an electric field of ∼ 10³ V/m, while separated conical forms with lengths of ∼ 0.5 μm and base width of ∼ 150 nm were observed after annealing under the same conditions but without any electric field. The rod growth rate and area density were ∼ 2.0-2.5 nm/s, and ∼ 3 × 10⁷ cm^− 2, respectively.     

Structural, optical and electrical properties of N-doped ZnO thin films prepared by thermal oxidation of pulsed filtered cathodic vacuum arc deposited ZnxNy films

In this study, N-doped ZnO thin films were fabricated by oxidation of Zn_xN_y films. The Zn_xN_y thin films were deposited on glass substrates by pulsed filtered cathodic vacuum arc deposition (PFCVAD) using metallic zinc wire (99.999%) as a cathode target in pure nitrogen plasma. The influence of oxidation temperature, on the electrical, structural and optical properties of N-doped ZnO films was investigated. P-type conduction was achieved for the N-doped ZnO obtained at 450 °C by oxidation of Zn_xN_y, with a resistivity of 16.1 Ω cm, hole concentration of 2.03 × 10¹⁶ cm⁻³ and Hall mobility of 19 cm²/V s. X-ray photoelectron spectroscopy (XPS) analysis confirmed the incorporation of N into the ZnO films. X-ray diffraction (XRD) pattern showed that the films as-deposited and oxidized at 350 °C were amorphous. However, the oxidized films in air atmosphere at 450-550 °C were polycrystalline without preferential orientation. In room temperature photoluminescence (PL) spectra, an ultraviolet (UV) peak was seen for all the samples. In addition, a broad deep level emission was observed.     

Dense La0.9Sr0.1Ga0.8Mg0.2O2.85 electrolyte for IT-SOFC's: Sintering study and electrochemical characterization

This paper presents the sintering behaviour of a La_0.9Sr_0.1Ga_0.8Mg_0.2O_2.85 coral-like microstructure powder. This is prepared by a successive freeze-drying and self-ignition process followed by calcination at 1200 °C during 1 h. This synthesis method gives great uniformity of the powder and allows shaping into compacts without requiring a grinding step. The grain size distribution (between 0.5 and 4 μm) favours a good sintering behaviour: open porosity disappear at 1400 °C and relative densities over 99% can be achieved after 6 h at 1450 °C. The same powder can also be sintered into a thin disc of ∼100 μm thickness. The characterization of the dense material by impedance spectroscopy shows that the activation energies below and above 600 °C are 1.0 eV and 0.7 eV, respectively. The conductivity at 800 °C is ∼0.11 S cm⁻¹. Special attention is devoted to the temperature range between 200 °C and 400 °C, where the intragrain and intergrain contributions can be distinguished. The analysis of the parameters describing the intragrain constant phase element in the equivalent circuit suggests that, above 325 °C, the system evolves from a distribution of relaxation time to only one relaxation time. The analysis of the data by the complexes permittivity show that ionic oxide conduction mechanism would occur in two steps. In the first, an oxygen vacancy would be released and, in the second, the migration of the ionic oxide would take place in the material.     

Structural, morphological and electrical properties of spray deposited nano-crystalline CeO2 thin films

Nanocrystalline, uniform, dense, and adherent cerium oxide (CeO₂) thin films have been successfully deposited by a simple and cost effective spray pyrolysis technique. CeO₂ films were deposited at low substrate and annealing temperatures of 350 °C and 500 °C, respectively. Films were characterized by differential thermal analysis, X-ray diffraction, scanning electron microscopy, atomic force microscopy; two probe resistivity method and impedance spectroscopy. X-ray diffraction analysis revealed the formation of single phase, well crystalline thin films with cubic fluorite structure. Crystallite size was found to be in the range of 10-15 nm. AFM showed formation of smooth films with morphological grain size 27 nm. Films were found to be highly resistive with room temperature resistivity of the order of 10⁷ Ω cm. Activation energy was calculated and found to be 0.78 eV. The deposited film showed high oxygen ion conductivity of 5.94 × 10⁻³ S cm⁻¹ at 350 °C. Thus, the deposited material shows a potential application in intermediate temperature solid oxide fuel cells (IT-SOFC) and might be useful for μ-SOFC and industrial catalyst applications.