A low silica, barium borate glass-ceramic for use as seals in planar SOFCs

A low silica, barium borate glass-ceramic for use as seals in planar SOFCs containing 64 mol%BaO, 3 mol%Al₂O₃ and 3 mol%SiO₂ was studied. Coefficient of thermal expansion (CTE) between 275-550 °C, glass transition temperature (T_g), and dilatometric softening point (T_s) of the parent glass were 11.9 × 10⁻⁶ °C⁻¹, 552 °C, and 558 °C, respectively. Glass-ceramic was produced by devitrification heat treatment at 800 °C for 100 h. It was found that nucleation heat treatment, seeding by 3 wt%ZrO₂ as glass-composite and pulverization affected the amount, size and distribution of crystalline phases. SEM-EDS and XRD results revealed that crystalline phases presented in the devitrified glass-ceramic were barium aluminate (BaAl₂O₄), barium aluminosilicate (BaAl₂Si₂O₈) possibly with boron associated in its crystal structure, and barium zirconate (BaZrO₃). CTE of the devitrified glass-ceramic was in the range of (10.1-13.0) × 10⁻⁶ °C⁻¹. Good adhesion was obtained both in the cases of glass and devitrified glass-ceramic with YSZ and AISI430 stainless steel. Interfacial phenomena between these components were discussed.     

Synthesis optimization of organic xerogels produced from convective air-drying of resorcinol-formaldehyde gels

Resorcinol-formaldehyde gels were produced at 50, 70 and 90 °C and with three different R/C ratios (500, 1000 and 2000). The effect of these variables combined with that of aging time was studied in order to optimize the synthesis conditions. The convective air-drying process was used, and the drying duration was studied with regard to the synthesis conditions. The aging time has no effect on the pore texture after 24 h at 90 °C or 48 h at 70 °C, whatever the R/C value. The synthesis-aging step can be shortened by increasing the temperature. Nevertheless, the pore size tends then to decrease, especially when R/C is high, but this can be counterbalanced by increasing R/C. Moreover, bubbles often appear in the gel at high synthesis temperature, which limits the temperature to about 70 °C in the case of monolithic parts. At 70 °C and with an air velocity of 2 m/s, the elimination of 90% of the solvent requires 1 h drying when the pore size reaches 400-600 nm, 2.5 h for 50 nm wide pores and 3 h when the pore size decreases to 15-20 nm. The drying duration does not exceed 8 h in all cases and could be shortened by increasing the temperature at the end of the process.     

On the temperature dependence of the enthalpies of mixing in liquid binary (Ag, Cu, Ni)-Sn alloys

The partial and integral enthalpies of mixing of liquid binary alloys in the systems Ag-Sn, Cu-Sn and Ni-Sn were determined at different temperatures from 500 to 1500 °C using drop calorimetry techniques. Generally, our measured values fit well to most of the hitherto reported results. The data were fitted using a Redlich-Kister polynomial and the binary interaction parameters were evaluated. For all three systems the enthalpy curves at various temperatures are discussed focusing on the association theory. C^ass,C^A₁,B₁,C^A₁,A_iB_j,C^B₁,A_iB_j, the interaction parameters and K_AiBj were determined. The general shape and supposed temperature dependence of the enthalpy of mixing in Ag-Sn and Cu-Sn could be confirmed. No significant temperature dependence could be found experimentally for Ni-Sn at temperatures above 1100 °C. Extrapolations into the metastable liquid regions based on the association theory, however, indicate a small drop of Δ_MixH with temperature. A second series of measurements limited to low concentrations of Ag, Cu, or Ni, respectively in Sn has been performed in order to determine the partial enthalpies of mixing at infinite dilution at 500, 600, 700, and 800 °C. Temperature dependence could be observed for all three binary systems, most developed for Ni-Sn.     

Viscosity, relaxation and elastic properties of photo-thermo-refractive glass

Viscometry, ultrasonic echography and mechanical spectroscopy were applied to explore the thermo-mechanical properties of a photo-thermo-refractive (PTR) glass. Newtonian shear viscosity and ultrasonic velocity were used to determine the Maxwell time of structural relaxation. Two fast relaxation modes are found in PTR glass below glass transition temperature, which are attributed to alkali and mixed cation mobility. Respective activation energies, E_γ = 72 ± 4 kJ mol⁻¹ and E_β = 117 ± 4 kJ mol⁻¹, are considerably lower than that of viscous flow at the glass transition E_α ≈ 465 kJ mol⁻¹ as quantified from mechanical spectroscopy. Decoupling ratios of E_γ/E_α = 0.155 and E_β/E_α = 0.255 are similar to those of sodium trisilicate glass but at considerably longer timescales. These observations imply that β- and γ-relaxations are delayed as local structural arrangements are more complex for the multi-component PTR glass.     

1H-1,2,3-triazole,a promising precursor for chemical vapor deposition of hydrogenated carbon nitride

Well-crystallized hydrogenated carbon nitride thin films have been prepared by microwave plasma enhanced chemical vapor deposition (MWPECVD). 1H-1,2,3-triazole+N₂ and Si (1 0 0) were used as precursor and substrate, respectively. Substrate temperature during the deposition was recorded to be 850 °C. The synthesized samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photo-electron spectroscopy (XPS) analyses. The plasma compositions were checked by optical emission spectroscopy (OES). XRD observation strongly suggests that the films contain polycrystalline carbon nitride with graphitic structure of (1 0 0), (0 0 2), (2 0 0) and (0 0 4). XPS peak quantification reveals that the atomic ratio of the materials C:N:O:Si is 32:41:18:9. X-ray photo-electron peak deconvolution shows that the most dominant peak of C (1s) and N (1s) narrow scans correspond to sp² hybrid structure of C₃N₄. These observations indicate that 1H-1,2,3-triazole favors the formation of hydrogenated carbon nitride with graphitic phase by CVD method and thus is in good agreement with XRD results. SEM of surface and OES of plasma also support the formation of polycrystalline carbon nitride films from 1H-1,2,3-triazole+N₂ by CVD.     

Optical,structural investigations and band-gap bowing parameter of GaInN alloys

We have performed a detailed investigation of the photoluminescence features taken at 2 K on a series of Ga_xIn_1−xN alloys grown by metal-organic vapour-phase epitaxy through the whole composition range. The evolution of the photoluminescence lineshape of GaInN alloys in the indium-rich region is dominated by doping effects rather than by band-gap tailing effects correlated to existence of random chemical crystal inhomogeneities. The lineshape of the photoluminescence indicates a residual electron concentration of about 10¹⁸–10¹⁹ cm⁻³ in the bulk part of the epilayers. The value we get for the bowing parameter is b=2.8 eV.     

Thermal and optical investigation of EuF3-doped lead fluorogermanate glasses

Europium-doped lead germanate and lead fluorogermanate glasses are studied by using differential thermal analysis, X-ray diffraction, photoluminescence and fluorescence lifetimes measurements of the ⁵D_j, j = 0, 1, 2 levels. PbF₂ addition increases the thermal stability of the lead germanate glass, while Eu³⁺ ions promote the crystallization of β-PbF₂:Eu³⁺ nano-crystals embedded in a glassy matrix. In the lead fluorogermanate glasses, Eu³⁺ ions exhibit a strong affinity for F⁻ ions although oxygen ions are much more numerous. It appears that luminescence concentration quenching is not important, while cross relaxation is very efficient in the glasses. The results allow to propose for these glasses a molecular model in which small fluorine rich island, incorporating the Eu³⁺ ions in low symmetry sites, are separated from each other by chains of germanate (GeO₄)⁴⁻ ions linked together.     

Positron annihilation and broadband dielectric spectroscopy: A series of propylene glycols

We report a thorough joint analysis of the behavior of the ortho-positronium lifetime as obtained from positron annihilation lifetime spectroscopy and of the dipolar relaxation spectra investigated by broadband dielectric relaxation spectroscopy in a series of glass-forming propylene glycols including propylene glycol, dipropylene glycol and tripropylene glycol. A number of empirical correlations between the temperature dependence of the ortho-positronium annihilation lifetime, τ₃(T), and the various spectral and relaxational quantities have been found. The phenomenological evaluation of the quasi-sigmoidal τ₃(T) dependence reveals three characteristic temperatures: T_g^PALS, T_b1 = (1.23 − 1.27)T_g^PALS and T_b2 = (1.46 − 1.53)T_g^PALS, which are found to decrease with increasing fragility. The slighter change of slope in the PALS response at T_b1 in this series of propylene glycols appears to be related to the crossover from the α-process to the excess wing or secondary relaxation, found in the dielectric spectra. The onset of the high-temperature plateau in the τ₃(T) plot at T_b2 occurs when τ₃ matches the average relaxation time of the primary α process. Moreover, the plateau region lies in the vicinity of the crossover in the dielectric parameters of the structural relaxation in all the samples, i.e. spectral width and relaxation strength. In addition it is approximately related to a crossover of the α relaxation time τ_α(T) from non-Arrhenius to Arrhenius regime. In summary, all the empirical correlations support further very close connections between the PALS response and the dielectric relaxation behavior in the series of propylene glycols.     

Preparation of single-crystalline ZnO films on ZnO-buffered a-plane sapphire by chemical bath deposition

High-quality zinc oxide (ZnO) films were successfully grown on ZnO-buffered a-plane sapphire (Al₂O₃ (1 1 2¯ 0)) substrates by controlling temperature for lateral growth using chemical bath deposition (CBD) at a low temperature of 60 °C. X-ray diffraction analysis and transmission electron microscopy micrographs showed that the ZnO films had a single-crystalline wurtzite structure with c-axis orientation. Rocking curves (ω-scans) of the (0 0 0 2) reflections showed a narrow peak with full width at half maximum value of 0.50° for the ZnO film. A reciprocal space map indicated that the lattice parameters of the ZnO film (a=0.3250 nm and c=0.5207 nm) were very close to those of the wurtzite-type ZnO. The ZnO film on the ZnO-buffered Al₂O₃ (1 1 2¯ 0) substrate exhibited n-type conduction, with a carrier concentration of 1.9×10¹⁹ cm⁻³ and high carrier mobility of 22.6 cm² V⁻¹ s⁻¹.     

Effect of cooling rate on enthalpy and volume relaxation of polystyrene

This paper presents the results of measurements of physical aging on polystyrene with a narrow molecular weight distribution (M_w/M_n = 1.03). The evolution of the aging process was followed by recording the relaxed enthalpy and the accompanying decrease in volume, using differential scanning calorimetry and mercury-in-glass dilatometry, respectively. The measurements were carried out after cooling the sample at constant rate to the aging temperature. The cooling rate varied between 0.0037 and 1 °C/min. The aging data were fitted with the KWW and the TNM functions. The differences in the time scales of enthalpy, h, and volume, v, relaxation were relatively small. From the h(v) graphs the derivative dh/dv was found to amount to about 1.8 GPa, a value significantly exceeding the predictions of the thermodynamic model containing an additional internal variable.     

Metastable photoexpansion of hydrogenated amorphous silicon produced by exposure to short laser pulses

The study of the metastable expansion of hydrogenated amorphous silicon after exposure to nanosecond laser pulses as well as to cw light of similar average intensity has revealed a decrease from 1 to 0.5 in the short-time power-law exponent of photon flux dependence of the effect. This transition appears at a carrier generation rate of approximately G = 10²³ cm⁻³ s⁻¹ and is compatible with the assumption that the underlying structural change is produced by band-to-band/tail recombination of photo-excited carriers. This view is further supported by our observation that the quantum efficiency of photoexpansion does not depend on photon energy.     

Underlying reverse current mechanisms in a-Si:H p-i-n solar cell and compact SPICE modeling

The defect states in bulk of i-layer and at p⁺/i interface have been studied by using dark reverse current-voltage (J-V) measurements. The dark reverse current as a function of voltage has been analyzed on the basis of thermal generation of the carriers from mid-gap states in i-layer. Based on its behavior the thermal generation mechanism has been divided into two types. Thermal generation at lower bias (<5 V) shows V^1/2 behavior, whereas at higher bias follows an exponential dependence of voltage (>5 V). This was explained using a thermal generation zone at lower bias, which is a source of reverse currents, and its evolution towards p⁺/i interface with increasing voltage. The analytical result has shown that at lower reverse bias (V < 5 V) the defect states in the bulk of i-layer and at higher bias (V ∼ 25 V) the defect states at p⁺/i interface are contributing to the reverse currents. Reverse bias annealing (RBA) treatment which has been performed on these cells shows that a reduction of defect states more in the i-region near to the p⁺-layer and at p⁺/i interface as compared to the deep regions in bulk of i-layer. The calculated defect state density (DOS) is varying from its intrinsic value of 2.4 × 10¹⁷ cm⁻³ in the bulk of the i-layer up to 2.1 × 10¹⁹ cm⁻³ near and at p⁺/i interface. These values decrease to 7.1 × 10¹⁶ cm⁻³ and 2.7 × 10¹⁷ cm⁻³, respectively, in the samples annealed under reverse bias at 2 V. The bias dependent leakage current behavior has been modeled and implemented in simulation program with integrated circuit emphasis (SPICE) using simple circuit elements based on voltage controlled current sources (VCCS). Simulated and measured reverse leakage current characteristics are in reasonable agreement.     

Structure of potassium germanophosphate glasses by X-ray and neutron diffraction: 2. Medium-range order

Characteristics of the medium-range order (MRO) of K₂O-GeO₂-P₂O₅ (KGP) glasses are obtained from X-ray and neutron scattering data. The behavior of the MRO is expressed in changes of pre-peaks and smooth contributions in the structure factors, S(Q), for Q < 12 nm^-1. Peaks at Q = (7.5 ± 0.5) nm^-1 (Q - magnitude of the scattering vector) are the outstanding features and reach maximum intensity for a glass of ∼25/50/25 mol% K₂O/GeO₂/P₂O₅. The pre-peaks are explained by a structural model in which K-rich and Ge-rich regions are separated by PO₄ units. The distance of repetition of similar regions (∼1 nm) is responsible for the pre-peak at ∼7.5 nm^-1. The intensity of this pre-peak is reduced and finally eliminated for glass compositions approaching the binary GeO₂-P₂O₅ system. The pre-peak is changed to a smooth scattering contribution and finally shifted to ∼9 nm^-1 for glass compositions approaching the binary K₂O-GeO₂ system. The strong tendency of the PO₄ units to coordinate K⁺ and Ge neighbors at their four corners is the source for the special MRO of the KGP glasses.     

Influence of annealing on the physical properties of filtered vacuum arc deposited tin oxide thin films

Tin oxide (SnO₂) thin films were deposited on UV fused silica (UVFS) substrates using filtered vacuum arc deposition (FVAD). During deposition, the substrates were at room temperature (RT). As-deposited films were annealed at 400 and 600 °C in Ar for 30 min. The film structure, composition, and surface morphology were determined as function of the annealing temperature using X-ray diffraction (XRD), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The XRD patterns of the SnO₂ thin films deposited on substrates at RT indicated that the films were amorphous, however, after the annealing the film structure became polycrystalline. The grain size of the annealed films, obtained from the XRD analysis, increased with the annealing temperature, and it was in the range 8-34 nm. The AFM analysis of the surface revealed an increase in the film surface average grain size from 15 nm to 46 nm, and the surface roughness from 0.2 to 1.8 nm, as function of the annealing temperature. The average optical transmission of the films in the visible spectrum was >80%, and increased by the annealing ∼10%. The films’ optical constants in the 250-989 nm wavelength range were determined by variable angle spectroscopic ellipsometry (VASE). The refractive indexes of as-deposited and annealed films were in the range 1.83-2.23 and 1.85-2.3, respectively. The extinction coefficients, k(λ), of as-deposited and annealed films were in the range same range ∼0-0.5. The optical energy band gap (E_g), as determined by the dependence of the absorption coefficient on the photon energy at short wavelengths, increased with the annealing temperature from 3.90 to 4.35 eV. The lowest electrical resistivity of the as-deposited tin oxide films was 7.8 × 10⁻³ Ω cm, however, film annealing resulted in highly resistive films.     

Influence of TM and RE elements on glass formation of the ternary Al-TM-RE systems

The effects of TM and RE elements on glass formation ability (GFA) of the Al-TM-RE systems are studied systematically. The TM elements show distinct differences: critical sizes of the Al-TM-Ce systems are in the order of Ni > Co > Fe > Cu. However, the RE elements show similar effect on glass formation. These results are discussed in terms of the GFA-related factors, i.e., reduced glass transition temperature (T_rg = T_g (T_x)/T_L, where T_g, T_x and T_L are the glass transition temperature, onset crystallization temperature and liquidus temperature, respectively) and the mixing enthalpy ΔH_Al-TM. A new parameter of T_L − T_g (T_x) is potentially proposed and used to evaluate the GFA of the Al-based alloys, as well as bulk glass-formers.     

Johari-Goldstein relaxation as the origin of the excess wing observed in metallic glasses

Measurements of the shear loss modulus G″ of amorphous Zr₆₅Al_7.5Cu_27.5 at 5.4 kHz were reported by Rösner, Samwer and Lunkenheimer. They observed that the measured G″ are in excess of the contribution from the α-relaxation, indicating the existence of an ‘excess wing’ in amorphous metals like that found in molecular glass-formers. They speculated that the excess wing found in amorphous metal is due to the presence of an unresolved Johari-Goldstein (JG) secondary relaxation. In this work, the coupling model is used to calculate the temperature T_JG at which the JG relaxation frequency coincides with the experimental frequency of the isochronal measurement. The location of T_JG is well within the temperature range where the excess wing of Zr₆₅Al_7.5Cu_27.5 appears at 5.4 kHz. Hence, the result supports the assertion of Rösner et al. that the excess wing found in the metallic glass originates from the intrinsic JG relaxation.     

Preparation, phase transformation and microstructure of ZrxTi1−xO2 (x = 0.1-0.9) fine fibers

Zr_xTi_1−xO₂ (x = 0.1-0.9) fibers were prepared by the sol-gel dry-spinning method. Polyacetylacetonatozirconium (PAZ) and tetrabutyl titanate (C₁₆H₃₆O₄Ti) were used as raw materials. The green fibers were obtained from the amorphous spinnable solution and then heat-treated to convert into polycrystalline fibers. The main phase changes from TiO₂ to zirconium titanate (ZT) and then tetragonal ZrO₂ with increasing ZrO₂ content. The crystallization temperature varied with the molar ratio of Zr:Ti. The heat-treated fibers at 1050 °C have few pores and no cracks with diameters of 10-20μm and lengths of 1-5 cm.     

Generation and annealing of defects in virgin fused silica (type III) upon ArF laser irradiation: Transmission measurements and kinetic model

The transmission of ArF laser pulses in virgin fused silica (type III) samples changes during N = 10⁶ pulses at an incoming fluence H_in = 5 mJ cm⁻² pulse⁻¹. The related absorption is determined by the pulse energy absorption coefficient α(N, H_in) using a modified Beer’s law, yielding initial values α_ini around 0.005 cm⁻¹, a maximum α_max ? 0.02 cm⁻¹ at N = 10³-10⁴ and stationary values 0.0045 cm⁻¹ ? α_end ? 0.0094 cm⁻¹ after N ≈ 6 × 10⁵ pulses. The development α(N, H_in = const.) is simulated by a rate equation model assuming a pulse number dependent E′ center density E′(N). E′(N) is determined by a dynamic equilibrium between E′ center generation and annealing. Generation occurs photolytically from the precursors ODC II and unstable SiH structures upon single photon absorption and from strained SiO bonds via two-photon excitation. Annealing in the dark periods between the laser pulses is dominated by the reaction of E′ with H₂ present in the SiO₂ network. The development α(N, H_in = const.) is observed for the very first sample irradiation only (virgin state). The values α_end are not accessible by simple spectrophotometer measurements.     

Low-temperature RPCVD of Si,SiGe alloy,and Si1−yCy films on Si substrates using trisilane (Silcore)

Si homo-epitaxial growth by low-temperature reduced pressure chemical vapor deposition (RPCVD) using trisilane (Si₃H₈) has been investigated. The CVD growth of Si films from trisilane and silane on Si substrates are compared at temperatures between 500 and 950 °C. It is demonstrated that trisilane efficiency increases versus silane's one as the surface temperature decreases. Si epilayers from trisilane, with low surface roughness, are achieved at 600 and 550 °C with a growth rate equal to 12.4 and 4.3 nm min⁻¹, respectively. It is also shown that Si_1−xGe_x layers can be deposited using trisilane chemistry.     

Molecular dynamics in glass-forming poly(phenyl methyl siloxane) as investigated by broadband thermal,dielectric and neutron spectroscopy

The molecular dynamics of glass-forming poly(methyl phenyl siloxane) (PMPS) is studied by thermal (10⁻³–5 × 10² Hz), dielectric (10⁻³–10⁹ Hz) and neutron (5 × 10⁸–10¹² Hz) spectroscopy. Because of the broad frequency range of 15 orders of magnitude the study provides a precise determination of glassy dynamics in a wide temperature range using different probes. The relaxation rates extracted from the different methods agree quantitatively in both their absolute values and in their temperature dependencies. A detailed analysis of the temperature dependence of the relaxation rate f_p by a derivative technique shows that the α-relaxation of PMPS has to be characterized by a high and a low temperature branch separated by a crossover temperature T_B = 250 K. In both temperature ranges the temperature dependence of f_p has to be described by Vogel/Fulcher/Tammann laws with different Vogel temperatures. Also the analysis of the dielectric strength in its temperature dependence gives a crossover behavior from a low to a high temperature region with a similar value of T_B. T_B can be interpreted as onset of cooperative fluctuations and the formation of dynamical heterogeneities. The dependence of the relaxation rate on the scattering vector Q extracted from neutron scattering obeys a power law τ ∼ Q^−Slope, where the power Slope varies between Slope = 2 and Slope = 3.5 with increasing temperature. This anomalous dependence of the relaxation time on the momentum transfer is discussed in terms of dynamic heterogeneities in the underlying motional processes even at temperatures above T_B. Besides the segmental dynamics the fast Methyl group rotation is considered as well. The relaxation rates of this process have an activated temperature dependence with an activation energy of 8.3 kJ/mol. The data were discussed in the framework of the threefold jump model were the incoherent elastic scattering from ‘fixed’ atoms which are frozen on the time scale of the Methyl group rotation was taken into account.