Mechanical behavior of La0.8Sr0.2Ga0.8Mg0.2O3 perovskites

This paper examines the important mechanical properties of commercially purchased La_0.8Sr_0.2Ga_0.8Mg_0.2O₃ at room temperature and 800 °C. Sr and Mg-doped lanthanum gallates (LSGM) are strong candidates for use as solid electrolytes in lower temperature solid oxide fuel cells operating at or below 800 °C. The material was found to be phase pure with a Young's modulus value of ∼175 GPa. The four point bending strength of the LSGM samples remained almost constant from 121 ± 35 MPa at room temperature to 126 ± 20 MPa at 800 °C. The fracture toughness, as measured by the single edge V notch beam (SEVNB) method, was 1.22 ± 0.06 MPa√m at room temperature, 1.04 ± 0.09 MPa√m at 700 °C followed by a small increase 1.31 ± 0.16 MPa√m at 800 °C. We also report, for the first time, the static subcritical (or slow) crack-growth (SCG) behavior of natural cracks in LSGM performed in four point bending tests at room temperature. The exponent of a power-law representation in the SCG tests was found to be n = 15, a rather low value showing LSGM to be highly susceptible to room temperature SCG.     

Microstructure and dielectric properties of Dy/Mn doped BaTiO3 ceramics

Dy/Mn doped BaTiO₃ with different Dy₂O₃ contents, ranging from 0.1 to 5.0 at% Dy, were investigated regarding their microstructural and dielectric characteristics. The content of 0.05 at% Mn was constant in all the investigated samples. The samples were prepared by the conventional solid state reaction and sintered at 1290°, and 1350 °C in air atmosphere for 2 h. The low doped samples (0.1 and 0.5 at% Dy) exhibit mainly fairly uniform and homogeneous microstructure with average grain sizes ranged from 0.3 μm to 3.0 μm. At 1350 °C, the appearance of secondary, abnormal, grains in the fine grain matrix and core–shell structure were observed in highly doped Dy/BaTiO₃. Dielectric measurements were carried out as a function of temperature up to 180 °C. The low doped samples sintered at 1350 °C, display the high value of dielectric permittivity at room temperature, 5600 for 0.1Dy/BaTiO₃. A nearly flat permittivity–temperature response was obtained in specimens with 2.0 and 5.0 at% additive content. Using a Curie–Weiss and modified Curie–Weiss low, the Curie constant (C), Curie like constant (C′), Curie temperature (T_C) and a critical exponent (γ) were calculated. The obtained values of γ pointed out the diffuse phase transformation in highly doped BaTiO₃ samples.     

Effects of sintering temperature and poling conditions on the electrical properties of Ba0.70Ca0.30TiO3 diphasic piezoelectric ceramics

The effects of sintering temperature and poling conditions on the electrical properties of tetragonal and orthorhombic diphasic Ba_0.70Ca_0.30TiO₃ (BCT) lead-free ceramics have been systematically investigated. On the one hand, with increasing sintering temperature from 1270 °C to 1400 °C, the bulk density increases monotonically and the Curie temperature keeps almost constant with the value of ∼120 °C, whereas the grain size, the maximum relative dielectric constant, room temperature polarization reach the maximum values for samples sintered at 1340 °C. On the other hand, it is found that the piezoelectric property depends on poling electric field and poling temperature significantly. An enhanced piezoelectric behavior of d₃₃=126 pC/N, k_p=0.29, and Q_m=588 is obtained for the BCT ceramics poled at 100 °C with 30 kV/cm field for 20 min. The aging behavior of the piezoelectric property is also investigated.     

Effect of Bi2O3 additives on sintering and microwave dielectric behavior of La(Mg0.5Ti0.5)O3 ceramics

Bi₂O₃ was selected as liquid phase sintering aid to lower the sintering temperature of La(Mg_0.5Ti_0.5)O₃ ceramics. The sintering temperature of La(Mg_0.5Ti_0.5)O₃ ceramics is generally high, about 1600 °C. However, the sintering temperature was significantly lowered about 275 °C from 1600 °C to 1325 °C by incorporating in 15 mol% Bi₂O₃ and revealed the optimum microwave dielectric properties of dielectric constant (?_r) value of 40.1, a quality factor (Q × f) value of 60,231 GHz, and the temperature coefficient (τ_f) value of 70.1 ppm/°C. During all addition ranges, the relative dielectric constants (?_r) were different and ranged from 32.0 to 41.9, the quality factors (Q × f) were distributed in the range of 928–60,231 GHz, and the temperature coefficient (τ_f) varies from 0.3 ppm/°C to 70.3 ppm/°C. Noticeably, a nearly zero τ_f can be found for doping 5 mol% Bi₂O₃ sintering at 1325 °C. It implies that nearly zero τ_f can be achieved by appropriately adjusting the amount of Bi₂O₃ additions and sintering temperature for La(Mg_0.5Ti_0.5)O₃ ceramics.     

Analysis of structural and thermal properties of Li2TiO3 ceramic powders

Li₂TiO₃ ceramic powders have been developed by a solid state reaction method and those have been sintered at four different temperatures (600 °C, 700 °C, 800 °C and 900 °C) towards the optimization of sintering temperature that has been found to be at 800 °C based on the nature of the XRD profiles. The sample sintered at 800 °C has shown a good crystallinity situation from its XRD peaks and the sample is found to be in monoclinic structure which is in accordance with the reported data of JCPDS 33-0831. The SEM images for samples sintered at 600 °C, 700 °C, 800 and 900 °C, EDAX peaks, FTIR profile have been measured for the temperature optimized (800 °C) sample for understanding the structural details of Li₂TiO₃ ceramic powders. Besides these, dielectric constant, dielectric loss and a.c. conductivities have been measured for the temperature optimized sample. In order to strengthen the observations made in the XRD profiles at four different temperatures, Raman spectra of those four sintered ceramic powders have also been studied. In respect of the thermal properties, only for the as synthesized (precursor) sample, simultaneous measurement of TG-DTA profiles has been carried out for analysis.     

Comparison of the superconducting properties of Cu0.5Tl0.5Ba2Ca2(Cu3−yZny)O10−δ prepared at different synthesis temperatures

The superconducting properties of Zn-doped Cu_0.5Tl_0.5Ba₂Ca₂(Cu_3−yZn_y)O_10−δ {CuTlZn-1223} (y=0, 0.83, 1.66, 2.5) samples prepared at 820, 830, 850 and 860 °C have been compared. The samples were investigated by x-ray diffraction (XRD), dc-resistivity, ac-susceptibility and Fourier Transform Infrared (FTIR) absorption measurements. Almost all the superconducting properties have been increased to their maximum in all CuTlZn-1223 samples synthesized at 860 °C, which shows that 860 °C is the optimum temperature to achieve CuTlZn-1223 with enhanced superconducting properties.     

Phase structure and nano-domain in high performance of BaTiO3 piezoelectric ceramics

BaTiO₃ ceramics were prepared by conventional sintering technique with a special emphasis on the effects of sintering temperature (1100-1230 °C) on the crystalline structure and piezoelectric properties. XRD patterns indicated that the crystallographic structure changed from tetragonal phase to orthorhombic one with raising sintering temperature from 1160 °C to 1180 °C. Domains were shaped in a stripe and a herringbone in orthorhombic samples for BaTiO₃ ceramics. The domain width and domain density increased with raising sintering temperature. The BaTiO₃ ceramic sintered at 1190 °C showed the excellent electrical properties, d₃₃ = 355 pC/N, k_p = 40%, P_r = 10.2 μC/cm², respectively, which are originated to the contributions of both the crystallographic structure transition and nano-domain.     

Synthesis, preparation and properties of novel high-performance allyl-maleimide resins

Three novel allyl-maleimide monomers (i.e., A₂B, AB and AB₂) were designed, synthesized and thermally cured to yield a series of high-performance allyl-maleimide resins. All the monomers obtained are readily soluble in common organic solvents enabling an easy solution processing. The thermal properties of the three monomers were studied by the differential scanning calorimetry (DSC). A₂B and AB showed fairly low melting temperature (T_m < 90 °C) and wide processing window ranging from 90 °C to 260 °C. The thermal stability of the cured allyl-maleimide resins (i.e., PA₂B, PAB and PAB₂) was studied by the thermogravimetric analysis (TGA). Dynamic mechanical analysis (DMA) was used to investigate the dynamic mechanical properties of the composites based on the cured allyl-maleimide resins. PA₂B and PAB₂ showed good glass transition temperatures (T_g > 270 °C) and their corresponding composites showed high bending modulus (E′ > 1900 MPa). Allyl-compound-modified BMI resins based on AB monomer were prepared. Rheometer revealed that the processability of the prepolymer (BR-AB-pre) was improved by the addition of AB monomer. The cured BMI resins (BR and BR-AB) showed good thermal stability (T_d > 400 °C, both in nitrogen and in the air), high glass transition temperature (T_g > 320 °C), and good mechanical properties and low water uptake (<2.6%, 120 h).     

Effect of Ni substitution on electrical and thermoelectric properties of LaCoO3 ceramics

LaCo_1−xNi_xO₃ (0 ≤ x ≤ 0.2) ceramics were prepared by solid state reaction and their thermoelectric properties were investigated from room temperature (RT) to 400 °C. In the range from RT to 180 °C, LaCoO₃ showed a large negative Seebeck coefficient, but it changed to a positive value above 180 °C. However, the Seebeck coefficient became positive in the whole investigated temperature span due to Ni substitution for Co even for a tiny amount, but its absolute value decreased significantly with increasing Ni content. The LaCo_0.9Ni_0.1O₃ composition showed an enhanced power factor with a maximum value of 1.41 × 10⁻⁴ W m⁻¹ K⁻² at room temperature, which is about 3.5 times higher than that of un-doped LaCoO₃. Because the power factor decreased and the thermal conductivity increased apparently with temperature, the ZT values were not increased at elevated temperatures, in spite of a relatively large ZT value of 0.031 at a low temperature (50 °C) obtained in the composition LaCo_0.9Ni_0.1O₃.     

Densification and characterization of SiO2B2O3CaOMgO glass/Al2O3 composites for LTCC application

A glass/ceramic composite using lead-free low melting glass (SiO₂B₂O₃CaOMgO glass) with Al₂O₃ fillers was investigated. X-ray diffraction analysis revealed that the anorthite and cordierite phase appeared in the sintered composites. The dilatometric analysis showed that the onset of shrinkage took place at ∼624 °C for all the samples and the onset temperature was independent on the content of glass. The low melting glass significantly promoted densification of the composites and lowered the sintering temperature to ∼875 °C. The addition of 50 wt% glass sintered at 875 °C showed ε_r of 7.3, tan δ of 1.15×10⁻³, TEC of 5.41 ppm/°C, thermal conductivity of 3.56 W/m °C, and flexural strength of 184 MPa. The results showed that the SiO₂B₂O₃CaOMgO glass/Al₂O₃ composites were strong potential candidates for low temperature cofired ceramic substrate applications.     

Preparation and properties of yttrium-doped SrTiO3 anode materials

Direct electrochemical oxidation of hydrocarbon fuels is a current development trend of solid oxide fuel cells (SOFCs) and finding new anode materials for this application is a key issue. In this study, promising candidates, Y₂O₃-doped SrTiO₃ perovskite compounds Sr_1−1.5xY_xTiO₃ (x = 0.02, 0.04, 0.06, 0.08, 0.10), were synthesized by solid-state reaction. The structure of the calcined powders was examined by X-ray diffraction (XRD). The sinterability and high temperature conductivity were measured by the Archimedes principle and a dc four-probe method, respectively. The effect of sintering temperature on the electrical conductivity was studied. The results indicated that the optimal sintering temperature is around 1400 °C. From 400 °C to 1000 °C, the conductivity decreased with increasing temperature. At 800 °C the highest conductivity (26.8 S/cm) was observed for x = 0.08.     

Synthesis of spherical shape borate-based bioactive glass powders prepared by ultrasonic spray pyrolysis

Spherical shape borate-based bioactive glass powders with fine size were directly prepared by high temperature spray pyrolysis. The powders prepared at temperatures between 1200 and 1400 °C had mixed phase with small amounts of fine crystal and an amorphous rich phase. Glass powders with amorphous phase were prepared at a temperature of 1500 °C. The mean size of the glass powders prepared by spray pyrolysis was 0.76 μm. The glass powders prepared at a temperature of 1200 °C had two distinct exothermic peaks (T_c1 and T_c2) at temperatures of 588 and 695 °C indicating crystallization. The glass transition temperature (T_g) of the powders prepared at a temperature of 1200 °C was 480 °C. Phase-separated crystalline phases with spherical shape were observed from the surface of the pellet sintered at a temperature of 550 °C. Crystallization of the pellet was completely occurred at temperatures of 750 and 800 °C. The pellets sintered at temperatures below 700 °C had single crystalline phase of CaNa₃B₅O₁₀. The pellet sintered at a temperature of 800 °C had two crystalline phases of CaNa₃B₅O₁₀ and CaB₂O₄.     

High permeability Ni-Cu-Zn ferrites through additive-free low-temperature sintering of nanocrystalline powders

Nanocrystalline Ni-Cu-Zn ferrite powders Ni_0.20Cu_0.20Zn_0.62Fe_1.98O_3.99 were prepared by thermal decomposition of an oxalate precursor. The particle size is 6 nm and 350 nm, respectively, for powders obtained through calcinations at 350 °C or 750 °C. The shrinkage behavior significantly changes with particle size; the temperature of maximum shrinkage rate is T_MSR = 700 °C for particles of 6 nm size and increases to T_MSR = 880 °C for particles 350 nm in size. Dense samples with a permeability of μ = 780 are obtained by sintering at 900 °C for 2 h. Mixtures of nanocrystalline and sub-micron powders allow tailoring of the shrinkage behavior. A maximum permeability of μ = 840 is obtained after sintering of a 1:1-mixture at 900 °C. This demonstrates the potential of nanocrystalline ferrites for co-firing without additives at 900 °C and integration of ferrite inductors into LTCC modules.     

Free-radical propagation and termination kinetics of the butyl acrylate dimer studied by pulsed laser polymerization techniques

The propagation and termination rate coefficients for bulk polymerization of the butyl acrylate dimer (BA dimer) are determined by pulsed laser techniques. The rate coefficient for propagation, k_p, is deduced for temperatures from 20 to 90 °C via the pulsed laser polymerization-size exclusion chromatography (PLP-SEC) method at pulse repetition rates between 1 and 10 Hz. The Arrhenius parameters were found to be: E_A(k_p) = (34.2 ± 1.0) kJ mol⁻¹ and A(k_p)/L mol⁻¹ s⁻¹ = (1.08 ± 0.49) × 10⁷ L mol⁻¹ s⁻¹. The termination rate coefficient, k_t, has been measured via SP-PLP-ESR, single pulse-pulsed laser polymerization in conjunction with time-resolved electron spin resonance detection of radical concentration. The resulting Arrhenius parameters as deduced from the temperature range −15 to +30 °C are: E_A(〈k_t〉) = (22.8 ± 3.7) kJ mol⁻¹ and log(A/L mol⁻¹ s⁻¹) = 10.6 ± 1. The chain-length dependence of k_t was studied at 30 °C. For short chains a significant dependence was found which may be represented by an exponent α = 0.79 in the power-law expression k_t(i) = k_t⁰i^−α.     

Effects of CaTiO3 addition on the densification and microwave dielectric properties of BiSbO4 ceramics

In this study, the effects of CaTiO₃ addition on the sintering characteristics and microwave dielectric properties of BiSbO₄ were investigated. Pure BiSbO₄ achieved a sintered density of 8.46 g/cm³ at 1100 °C. The value of sintered density decreased with increasing CaTiO₃, and sintering at a temperature higher than 1100 °C led to a large weight loss (>2 wt%) caused by the volatile nature of the compound. Samples either sintered above 1100 °C or with a CaTiO₃ content exceeding 3 wt% showed poor densification. SEM micrographs revealed microstructures with bimodal grain size distribution. The size of the smaller grains ranged from 0.5 to 1.2 μm and that of the larger grains between 3 and 7 μm. The microwave dielectric properties of the (1−x) BiSbO_4−x CaTiO₃ ceramics are dependent both on the x value and on the sintering temperature. The 99.0 wt% BiSbO₄–1.0 wt% CaTiO₃ ceramic sintered at 1100 °C reported overall microwave dielectric properties that can be summarized as ε_r≈21.8, Q×f≈61,150 GHz, and τ_f≈−40.1 ppm/°C, all superior to those of the BiSbO₄ ceramics sintered with other additives.     

Radiochemical ageing of an amine cured epoxy network. Part I: change of physical properties

An aromatic rich, amine cured epoxy network (initial glass transition temperature 250 °C), was irradiated in air (pressure 0.22 MPa), at 30 and 120 °C, by gamma rays with two dose rates 2 and 20 kGy/h, for doses upto 70 MGy. The following characteristics were recorded, thickness of oxidised layer (TOL) from IR microspectrophotometry, flexural strength σ_R, toughness K_IC and glass transition temperature T_g. σ_R decreases from 120 MPa to about 40 MPa in the most degraded samples. This decrease is sharply linked to TOL showing the key role of the oxidised layer in crack initiation. K_IC decreases from 0.7 to 0.55 MPa m^1/2. Data are too much scattered to allow a kinetic study but it appears that, in the early period of exposure, K_IC decreases more rapidly at 120 °C than at 30 °C. T_g decreases from 250 to 140 °C in the most degraded samples, and the decrease is faster at 30 °C than at 120 °C. The decrease of T_g is attributed to a predominant chain scission process. The decrease of K_IC can be attributed to a combination of chain scission and physical ageing or chain scission and crosslinking. A relationship between T_g and the number of chain scissions, derived from the Di Marzio's theory, is proposed.     

Development of metal oxide nanoparticles by soft chemical method

An extensive work for the study of SnO₂ samples doped with x-mol% of Sb (x = 0, 6, 10, 14 and 18) is reported. The materials were prepared by the polymeric precursor method (Pechini method), calcined for 4 h between 800 °C and 1200 °C. The Rietveld method with X-ray diffraction data (XRD) was used to analyze the unit cell dimensions, crystallite size and microstrain. It was observed the crystallite size increasing and decrease of the microstrain with the increase of the calcining temperature. The synthesis of tin oxide nanoparticles with high thermal stability against particle growth rate was achieved by doping SnO₂ particles with Sb₂O₃. All the phases tend to have the same dimension when the temperature increases, although its values varies with x and reaches the maximum value when fired at 1100 °C. These variations seem to be an indication that the oxidation state of the antimony changes with the amount of Sb added to the material.     

Characterization of gases and solid residues from closed system pyrolysis of peat and coals at two heating rates

Closed system gold-tube pyrolysis experiments were performed on a peat and two coals (TY: R_o = 0.51%; SX: R_o = 0.94%) at temperatures ranging from 337 to 600 °C and a pressure of 50 MPa with heating rates of 2 and/or 20 °C/h. Solid reaction residues were analyzed microscopically. Yields and chemical and isotopic compositions of the generated gases were also determined. All three samples had similar thermal evolution pathways. With increasing heating temperature, vitrinite reflectances (VR_r) of the residues increased linearly from 0.72% to 4.50%. This increase was lesser for the sample with a higher hydrocarbon generation potential and at faster heating rates. Gas compositions are dominated by CO₂ and CH₄ throughout the experimental process. Total gas and CH₄ yields gradually increase with pyrolysis temperature for all samples. The carbon isotopic compositions of CH₄ generated from the peat are lighter than those from the coals. The δ¹³C_CH4 values exhibit a generic evolution pattern which the initial CH₄ is isotopically heavy, then becomes lighter at moderate temperatures, and finally becomes heavier again. Methane produced from the samples at low heating rate has higher transformation ratio than that at high heating rate under the same temperature, so tends to be isotopically heavy after pyrolysis temperature of more than 408 °C.     

Enhanced electrochemical stability of Al-doped LiMn2O4 synthesized by a polymer-pyrolysis method

LiAl_xMn_2−xO₄ samples (x = 0, 0.02, 0.05, 0.08) were synthesized by a polymer-pyrolysis method. The structure and morphology of the LiAl_xMn_2−xO₄ samples calcined at 800 °C for 6 h were investigated by powder X-ray diffraction and scanning electron microscopy. The results show that all samples have high crystallinity, regular octahedral morphology and uniform particle size of 100-300 nm. The electrochemical performances were tested by galvanostatic charge-discharge and cyclic voltammetry. The results demonstrate that the Al-doped LiMn₂O₄ can be very well cycled at an elevated temperature of 55 °C without severe capacity degradation. In particular, the LiAl_0.08Mn_1.92O₄ sample demonstrates excellent capacity retention of 99.3% after 50 cycles at 55 °C, confirming the greatly enhanced electrochemical stability of LiMn₂O₄ by a small quantity of Al-doping.     

The synthesis and characterization of a super-activated carbon containing substitutional boron (BCx) and its applications in hydrogen storage

A new family of porous boron-substituted carbon (BC_x) materials with controlled structure is investigated. The chemistry involves a B-precursor polymer, i.e., poly(borachlorophenyldiacetylene), containing inorganic additives (templates). At pyrolysis <400 °C, the B-precursor engages in easy inter-chain reactions to form dark solid with high yield (>85%). Above 600 °C, the amorphous carbon-like BC_x materials containing up to 12% B have been prepared, which show an extended fused hexagonal ring structure with B-puckered curvature. This out of planar B moiety maintains its electron deficiency, due to limited π-electron delocalization, and exhibits super-activated properties to enhance H₂ binding energy (20-10 kJ/mol) and adsorption capacity. After removing the inorganic additives by water-washing, the resulting porous BC_x shows a surface area 500-800 m²/g. Evidently, the pore size distribution is directly related to melting temperature and distribution of the inorganic salts. As the temperature increases to >1400 °C, the distorted ring structure gradually flatten out to form a multi-layer (crystalline) BC_x structure. The resulting planar graphitic layer only can accommodate a reduced B content (<3% at 1800 °C) and low surface area. The B moieties also lose their acidity due to the extensive π-electron delocalization.