Microstructural evolution during direct laser sintering in the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> system

The microstructural evolution during direct laser sintering of LSD (Layerwise Slurry Deposition)—samples in the Al₂O₃–SiO₂ system has been investigated. Slurries with a water content of 34 wt.% and a SiO₂/Al₂O₃—ratio of about 3:1 have been used to manufacture layers which—after consecutive drying—have been sintered and laminated by laser treatment. Densified samples can be obtained with laser irradiances from 190 to 270 kW/cm² and scan velocities between 35 and 65 mm/s. Elemental mappings of the layers’ cross sections suggest an inhomogeneous phase distribution in the laser sintered LSD samples with a slight alumina concentration gradient. A lower degree of particle melting in the bottom region of the layers is plausible due to attenuation of the laser beam intensity. SEM and HRTEM micrographs show that after a few seconds of laser treatment relictic starting phase, crystalline alumina plus amorphous silica, occur together with needle like mullite, the latter formed within an amorphous aluminosilicate phase. The resulting phase assemblage reflects the non-equilibrium conditions which can be expected for short time laser treatments. Mullite nucleation within the bulk of the liquid phase rather than in the vicinity of the parent alumina phase suggests that dissolution of alumina is the rate controlling step. Subsequent thermal post treatment in air in a conventional sintering furnace causes an increase of density to about 96% and leads to additional phase reactions. Amorphous silica transforms into cristobalite and the amount of alumina is reduced by additional mullite formation. By both coalescence of individual crystals and grain growth the morphology of the newly formed mullite changes during post heat treatment.     

Mechanical properties and microstructure of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/mullite composite

An Al₂O₃/5 vol.% mullite composite was synthesized by using reaction sintering of Al₂O₃/0.78 wt.% SiC at 1,600 °C for 2 h in air. The phase analysis of the Al₂O₃/mullite composite was carried out using X-ray diffraction (XRD). There were two kinds of mullite in alumina/mullite composite, namely, 3Al₂O₃·2SiO₂ and Al_5.65Si_0.35O_9.175. The microstructure of the Al₂O₃/mullite composite was investigated using scanning electron microscope (SEM) and transmission electron microscope (TEM). The mechanical properties such as Young’s modulus, Poisson’s ratio, hardness, toughness and strength of the Al₂O₃/mullite composite were investigated. The influence of mullite on the composite is discussed.     

Enhanced thermal stability in K<Subscript>2</Subscript>O-metakaolin-based geopolymer concretes by Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and SiO<Subscript>2</Subscript> fillers addition

Based on the principle of stability of geopolymer gel as refractory binder, a geopolymeric paste in the K₂O–Al₂O₃–SiO₂ system was developed and used to produce refractory concretes by adding various amount of α-quartz sand (grain size in the range 0.1 μm to 1 mm) and fine powder alumina (grain size in the range 0.1–100 μm). The consolidated samples were characterized before and after sintering using optical dilatometer, DSC, XRD and SEM. The total shrinkage in the range of 25–900 °C was less than 3%, reduced with respect to the most diffused potassium or sodium based geopolymer systems, which generally records a >5% shrinkage. The maximum shrinkage of the basic geopolymer composition was recorded at 1000 °C with a 17% shrinkage which is reduced to 12% by alumina addition. The temperature of maximum densification was shifted from 1000 °C to 1150 or 1200 °C by adding 75 wt% α-quartz sand or fine powder alumina respectively. The sequences of sintering of geopolymer concretes could be resumed as dehydration, dehydroxylation, densification and finally plastic deformation due to the importance of liquid phase. The geopolymer formulations developed in this study appeared as promising candidates for high-temperature applications: refractory, fire resistant or insulating materials.     

Role of Ti diffusion on the formation of phases in the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> brazed interface

Diffusivities of Ti, Cu, Al and Ag in the interface of Al₂O₃–Al₂O₃ braze joints using Ag–Cu–Ti active filler alloy, have been calculated by Matano–Boltzman method. The Matano plane has been identified for each elemental diffusion at various brazing temperatures. The diffusivities of Ag, Cu and Al are almost insignificant on formation of interface during brazing, whereas the diffusivity of Ti changes significantly with the brazing temperature and controls the formation of different reaction product in the interface. Presence of TiO and Ti₃Cu₃O phases in the interface has been confirmed by transmission electron microscopy (TEM).     

Properties of nanocrystalline ZrO<Subscript>2</Subscript>-Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-CeO<Subscript>2</Subscript>-CoO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> powders

We have studied the properties of nanocrystalline ZrO₂-Y₂O₃-CeO₂-CoO-Al₂O₃ powders prepared via hydrothermal treatment of a mixture of coprecipitated hydroxides at 210°C. A number of general trends are identified in the variation of the properties of the synthesized powders during heat treatment at temperatures from 500 to 1200°C. Our results demonstrate that the addition of 0.3 mol % CoO to nanocrystalline ZrO₂-based powders containing 1 to 5 mol % Al₂O₃ allows one to obtain composites with good sinterability at a reduced temperature (1200°C).     

A novel Sn<Subscript>2</Subscript>Sb<Subscript>2</Subscript>O<Subscript>7</Subscript> nanophotocatalyst for visible-light-driven H<Subscript>2</Subscript> evolution

A novel pure cubic-phase pyrochlore structure tin(II) antimonate nanophotocatalyst, stoichiometric Sn₂Sb₂O₇, has been prepared by a modified ion-exchange process using an antimonic acid precursor, and employed in visible-light-driven photocatalytic H₂ evolution for the first time. The physicochemical properties (crystal phase, chemical composition and state, textural properties, and optical properties) of the material were investigated by different instrumental techniques. Compared with the antimonic acid precursor, the as-prepared Sn₂Sb₂O₇ had a narrower bandgap, smaller crystal size, and larger BET surface area. The as-prepared Sn₂Sb₂O₇ was validated as a promising candidate for visible-light-driven photocatalytic H2 evolution with a constant rate of 40.10 μmol·h⁻¹·g_cat ⁻¹.      

Dynamic deformation and fracture of mullite (3Al2O3·2SiO2) ceramics under hypervelocity impact

Shock-recovery experiments have been performed on mullite ceramics to clarify the effect of a phase transition on the microstructural change and deformation mechanism under shock loading. The recovered samples have been examined using the X-ray diffraction method and transmission electron microscope observation. In the samples shocked above the phase-transition pressure, an amorphization of mullite occurs. Mullite nano-crystals with grain sizes less than 10 nm are dispersed in the amorphous phase, indicating that the relatively large starting mullite crystals become nano-crystals accompanied with the amorphization. Mullite bumper-shield experiments have also been performed to examine the influence of shock-induced microstructural changes to ultimate fracture under hypervelocity impact. The results suggest that the phase transition of mullite has an effect on protection against high-velocity impact.     

Preparation of magnetic composites through SrO-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> glass crystallization

Glasses with nominal compositions 11SrO · 5.5Fe₂O₃ · 4.5Al₂O₃ · 4B₂O₃ (1) and 15SrO · 5.5Fe₂O₃ · 4.5Al₂O₃ · 4B₂O₃ (2) were prepared by rapidly quenching oxide melts between counterrotating steel rollers. The glasses were then heat-treated in the range 650–950°C to produce glass-ceramic samples. The samples were characterized by X-ray diffraction, electron microscopy, and magnetic measurements. The phase composition of the glass-ceramics was determined, and their microstructure and magnetic properties were studied. The annealing temperature was shown to have a strong effect on the coercivity of the materials, which reaches 650 and 570 kA/m for compositions 1 and 2, respectively.     

Dielectric and ferromagnetic properties of BaTiO<Subscript>3</Subscript>/Ni<Subscript>0.93</Subscript>Co<Subscript>0.02</Subscript>Cu<Subscript>0.05</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript> composites

xBaTiO₃ + (1 − x)Ni_0.93Co_0.02Cu_0.05Fe₂O₄ (x = 0.5, 0.6, 0.7, 0.8) composites with ferroelectric–ferromagnetic characteristics were synthesized by the ceramic sintering technique. The presence of constituent phases in the composites was confirmed by X-ray diffraction studies. The average grain size was calculated by using a scanning electron micrograph. The dielectric characteristics were studied in the 100 kHz to 15 MHz. The dielectric constant changed higher with ferroelectric content increasing; and it was constant in this frequency range. The relation of dielectric constant with temperature was researched at 1, 10, 100 kHz. The Curie temperature would be higher with frequency increasing. The hysteresis behavior was studied to understand the magnetic properties such as saturation magnetization (M _s). The composites were a typical soft magnetic character with low coercive force. Both the ferroelectric and ferromagnetic phases preserve their basic properties in the bulk composite, thus these composites are good candidates as magnetoelectric materials.     

Synthesis and microwave absorption property of ternary composites: polyaniline/CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/Ba<Subscript>3</Subscript>Co<Subscript>2</Subscript>Fe<Subscript>24</Subscript>O<Subscript>41</Subscript>

Polyaniline (PANI)/CoFe₂O₄/Ba₃Co₂Fe₂₄O₄₁ composite was prepared by an in-situ polymerization method. The phase structure, morphology and magnetic properties of the as-prepared PANI/CoFe₂O₄/Ba₃Co₂Fe₂₄O₄₁ composite were characterized by XRD, FT-IR, SEM, TEM, and VSM, respectively. The microwave absorption properties of the composite were investigated by using a vector network analyzer in the 2–18 GHz frequency range. The results show that the maximum reflection loss value of the PANI/CoFe₂O₄/Ba₃Co₂Fe₂₄O₄₁ composite reaches ?30.5 dB at 10.5 GHz with a thickness of 3 mm and the bandwidth of reflection loss below ?10 dB reaches up to 1.2 GHz. The excellent microwave absorption properties of the as-prepared PANI/CoFe₂O₄/Ba₃Co₂Fe₂₄O₄₁ composite due to the enhanced impedance match between dielectric loss and magnetic loss.     

Superconductivity,Magnetism, and Magnetoresistancein RuSr<Subscript>2</Subscript>R<Subscript>1.4</Subscript>Ce<Subscript>0.6</Subscript>Cu<Subscript>2</Subscript>O<Subscript>10–δ</Subscript> (R = Eu,Sm)

Samples with nominal compositions RuSr₂R_1.4Ce_0.6Cu₂O_10–δ (R = Eu, Sm) were synthesized and their superconducting (SC) and magnetic properties were compared. A coexistence of AFM and FM ordering below the FM transition temperature was established in the two samples. It was shown that their SC properties are affected by a spontaneous vortex phase (SVP). The first critical fields of the two samples were calculate — H_cl≈ 70 Oe for R=Eu and 60 Oe for R=Sm. It was shown that the improved superconducting properties of the Sm-containing sample do not affect its FM behavior. A sizable magnetoresistance was observed in the two samples at T<T _c.     

Electrical properties of perovskite-like compounds in the Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-TiO<Subscript>2</Subscript> system

The electrical properties of layered perovskite-like compounds with the general formula Bi _{m + 1}Fe _{m − 3}Ti₃O_{3m + 3} have been studied in relation to their physicochemical properties and structure.     

Synthesis and High-Temperature Heat Capacity of Sm<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript> and Eu<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript>

The Sm₂Ge₂O₇ and Eu₂Ge₂O₇ germanates have been prepared by solid-state reactions via multistep firing of stoichiometric mixtures of Sm₂O₃ (Eu₂O₃) and GeO₂ in air at temperatures from 1273 to 1473 K. The molar heat capacity of the samarium and europium germanates has been determined by differential scanning calorimetry in the range 350–1000 K and the C _p (T) data have been used to evaluate their thermodynamic properties.     

Elastic properties of Na<Subscript>2</Subscript>O-ZnO-ZnF<Subscript>2</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> oxyfluoride glasses

Elastic properties of Na₂O-ZnO-ZnF₂-B₂O₃ oxyfluoride glasses with different ZnF₂ concentrations have been investigated using ultrasonic velocity measurements at room temperature, at a frequency of 10 MHz. Glasses prepared by melt quenching method were suitably polished for the ultrasonic velocity measurements using pulse-echo superposition method. Various elastic moduli have been calculated and their compositional dependence has been examined. The compositional dependence of elastic moduli with the concentration of ZnF₂ shows decrease in the moduli initially, with further increase in ZnF₂ the moduli sharply increases and then again tend to decrease when ZnF₂ concentration is 20 mol%. The values of Poisson’s ratio lie in the range of 0·24–0·30, which is typical to covalent bonded network. The variation of θ _D with ZnF₂ indicates complex behaviour of the glass network. The results have been analysed in view of the modified borate glass network. Addition of ZnF₂ into the pure glass seems to influence the borate network by replacement of B-O-B linkages with B-O-Zn.     

Structure and microwave dielectric properties of ZnTa<Subscript>2</Subscript>O<Subscript>6</Subscript> ceramics with TiO<Subscript>2</Subscript> and ZrO<Subscript>2</Subscript> additions

Ceramic samples based on ZnTa2O₆ and ZnTa₂O₆–MO₂ (M = Ti, Zr) systems have been obtained by the solid state ceramic route. The phase composition and microstructure of samples were investigated. The effect of the aliovalent substitution of ions Zn²⁺ and Ta⁵⁺ by M⁴⁺ (M = Ti, Zr) in the structure of ZnTa₂O₆ on microwave dielectric properties of ceramics was studied. The way of the compensation of the positive temperature coefficient of resonant frequency of dielectric resonators based on ZnTa₂O₆ ceramics with using the aliovalent substitution of cations was proposed. Dielectric resonators with the high temperature stability of the resonant frequency and high dielectric properties in the microwave range based on the ZnTa₂O₆–ZrO₂ system were obtained for application in electronics.     

Temperature-stable and low loss Fe-containing dielectrics in BaO-Ln<Subscript>2</Subscript>O<Subscript>3</Subscript>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> system

Polycrystalline samples of Ba₄Ln₂Fe₂Ta₈O₃₀ (Ln = La and Nd) were prepared by a high temperature solid-state reaction technique. The formation, structure, dielectric and ferroelectric properties of the compounds were studied. Both compounds are found to be paraelectrics with filled tetragonal tungsten bronze (TB) structure at room temperature. Dielectric measurements revealed that the present ceramics have exceptional temperature stability, a relatively small temperature coefficient of dielectric constant (τ _ε ) of −25 and −58 ppm/°C, with a high dielectric constant of 118 and 96 together with a low dielectric loss of 1.2 × 10⁻³ and 2.8 × 10⁻³ (at 1 MHz) for Ba₄La₂Fe₂Ta₈O₃₀ and Ba₄Nd₂Fe₂Ta₈O₃₀, respectively. The measured dielectric properties indicate that both materials are possible candidates for the fabrication of discrete multilayer capacitors in microelectronic technology.     

Sorption of U(VI) onto TiO<Subscript>2</Subscript>/ZrO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> Mesoporous Materials from Sulfate Solutions

New nanostructured mesoporous materials of the composition TiO₂/ZrO₂/SiO₂ were prepared by the template sol–gel method using a siloxane–acrylate emulsion as a template. The morphology and structure of these materials and their ability to take up U(VI) were studied. The influence of various factors (ZrO₂ content, pH of solution) on the sorption properties was studied. The suggested materials allow efficient sorption of U(VI) from sulfate solutions with low U(VI) concentrations and can be used in final purification processes.     

Synthesis and high-temperature heat capacity of Yb<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript> and Lu<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript>

Yb₂Sn₂O₇ and Lu₂Sn₂O₇ have been prepared by solid-state reactions, by firing mixtures of Yb₂O₃ or Lu₂O₃ and SnO₂ at 1473 K, and the molar heat capacity of these compounds (pyrochlore structure) has been determined by differential scanning calorimetry. The C _p (T) data have been used to evaluate the thermodynamic properties of the stannates: enthalpy increment, entropy change, and reduced Gibbs energy.     

Effective elastic properties and residual stresses in directionally solidified eutectic Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/YAG/ZrO<Subscript>2</Subscript> ceramics estimated by finite element analysis

Effective elastic properties and residual stresses were assessed in directionally solidified ternary eutectic ceramic, Al₂O₃/YAG/ZrO₂, by finite element analyses. A 3D finite element model was generated from a CT scan, representative of the microstructure and with a similar volume fraction. Effective elastic properties were calculated by numerical homogenisation. They highlight a quasi-isotropic behaviour of the ternary eutectic ceramics. Despite the difficulties to measure the strain, the dispersion observed in the results and the limited reliability of the materials properties, the results constitute a step towards a better understanding of the material behaviour. Thermal residual stresses induced by the manufacturing were also evaluated. Tensile residual stresses in yttria-stabilised zirconia and compressive residual stresses in YAG and alumina were highlighted. This evaluation also shed light on the influence of the phase morphology in the microstructure. Indeed, the computed spatial distribution of the residual stresses showed that they are different from one position to another due to the variation in phase morphology and also to material properties variability. Therefore, it is important when numerically assessing the thermomechanical properties to take into account the microstructure morphology as well as the variability of material properties.     

Investigation of density of states and electrical properties of Ba<Subscript>0.5</Subscript>Co<Subscript>0.5</Subscript>Bi<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript> nanoceramics prepared by chemical route

Barium-cobalt-bismuth-niobate, Ba_0.5Co_0.5Bi₂Nb₂O₉ (BCoBN) nanocrystalline ferroelectric ceramic was prepared through chemical route. XRD analysis showed single phase layered perovskite structure of BCoBN when calcined at 650 °C, 2 h. The average crystallite size was found to be 18 nm. The microstructure was studied through scanning electron microscopy. The dielectric and ferroelectric properties were investigated in the temperature range 50–500 °C. The dielectric constant and dielectric loss plot with respect to temperature both indicated strong relaxor behavior. Frequency versus complex impedance plot also supported the relaxor properties of the material. The impedance spectroscopy study showed only grain conductivity. Variation of ac conductivity study exhibited Arrhenius type of electrical conductivity where the hopping frequency shifted towards higher frequency region with increasing temperature. The ac conductivity values were used to evaluate the density of state at the Fermi level. The minimum hopping distance was found to be decreased with increasing temperature.