Synthesis of (Ni,Mn,Co)O4 nanopowder with single cubic spinel phase via combustion method

(Ni,Mn,Co)O₄ nanopowders with single cubic phase were successfully synthesized using combustion methods. Particle size of the as-burnt nanopowders after combustion was about 20 nm. Crystallization behavior of the NMC was investigated using various techniques such as X-ray diffraction (XRD), thermogravimetric (TG), Fourier transform infrared (FT-IR) spectroscopy, and transmission electron microscopy (TEM). Calcination at different temperature from 400 °C to 700 °C provides the powders with increased crystallinity and grain size. However, further increasing temperature above 800 °C for calcination, cubic spinel phase of NMC partly transformed to tetragonal spinel phase, which implies that cubic spinel phase of NMC nanopowder synthesized by combustion method becomes unstable above 800 °C.     

Time-resolved powder neutron diffraction study of the phase transformation sequence of kaolinite to mullite

Mullite formation from kaolinite was studied by means of high-temperature in situ powder neutron diffraction by heating from room temperature up to 1370 °C. Neutron diffractometry under this non-isothermal conditions is suitable for studying high-temperature reaction kinetics and to identify short-lived species which otherwise might escape detection. Data collected from dynamic techniques (neutron diffraction, DTA, TGA and constant-heating rate sintering) were consistent with data gathered in static mode (conventional X-ray diffraction and TEM). The full process occurs in successive stages: (a) kaolinite dehydroxylation yielding metakaolinite in the ∼400–650 °C temperature range, (b) nucleation of mullite in the temperature range ∼980–992 to ∼1121 °C (primary mullite) side by side with a crystalline cubic phase (Si-Al spinel) detected in the ∼983–1030 °C temperature interval; (c) growth of mullite crystals from ∼1136 °C, (d) high (or β) cristobalite crystallization at T > ∼1200 °C and (e) secondary mullite crystallization at T > ∼1300 °C. The calculated activation energy for the kaolinite dehydration was 115 kJ/mol; for the mullite nucleation was 278 kJ/mol and for the growth of mullite process was 87 kJ/mol; finally for cristobalite nucleation the calculated apparent activation energy was 481 kJ/mol.     

Fabrication of Si3N4–SiC nano-composite ceramics through temperature-induced gelation and liquid phase sintering

This paper describes the fabrication of Si₃N₄–SiC nano-composite ceramics through a novel direct casting method (temperature-induced gelation) followed by liquid-phase sintering. A kind of polyester/polyamine condensation copolymer (hypermer KD1) was used as dispersant and gelling agent. At room temperature (≈20 °C), it plays the role of a steric dispersant, allowing the preparation of stable homogeneous and high concentrated suspension (57.5 vol.% solids) consisting of Si₃N₄, Y₂O₃, Al₂O₃ and 20 wt.% nano-SiC. At low temperature it acts as gelling agent, inducing incipient flocculation due to the collapse of adsorbed layer. The low values of viscosity and elastic modulus at room temperature, increased dramatically within a moderate decrease of temperature from 20 to 5 °C. A completely solidified green body with precise dimensions, smooth surface, high strength and homogeneous density has been obtained, which could be gas-pressure sintered to near theoretical density at 1850 °C.     

Preparation and characterization of porous mullite ceramics via foam-gelcasting

Porous mullite ceramics were prepared via foam-gelcasting using industrial grade mullite powder as the main raw materials, Isobam-104 as the dispersing and gelling agent, sodium carboxymethyl cellulose as the foam stabilizing agent, and triethanolamine lauryl sulfate as the foaming agent. The effects of processing parameters such as type and amount of additive, solid loading level and gelling temperature on rheological properties and gelling behaviors of the slurries were investigated. The green samples after drying at 100 °C for 24 h were fired at 1600 °C for 2 h, and the microstructures and properties of the resultant porous ceramic samples were characterized. Based on the results, the effects of foaming agent on the porosity level, pore structure and size and mechanical properties of the as-prepared porous mullite ceramics were examined. Porosity levels and pore sizes of the as-prepared samples increased with increasing the foaming agent content up to 1.0%, above which both porosity levels and pore sizes did not change. The compressive strength and flexural strength of the as-prepared sample with porosity of 76% and average pore size of 313 μm remained as high as 15.3±0.3 MPa and 3.7±0.2 MPa, respectively, and permeability increased exponentially with increasing the porosity.     

Structural parameters and oxygen ion conductivity of Y2O3–ZrO2 and MgO–ZrO2 at high temperature

The oxygen ion conductivity of zirconia-based solid electrolytes doped with 8 mol% Y₂O₃–ZrO₂ (YSZ) and 9 mol% MgO–ZrO₂ (Mg-PSZ) at high temperature was investigated in terms of their thermal behavior and structural changes. At room temperature, YSZ showed a single phase with a fluorite cubic structure, whereas Mg-PSZ had a mixture of cubic, tetragonal and some monoclinic phases. YSZ exhibited higher ionic conductivity than Mg-PSZ at temperatures from 600 °C to 1250 °C because of the existence of the single cubic structure and low activation energy. A considerable increase in the conductivity with increasing temperature was observed in Mg-PSZ, which showed higher ionic conductivity than YSZ within the higher temperature range of 1300–1500 °C. A monoclinic-to-tetragonal phase transformation was found in Mg-PSZ and the lattice parameter of the cubic phase increased at 1200 °C. The phase transformation and the large lattice free volume contributed to the significant enhancement of the ionic conductivity of Mg-PSZ at high temperatures.     

Synthesis of a biocompatible polymer using siloxane-based surfactants in supercritical carbon dioxide

Poly(N-vinyl-2-pyrrolidone) (PVP) particles were prepared by dispersion polymerization in the presence of 2,2′-azobisisobutyronitrile as the initiator and siloxane-based surfactant in supercritical carbon dioxide (scCO₂). The dispersants used in this study were non-ionic, non-reactive and commercially produced siloxane-based surfactants (Monasil PCA and KF-6017). We investigated the effect of kinds and concentrations of the surfactants, in addition to the reaction temperature and the concentration of the monomer on the particle size and morphology. PVP microspheres were prepared in 0.23–0.74 μm size range with Monasil PCA and 0.71–1.98 μm size range with KF-6017, respectively. The resulting polymer particle of >90% yield was obtained. Particle size slightly increased with the amount of monomer in polymerization with Monasil PCA. In the case of KF-6017 as the surfactant, there was not an obvious variation in particle size with increasing monomer. Particle size of PVP decreased as surfactant concentration increased from 5.0 to 15.0 wt.% basis on concentration of monomer. The narrow particle size distribution (D_n = 0.23 μm and PSD = 1.06) was presented at the high concentration of Monasil PCA (15 wt.% on monomer concentration). As indicated by the reaction temperature and the addition of organic solvent, which affected solubility of monomer, polymer and surfactant in scCO₂, particle size and particle size distribution of PVP varied. PVP particles with Monasil PCA strongly aggregated at 75 °C in contrast to KF-6017 which showed discrete particles at 65 and 70 °C, but particle size distribution was broad. Particle size was slightly reduced with a little amount of hexane, with an inverse relationship of adding hexane reduced the particle size. The amount of the relative residual surfactants on surface of the polymer after extracting with supercritical fluid process (SFE) was measured by using SEM/EDS and EPMA analysis to map out the distribution of silicon element qualitatively. The original polymer particle before the extraction using CO₂ had the high level of silicon element, but the average level of silicon element became low after CO₂ extraction.     

Adsorption of an acid dye onto coal fly ash

In this study, we found the raw coal fly ash (CFA) that had not been subjected to any pretreatment process had superior adsorbing ability for the anionic dye Acid Red 1 (AR1) than did two modified coal fly ashes (CFA-600 and CFA-NaOH). The adsorption capacities followed the order CFA > CFA-600 > CFA-NaOH, and they each increased upon increasing the temperature (60 °C > 45 °C > 30 °C). The adsorptions of AR1 onto CFA, CFA-600, and CFA-NaOH all followed pseudo-second-order kinetics. The isotherms for the adsorption of AR1 onto the raw and modified coal fly ashes fit the Langmuir isotherm quite well; the adsorption capacities of CFA, CFA-600, and CFA-NaOH for AR1 were 92.59–103.09, 32.79–52.63, and 12.66–25.12 mg g^?1, respectively. According to the positive values of ΔH° and ΔS°, these adsorptions were endothermic processes. The ARE and EABS error function methods provided the best parameters for the Langmuir isotherms and pseudo-second-order equations, respectively, in the AR1–CFA adsorption system.     

Ni4Nb2O9 ceramics prepared by the reaction-sintering process

Fabrication of Ni₄Nb₂O₉ ceramics via a reaction-sintering process was investigated. A mixture of raw materials was sintered into ceramics by bypassing calcination and subsequent pulverization stages. Ni₄Nb₂O₉ phase appeared at 1300 °C and increased with increasing soak time. Ni₄Nb₂O₉ content was found >96% in 1350 °C/2 h sintering pellets. A density of 5.71 g/cm³ was obtained for pellets sintered at 1350 °C for 2 h. This reaches 96.5% of the theoretical density. As the sintering temperature increased to 1350 °C, an abnormal grain growth occurred and grains >100 μm could be found. ?_r of 15.4–16.9 are found in pellets sintered at 1200–1300 °C. Q × f increased from 9380 GHz in pellets sintered at 1200 °C to 14,650 GHz in pellets sintered at 1250 °C.     

The equilibrium phase boundary between hexagonal and cubic boron nitride

The equilibrium phase boundary between hexagonal and cubic boron nitride was determined over the pressure range 3–6 GPa and the temperature range 1200–2200°C. Absolute pressure and temperature were estimated based on the minimum P–T point of diamond formation in the conventional metal catalyst system using the Kennedy–Kennedy equilibrium line between graphite and diamond. Above 3.8 GPa, we determined the phase boundary by detecting the formation of cubic BN in the catalyst-containing system and by the reverse transformation from cubic BN to hexagonal BN. Below 3.8 GPa, we determined the boundary by careful observation of the transformation behavior of cubic BN powder. The rate of phase transformation from cubic BN to hexagonal BN was evaluated from the ratio of X-ray diffraction peak intensities of both phases. We found that the amount of cubic BN phase clearly changed at the phase boundary. Two sets of the results could be plotted with a uniquely determined boundary line expressed by the equation P(GPa)=T(°C)/465+0.79, which is located about 300°C higher at 5 GPa than the line determined by Bundy and Wentorf in 1963.     

The influence of ion beam assisted deposition parameters on the properties of boron nitride thin films

We studied ion beam assisted deposition of cubic boron nitride thin films on silicon (100) and high speed steel. The boron nitride films were grown by the electron beam evaporation of pure boron (99.4%) and the simultaneous ion bombardment of a mixture of nitrogen and argon ions from a Kaufman ion source. At a constant boron evaporation rate, the ion energy, ion current density, substrate temperature and process gas mixture was varied. The thickness of the films was kept between 200 and 300 nm. Boron nitride films with >80% of the cubic phase (determined by Fourier transform infrared spectroscopy) were obtained with nitrogen/argon mixtures of 50/50 at ion energies of 450 eV and substrate temperatures of 400°C. The current density amounted to 0.45 mA cm⁻² at a nominal boron rate of 200 pm s⁻¹. Cubic boron nitride films were deposited on high speed steel by introducing a titanium interlayer for adhesion improvement.     

Microstructure and mechanical properties of the spark plasma sintered TaC/SiC composites: Effects of sintering temperatures

TaC/SiC composites with 20 vol.% SiC addition were densified by spark plasma sintering at 1600–1900 °C for 5 min under 40 MPa. Effects of sintering temperatures on the densification, microstructures and mechanical properties of composites were investigated. The results showed the materials achieved >98% of theoretical density at a temperature as low as 1600 °C. While the TaC grains grew slightly with the sintering temperature increasing, the SiC particles in materials decreased in size. Equiaxed to elongated grain morphology transformation was observed in the SiC phase in the 1900 °C material to obtain a higher flexural strength and fracture toughness of 715 MPa and 6.7 MPa m^1/2, respectively. Lattice enlargement of the TaC phase in the 1900 °C material suggested possible Si diffusion into TaC grains. Ta was also detected in SiC grains by energy dispersive spectroscopy. Glassy pockets present at multi-grain junctions explained the enhanced densification.     

X-ray single phase LSGM at 1350 °C

Synthesis of X-ray-phase-pure (La_1−xSr_xGa_1−yMg_yO_3−δ, LSGM, where x = 0.1, y = 0.15 and 0.17) powders were achieved at temperatures as low as 1350 °C via organic precursor method using tartaric acid as the carrier material. LSGM materials were characterized for their phase purity, crystallization and electrical properties. Pellets sintered at 1350 °C for 6 h were single phase and dense (>99%). Electron microscopy analysis of X-ray single-phase pellets revealed MgO precipitates with sizes ranging from 50–300 nm. Phase formation and distribution in this complicated multi-cation-oxide system as a function of temperature were reported and discussed. Amorphous LSGM first crystallizes at 625 °C. However, elimination of undesired phases require higher temperatures. Impedance measurements as a function of temperature up to 545 °C revealed that the X-ray phase pure pellets may have extrapolated ionic conductivity values as high as 0.14–0.16 S/cm at 800 °C. Possible implications of limited MgO solubility on the ionic conductivity are presented.     

Effects of sintering on the mechanical and ionic properties of ceria-doped scandia stabilized zirconia ceramic

The effect of conventional sintering from 1300 to 1550 °C on the properties of 1 mol% ceria-doped scandia stabilized zirconia was investigated. In addition, the influence of rapid sintering via microwave technique at low temperature regimes of 1300 °C and 1350 °C for 15 min on the properties of this zirconia was evaluated. It was found that both sintering methods yielded highly dense samples with minimum relative density of 97.5%. Phase analysis by X-ray diffraction revealed the presences of only cubic phase in all sintered samples. All sintered pellets possessed high Vickers hardness (13–14.6 GPa) and fracture toughness (~3 MPam^1/2). Microstructural examination by using the scanning electron microscope revealed that the grain size varied from 2.9 to 9.8 µm for the conventional-sintered samples. In comparison, the grain size of the microwave-sintered zirconia was maintained below 2 µm. Electrochemical Impedance Spectroscopy study showed that both the bulk and grain boundary resistivity of the zirconia decreases with increasing test temperature regardless of sintering methods. However, the grain boundary resistivity of the microwave-sintered samples was higher than the conventional-sintered ceramic at 600 °C and reduced significantly at 800 °C thus resulting in the enhancement of electrical conduction.     

Environmental resistance of a Ti2AlC-type MAX phase in a high pressure burner rig

Alumina-forming commercial Ti₂AlC (MAXthal 211)™ phase samples were exposed in a jet-fueled, high pressure burner rig (HPBR) at 1100°, 1200°, and 1300 °C, operating at 6 atm (bar) and 25 m/s, in ∼10% water vapor. Weight change exhibited a rapid initial uptake associated with a TiO₂ transient phase followed by cubic kinetics of a slow-growing α-Al₂O₃ underlayer. The cubic rate constants, k_c, were approximately 20% of those measured in static thermo-balance furnace tests. A small recession rate of −0.012 mg/cm²/h was measured at 1300 °C for a pre-oxidized sample. The loss rate was ∼15% that observed for SiO₂ scales subject to volatile Si(OH)₄ formation for SiC tested under similar conditions. These kinetic features were fitted in a modified cubic-linear law. From thermodynamic, XRD, and SEM analyses, it is proposed that volatile TiO(OH)₂ was formed by the reaction of water vapor with TiO₂ and TiAl₂O₅ outer layers.     

Electrospinning and thermal treatment of yttria doped zirconia fibres

As compared to a bulk material, the fibres exhibit novel physical and chemical properties arising from their unique geometric features such as high surface area, surface to volume ratio and small fibre diameter. This paper is focused on the fabrication of nanosized 8 mol% yttria doped zirconia fibres by electrospinning from propoxide/polyvinylpyrrolidonebased precursors and physical-chemical characterization of the ceramic fibres with an energy application potential. Fully crystalline composition of cubic zirconia was detected after fibre heat treatment at 700 °C. The fibre morphology was changed with increasing temperature from flexible nonsintered nanoparticle system at 700 °C through porous nanograin structure at 900 °C and nonporous structure with coarser nanograins at 1100 °C to fragile chain-like fibre structure formed of elongated submicrometer grains at 1300–1450 °C. The densification and grain growth kinetics were described in two stages in the temperature range from 700 °C up to 1450 °C.     

Optical and mechanical properties of amorphous bulk and eutectic ceramics in the HfO2–Al2O3–Y2O3 system

Bulk glasses containing HfO₂ nano-crystallites of 20–50 nm were prepared by hot-pressing of HfO₂–Al₂O₃–Y₂O₃ glass microspheres at 915 °C for 10 min. By annealing at temperatures below 1200 °C, the bulk glasses were converted into transparent glass-ceramics with HfO₂ nano-crystallites of 100–200 nm, which showed the maximum transmittance of ～70% in the infrared region. An increase of annealing temperature (>1300 °C) resulted in opaque YAG/HfO₂/Al₂O₃ eutectic ceramics. The eutectic ceramics contained fine Al₂O₃ crystallites and showed a high hardness of 19.8 GPa. The fracture toughness of the eutectic ceramics increased with increasing annealing temperature, and reached the maximum of 4.0 MPa m^1/2.     

Broadband dielectric characterization of TiO2 ceramics sintered through microwave and conventional processes

In this work the microwave sintering (MW) of pure submicron rutile TiO₂ powder has been conducted in complete electric field using a single mode cavity of 2.45 GHz and without any susceptor. The sintering conditions were varied and similar sintering cycles were also done using a conventional furnace (CV), in carefully measuring the temperature in both processes. The dielectric properties, from kHz to GHz were determined and a comparison analysis was made between microwaved and conventional sintered specimens. It is shown that microwave sintering allows to obtain dense material (>95%) in a very short time (10–15 min) at a sintering temperature ranging from 1000 °C to 1300 °C. Some samples are fully dense (>99% theoretical density) after being microwave heated for ～10 min at ～1300 °C. Using the microwave heating, the processing temperature to get high dense material (i.e. >94%) is lowered by ～150–175 °C compared to conventionally sintered samples. It is also shown that an annealing in air at ～800 °C for ～4 h, leads to very low loss TiO₂ ceramic in the entire frequency range investigated. Owing to the lowest sintering temperature provided by microwaves, the low frequency dielectric losses are smaller for MW samples than for CV sintered samples. Among the highest reported microwave Q factors (～7350) have been measured on pure TiO₂ samples exhibiting the largest grain size (～1.5 μm) and density (>96%).     

Preparation and characterization of Ni–P/nanodiamond coatings: Effects of surfactants

In this study, the effects of different concentrations of surfactants on the properties of the Ni–P/nanodiamond (ND) coatings were investigated. Sodium dodecyl sulfate (SDS) and cetyltrimethyl ammonium bromide (CTAB) were used as the surfactants. Morphology, microhardness and some tribological properties of the coatings were evaluated and compared. Results showed that the composite coatings modified with high concentrations of SDS had smoother surface morphologies than the ones modified with CTAB and low concentrations of SDS. Moreover, it was observed that these coatings had the highest microhardness and wear resistance as well as the lowest friction coefficient (FC) among the coatings. It was found that the effect of NDs on the microhardness of as-plated composite coatings and the ones annealed at 200 °C/3 h was not significant, but became significant when heat treated at 300 °C/1 h and 400 °C/1 h.     

Dielectric properties and electrical behaviors of tunable Bi1.5MgNb1.5O7 thin films

The Bi_1.5MgNb_1.5O₇ (BMN) thin films were prepared on Au-coated Si substrates by rf magnetron sputtering. We systematically investigated the structure, dielectric properties and voltage tunable property of the films with different annealing temperatures. The relationships of leakage current and breakdown bias field with annealing temperature were firstly studied and a possible explanation was proposed. The deposited BMN thin films had a cubic pyrochlore phase when annealed at 550 °C or higher. With the increasing of annealing temperature, the dielectric constant and tunability also went up. BMN thin films annealed at 750 °C exhibited moderate dielectric constant of 106 and low dielectric loss of 0.003–0.007 between 10 kHz and 10 MHz. The maximum tunability of 50% was achieved at a bias field of 2 MV/cm. However, thin films annealed at 750 °C had lower breakdown bias field and higher leakage current density than films annealed below 750 °C. The excellent physical and electrical properties make BMN thin films promising for potential tunable capacitor applications.     

Structural and magnetic properties of the copper ferrite obtained by reactive milling and heat treatment

Copper ferrite (CuFe₂O₄) was synthesised from an equimolar mixture of copper and iron oxides by mechanosynthesis and subsequent heat treatment. After mechanosynthesis, depending on the milling time, the powder consists in a mixture of phases. The heat treatment at 600 °C did not lead to a complete reaction of the mechano-activated precursors. After the heat treatments at 800 and 1000 °C, the complete formation of copper ferrite for almost all the milling times was noticed. The crystal structure of the copper ferrite was found to be cubic for all the samples heat treated at 1000 °C and a mixture of tetragonal and cubic for the samples heat treated at 800 °C. The amount of copper ferrite with cubic structure predominates in the samples with prolonged milling duration and a decrease of the tetragonal distortion by increasing the milling time occurs. The crystallisation of CuFe₂O₄ in cubic structure for the samples milled for prolonged time is influenced by the powder contamination with iron. The magnetisations of the samples obtained after heat treatment at 1000 °C were found to be larger compared to the ones of the samples heat treated at 800 °C. The iron contamination, milling duration and heat treatment temperature influence the cations distribution, thus leading to the saturation magnetisation of the copper ferrite samples ranging from 11.9 μ_B/f.u. to 16.4 μ_B/f.u.