Hydrothermal synthesis of hierarchical micron flower-like γ-AlOOH and γ-Al2O3 superstructures from oil shale ash

The hierarchical micron flower-like γ-AlOOH and γ-Al₂O₃ superstructures were synthesized using oil shale ash (OSA) as a new raw material. In order to prepare the better quality alumina with uniform morphology, the effects of ethanol and surfactant CTAB on the formation of alumina particles were investigated and the formation mechanism of flower-like composite particles was also discussed. The structural and morphological properties of the uncalcined and calcined powders were characterized by X-ray diffractometer (XRD), Scanning electron microscope (SEM), Brunauer Emmett Teller (BET) and Fourier transform infrared (FT-IR). The results indicated that uniform flower-like γ-AlOOH and γ-Al₂O₃ assembled by nanosheets which thickness is less than 100 nm were prepared. After calcined at 600 °C, morphology of the flower-like superstructure was maintained perfectly. The results obtained in this work prove that the oil shale ash can be used for production of hierarchical superstructures alumina and open a new way for comprehensive application of OSA.     

Influence of processing route on microstructure and mechanical properties of MgAl2O4 spinel

This paper reports on process dependant microstructural and mechanical properties of MgAl₂O₄ spinel (MAS) ceramics. Two MAS powders with different chemical compositions were synthesized by solid-state reaction of alumina and calcined caustic magnesia at 1400 °C for 1 h. The surface of the as obtained MAS powders was passivated against hydrolysis by coating it with H₃PO₄ and Al(H₂PO₄)₃ species dissolved in ethanol at 80 °C for 24 h. The as protected powders could then be dispersed in aqueous solutions of tetramethylammonium hydroxide (TMAH) and Duramax D-3005 as dispersing agents to obtain stable slurries with 45 vol.% solids loading. The stable aqueous MAS slurries were consolidated by slip casting (SC), gelcasting (GC), hydrolysis assisted solidification (HAS) and hydrolysis induced aqueous gelcasting (GCHAS) routes, fully dried and then sintered for 1 h at 1650 °C. For comparison purposes, dense MAS ceramics were also prepared following a conventional dry-powder pressing (DP) and temperature induced gelation (TIG) routes. All the sintered MAS ceramics were thoroughly characterized for bulk density, apparent porosity, water absorption capacity, SEM microstructure, XRD phase, hardness, 3-point bend strength, and percentage of shrinkage to evaluate the suitability of the processing routes for fabricating defect free components with near-net shape. Among the various techniques employed, the GCHAS was found to be best for fabricating near-net shape MAS ceramics.     

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.     

Low-temperature molten salt synthesis of YAlO3 powders assisted by an electrochemical process

YAlO₃ (YAP) powders were successfully synthesized by a unique molten salt method, where YAP precursor was prepared by an electrochemical method at room temperature, followed by calcining it at a temperature of not exceeding 400 °C for 8 h using LiNO₃ as the molten salt medium. XRD analysis and TEM observation show that well-crystallized YAP powders can be obtained at 400 °C for a holding time of 8 h with 1:16 ratio of YAP precursor to LiNO₃ by weight. Greatly reduced temperature of forming YAP should be attributed to the incorporation of LiNO₃ salt in preparing process.     

Probing the oxidation behavior of Ti2AlC MAX phase powders between 200 and 1000 °C

Oxidation of commercial Ti₂AlC MAX phase powders at 200–1000 °C has been investigated by XRD, XPS, SEM, STA and TGA coupled with FTIR. These powders are a mixture of Ti₂AlC, Ti₃AlC₂, TiC and Ti_1.2Al_0.8. Oxidation at 400 °C led to disappearance of carbide phases from Ti 2p, Al 2p and C 1s XPS spectra. At 600 °C, powders changed from dark grey to light grey with a significant volume increase due to crack formation. Powders were severely oxidized by detecting rutile with minor anatase TiO₂. At 800 °C, α-Al₂O₃ was detected while anatase transformed into rutile TiO₂. The cracks were healed and disappeared. At 1000 °C, the Ti₂AlC powders were fully oxidized into rutile TiO₂ and α-Al₂O₃ with a change of powder color from light grey to yellow. FTIR detected the release of C as CO₂ from 200 °C onwards but with additional CO above 800 °C.     

Intense photoluminescence emission at room temperature in calcium copper titanate powders

A study was undertaken about the structural and photoluminescent properties at room temperature of CaCu₃Ti₄O₁₂ (CCTO) powders synthesized by a soft chemical method and heat treated between 300 and 800 °C. The decomposition of precursor powder was followed by thermogravimetric analysis (TG-DTA), X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Fourier transform Raman (FT-Raman) and photoluminescence (PL) measurements. XRD analyses revealed that the powders annealed at 800 °C are becoming ordered and crystallize in the cubic structure. The most intense PL emission was obtained for the sample calcined at 700 °C, which is not highly disordered (300–500 °C) and neither completely ordered (800 °C). From the spectrum it is clearly visible that the lowest wavelength peak is placed around 480 nm and the highest wavelength peak at about 590 nm. The UV/vis absorption spectroscopy measurements showed the presence of intermediate energy levels in the band gap of structurally disordered powders.     

Influence of heat treatment of powder mixture on the microstructure and optical transmission of Nd:YAG transparent ceramics

Transparent Nd:YAG ceramics were fabricated by solid-state reactive sintering of Y₂O₃, α-Al₂O₃ and Nd₂O₃ powders with TEOS and MgO as sintering aids. The powders were ball-milled, dried, sieved and calcined at different temperatures. Samples sintered at 1745 °C for 10 h were utilized to observe the microstructure and the optical transmission. It is found that heat treatments of the powder mixtures above 600 °C for 1 h are necessary to remove the carbon contamination but below 800 °C for 4 h can avoid strong aggregation of the powder. So there is a room for heat-treatment, between 600 °C and 800 °C that can obtain Nd:YAG ceramics with almost pore-free microstructures and high transparency. Highly transparent Nd:YAG ceramic with 84.3% in-line transmission at 1064 nm was fabricated by sintering the 800 °C-1 h-heat-treated powder mixture at 1745 °C for 50 h. Even at wavelength of 400 nm, the transmittance of the sample reached 82.9% and the optical scattering coefficient was as low as 0.71% cm⁻¹.     

Temperature effect on the morphology and catalytic performance of Co-MOF-74 in low-temperature NH3-SCR process

Co-MOF-74 materials were synthesized at different temperatures using solvothermal method. The effect of the synthetic temperature on the structure and low temperature NH₃-SCR catalytic performance of Co-MOF-74 was systematically investigated. Co-MOF-74 synthesized at 100 °C has flower-like morphology, while hexagonal prism structures could be obtained at other temperatures. Co-MOF-74 with flower-like morphology has a larger specific surface area and pore volume compared with the hexagonal prism ones. The highest catalytic activity was obtained at 200 °C under the optimal synthesis temperature, which was attributed to the combination of special morphology, the highest specific surface area and Co content.     

The effects of raw materials particle size and salt type on formation of nano-CaZrO3 from molten salts

Nano-CaZrO₃ was successfully synthesized at 800 °C using the molten-salt method, and the effects of salt type and raw materials particle size on the formation of CaZrO₃ were investigated. Na₂CO₃, CaCl₂, nano-ZrO₂ and micro-ZrO₂ were used as starting materials. On heating, Na₂CO₃ reacted with CaCl₂ to form NaCl and in situ CaCO₃. Na₂CO₃–NaCl molten eutectic salt provided a liquid medium for reaction of CaCO₃ and ZrO₂ to form CaZrO₃. The results demonstrated that in both nano- and micro-ZrO₂ inclusive samples, CaZrO₃ started to form at about 700 °C and that, after the temperature was increased to 1000 °C, the amounts of CaZrO₃ in the resultant powders increased with a concomitant decrease in CaCO₃ and ZrO₂ contents. After washing with hot-distilled water, the samples containing nano- and micro-ZrO₂ heated for 3 h at 800 °C and 1000 °C, were single-phase CaZrO₃ with 70–90 nm and 400–450 nm particle size, respectively. Also, the synthesis process was completed in lower temperatures using eutectic salts. Furthermore, the synthesized CaZrO₃ particles retained the size and morphology of the ZrO₂ powders, which indicated that a template formation mechanism dominated the formation of CaZrO₃ by molten-salt synthesis.     

Novel synthesis of CuO nanofiber balls and films and their UV–visible light filteration property

Self-assembled cupric oxide (CuO) nanofiber balls and films were synthesized via a facile solvothermal route directly from cupric acetate monohydrate (Cu(CH₃COO)₂·H₂O) in water and ethanol without any chemical additions or high temperature treatment. The CuO balls with size of 150 nm–1.5 µm had rough surfaces which consisted of lots of about 10 nm nanofibers in diameter. The sizes of CuO balls were controllable by changing reaction time and volume ratio of water to ethanol. CuO nanofiber films were prepared with the aid of the in situ hydrolysis of Cu(CH₃COO)₂·H₂O coating layer on a substrate at 60 °C. CuO films showed excellent UV–visible light filteration property and could be used as a potential candidate of UV–visible light filter. Compared with traditional method to fabricate CuO films, neither precursor nor Cu substrate was needed in this study. This technique could be used to produce CuO films without being confined to our template and to produce CuO powders in large scale with low cost.     

Structural,textural, surface chemistry and sensing properties of mesoporous Pr,Zn modified SnO2–TiO2 powder composites

Mesoporous Zn and Pr modified SnO₂-TiO₂ mixed powders (Sn:Ti:Zn:Pr contents 60:20:15:5) have been prepared by a modified sol–gel method involving Tripropylamine (TPA) as chelating agent, TritonX100 as template and Polyvinylpyrrolidone as dispersant and stabilizer, respectively. The obtained gels have been dried at different temperatures and calcined in air at 600 and 800 °C, respectively. Phase identification of the synthesized samples and their evolution with the calcination temperature has been performed by X-ray diffraction. N₂ adsorption/desorption isotherms were found to be characteristic for mesoporous materials, showing relatively low values for the specific surface area (15–32 m² g⁻¹) and nanometric sized pores. In case of the sample calcined at 800 °C, a bimodal pore size distribution can be observed, with maxima at 20 and 60 nm. SEM results demonstrate a porous nanocrystalline morphology stable up to 800 °C. The surface chemistry investigated by XPS reveals the presence of the elements on the surface as well as the oxidation states for the detected elements. At 800 °C a diffusion process of Sn from surface to the subsurface/bulk region accompanied by a segregation of Ti and Zn to the surface is noticed, while Pr content is unchanged. The sensing properties of the prepared powders for CO detection have been tested in the range of 250–2000 ppm and working temperatures of 227–477 °C.     

Synthesis of nanocrystalline cerium oxide by high energy ball milling

We have synthesized pure nanocrystalline CeO₂ powders of nearly spherical shape using high-energy attritor ball mill. Milling parameters such as the milling speed of 400 rpm, ball to powder ratio (40:1), milling time (30 h) and water cooled media were determined to be suitable for synthesizing nanosize (～10 nm) powders of CeO₂. The powders after milling for various durations (up-to 50 h) were characterized by X-ray Diffraction, Scanning Electron Microscopy, Energy-dispersive X-ray Spectrometry and Transmission Electron Microscopy. An average particle size of 10 nm was obtained at 30 h milling, after which the particle agglomeration started, and a mixture of nanocrystalline and amorphous phase was observed after 50 h milling.     

Effect of NiS addition on nitridation of alumina to aluminum nitride using polymeric carbon nitride as a nitridation reagent

We investigated the effect of adding nickel(II) sulfide (NiS) on nitridation of alumina (Al₂O₃) to aluminum nitride (AlN) using polymeric carbon nitride (PCN), which was synthesized by polymerization of dicyandiamide at 500 °C. The product powders obtained from nitridation of a mixture of δ-Al₂O₃ and NiS powders (mole ratio of 1:0.01) at various reaction temperatures were characterized by powder X-ray diffraction, ²⁷Al magic-angle spinning nuclear magnetic resonance, and Raman spectroscopy. δ-Al₂O₃ began to convert to AlN at 900 °C and completely converted to AlN at 1300 °C. The as-synthesized sample powders contained nitrogen-doped carbon microtubes (N-doped CMTs) with a length of several tens of mm and thickness of ca. 3 µm. The addition of NiS to δ-Al₂O₃ resulted in the enhancement of the amount of N-doped CMTs and nitridation rate, which might be due to the catalytic action of Ni particles on the thermal decomposition of vaporized PCN. The change in Raman spectra with reaction temperatures indicated that the crystallinity of N-doped CMTs was increased by calcining at higher reaction temperatures.     

Synthesis of zirconium diboride platelets from mechanically activated ZrCl4 and B powder mixture

ZrB₂ platelets were prepared by mechanochemical processing a zirconium (IV) chloride–boron mixture with subsequent annealing from 800 °C to 1200 °C. The phases present were identified by X-ray diffraction. The size and morphology of the synthesized ZrB₂ powders were characterized by scanning electron and transmission electron microscopy. At 800 °C, ZrO₂ was detected in absence of ZrB₂. At or above 1000 °C, ZrCl₄–B converted to ZrB₂. Moreover, at 1200 °C, ZrCl₄–B completely converted to ZrB₂ without trace quantities of residual ZrO₂. The synthesized ZrB₂ consisted of platelets with a diameter of 0.1–2.1 μm and a thickness of 40–200 nm.     

Preparation and characterization of LnMgAl11O19 (Ln=La,Nd, Gd) ceramic powders

Lanthanide hexaaluminate powders of LaMgAl₁₁O₁₉ (LMA), NdMgAl₁₁O₁₉ (NMA) and GdMgAl₁₁O₁₉ (GMA) were synthesized via the solid state reaction or sol–gel and calcination method. The LMA and NMA powders synthesized by the sol–gel and calcination method at 1600 °C for 8 h exhibit a single hexaaluminate phase with magnetoplumbite structure; however, the GMA powder synthesized by the sol–gel and calcination method at 1600 °C for 8 h contains both a hexaaluminate phase and a small amount of second phase GdAlO₃ with a perovskite structure. The powders synthesized by the solid state reaction method at 1500 °C for 4 h have a small particle size of 1–3 μm, and a large specific surface area and a good uniformity. The powders synthesized by the sol–gel and calcination method at 1600 °C for 8 h have a particle size of 5–20 μm, and exhibit to a certain extent agglomeration.     

Effects of precursor chemistry and thermal treatment conditions on obtaining phase pure bismuth ferrite from aqueous gel precursors

Phase pure BiFeO₃ powders are synthesized by an entirely aqueous solution–gel route, starting from water soluble Fe(III) nitrate or citrate, and Bi(III) citrate as precursors. In order to obtain stable solutions, which transform to homogeneous gels upon drying, the pH is adjusted to 7 and a citric acid content equimolar to the metal ions is selected.The presence of nitrate strongly accelerates the thermo-oxidative decomposition step of the precursor gel around 200 °C, and the decomposition is finished at a lower temperature for the nitrate containing precursor (460 °C) than without nitrates (500 °C) in dynamic dry air. An oxidative ambient is required to fully decompose the precursor.The presented synthesis allows very low temperature (400 °C) crystallization of BiFeO₃ together with a secondary phase, as shown by high temperature XRD. This parasitic phase remains up to high temperatures, where decomposition of BiFeO₃ is observed from 750 °C onwards, and Bi₂Fe₄O₉ is formed. However, optimization of the furnace treatment, considering anneal temperatures and heating rates showed that phase pure BiFeO₃ can be obtained, with the heating rate being the crucial factor (5 °C/min). The chemical purity of the powders is confirmed by FTIR, and the antiferromagnetic to paramagnetic phase transition is demonstrated by DSC measurements.     

The effects of temperature,holding time and salt amount on formation of nano CaZrO3 via molten salt method

Nano-particles of CaZrO₃ were successfully synthesized at 800 °C using the molten-salt method, and the effects of processing parameters, such as temperature, holding time and amount of salt on the crystallization of CaZrO₃ were investigated. Na₂CO₃, CaCl₂ and nano-ZrO₂ were used as starting materials. On heating, Na₂CO₃ reacted with CaCl₂ to form NaCl and in situ CaCO₃. Na₂CO₃–NaCl molten eutectic salt provided a liquid medium for reaction of CaCO₃ and ZrO₂ to form CaZrO₃. The results demonstrated that CaZrO₃ started to form at about 700 °C and that, after the temperature was increased to 1000 °C, the amounts of CaZrO₃ in the resultant powders increased with a concomitant decrease in CaCO₃ and ZrO₂ contents. After washing with hot-distilled water, the samples heated for 3 h at 800 °C were single-phase CaZrO₃ with 70–90 nm particle size. Furthermore, the synthesized CaZrO₃ particles retained the size and morphology of the ZrO₂ powders, which indicated that a template formation mechanism dominated the formation of CaZrO₃ by molten-salt synthesis.     

Charge–discharge curves and discharge capacities of LiNi1−yCoyO2 synthesized from lithium carbonate and nickel and cobalt oxides

LiNi_1?yCo_yO₂ (y=0.1, 0.3, and 0.5) were synthesized by a solid-state reaction method at 800 °C and 850 °C using Li₂CO₃, NiO, and Co₃O₄ as the starting materials. The electrochemical properties of the synthesized LiNi_1?yCo_yO₂ were then investigated. For samples with the same composition, the particles synthesized at 850 °C were larger than those synthesized at 800 °C. The particles of all the samples synthesized at 850 °C were larger than those synthesized at 800 °C. LiNi_0.5Co_0.5O₂ synthesized at 850 °C had the largest first discharge capacity (159 mA h/g), followed in order by LiNi_0.7Co_0.3O₂ synthesized at 800 °C (158 mA h/g) and LiNi_0.9Co_0.1O₂ synthesized at 850 °C (151 mA h/g). LiNi_0.9Co_0.1O₂ synthesized at 850 °C had the best cycling performance with discharge capacities of 151 mA h/g at n=1 and 156 mA h/g at n=5.     

Sol–gel derived alumina–hydroxyapatite–tricalcium phosphate porous composite powders

In this study, alumina–hydroxyapatite–tricalcium phosphate (α-Al₂O₃–HA–TCP) porous composite powders were produced and characterized. At first, boehmite sol (AlOOH) was obtained via sol–gel process by using aluminium isopropoxide (Al(OC₃H₇)₃) as the starting material. Bovine hydroxyapatite (BHA) powders derived from deproteinized bovine bones were added as 10, 20, 30 and 50% weight of the starting material to each boehmite sol. Also Na-alginate was added to the boehmite sol as the dispersive agent. Subsequently, gelation for 3 h at 110 °C was applied to each sol mixture. Finally, gelated samples were heat treated for 2 h at 500, 800, 1000 and 1300 °C. DTA–TGA, XRD, FTIR and SEM-EDS analyses were used to characterize the obtained composite powders composed of α-Al₂O₃–HA–TCP phases. In order to investigate porosity properties, powders were pressed with hydraulic manual press and formed into pellets. Later these pellets were sintered for 2 h at 1300 °C. Apparent porosity and bulk density tests were applied to the pellets. The evaluation of these tests results indicate that a novel α-Al₂O₃–HA–TCP composite material with ～38–44% apparent porosity has been produced.     

SrCo0.9Sc0.1O3−δ perovskite hollow fibre membranes for air separation at intermediate temperatures

SrCo_0.9Sc_0.1O₃ (SCSc) perovskite powders with sub-micron particle size were synthesized by a modified Pechini method combined with a post-treatment of sintering and ball-milling. From the prepared powders, the SCSc hollow fibre membranes with asymmetric structure and gas-tight property were fabricated by spinning a polymer solution containing 58.4 wt% SCSc followed by sintering at 1200 °C for 5 h. The oxygen permeation properties of the obtained SCSc fibres were measured under air/He gradients at 500–800 °C. This showed the oxygen flux of 1 mL cm^?2 min^?1 at 750 °C and 4.41 mL cm^?2 min^?1 at 900 °C. Modeling analysis reveals that the oxygen permeation process is predominated by oxygen surface exchange kinetics with an activation energy of 95.0 kJ mol^?1. The SCSc membranes showed excellent oxygen permeation performance while exhibiting high structural and permeating stability at intermediate temperatures (500–800 °C).