Fabrication of highly dispersed crystallized nanoparticles of barium strontium titanate in the presence of N,N-dimethylacetamide

Highly dispersed nanoparticles of barium strontium titanate (BST) were successfully synthesized by hydrolysis method using N,N-dimethylacetamide as a solvent at 120 °C and 140 °C. X-ray diffraction analysis (XRD) showed that the as-prepared particles presented a perovskite polycrystalline structure. The result of transmission electron microscopy (TEM) images revealed the particle size in the range of 5-30 nm. The composition without any annealing treatment characterized with the parallel plate capacitor method displayed good dielectric properties.     

Nano-twinned structure and photocatalytic properties under visible light for undoped nano-titania synthesised by hydrothermal reaction in water-ethanol mixture

Nano-TiO₂ crystals showing visible light driven photocatalytic activity were synthesized by hydrothermal reaction in an ethanol-water mixture. The experiments were conducted to optimise the synthesis conditions for nano titania, in the range of temperature from 200 to 400 °C. X-ray diffraction depicted that the products obtained were anatase at 250 °C and above. For the products obtained at 250 °C, detailed analysis was conducted since it depicted high crystallinity with smallest particle sizes. Shape of the crystal was rounded rectangular with the size of 4 ± 1 nm to 7 ± 1 nm. The high-resolution transmission electron microscopy (HRTEM) revealed the existence of novel nano-twin structure in anatase grains and surface defects around the nanocrystals. Photocatalytic property was investigated for these undoped titania samples under UV and visible light. The nano twin structure, surface defects, and nano-meter size of the synthesized titania are believed to play a crucial role for the high catalytic activity.     

A short solid-state synthesis leading to titanate compounds with porous structure and nanosheet morphology

A novel method was developed for the synthesis of titanate nanosheets with high surface area. A solid-state mixture of NaOH and TiO₂ was reacted at 600 °C for several minutes. The aqueous dispersion of the resulting melt was aged at room temperature for periods up to 14 days. After hydrochloric acid treatment and washing procedures, the reaction product was characterized by X-ray diffraction, Raman spectroscopy, N₂-sorption and small-angle X-ray scattering measurements. The titanate compound not subjected to the aging process was amorphous and possessed a microporous framework, while the aged samples displayed nanosheet morphology and high specific surface area (396-509 m² g⁻¹). It was revealed that the very short heat treatment is of crucial importance for the titania-titanate phase transformation, while the aging process is needed for the morphological evolution of the titanate samples. The effects of the aging time on the structure and the morphology are discussed.     

Reaction sintering of colloidal processed mixtures of sub-micrometric alumina and nano-titania

The fabrication of composites formed by alumina grains (95 vol%) in the micrometer size range and aluminium titanate nanoparticles (5 vol%) by reaction sintering of alumina (Al₂O₃) and titania (TiO₂) is investigated. The green bodies were constituted by mixtures of sub-micrometric alumina and nano-titania obtained from freeze-drying homogeneous water based suspensions, and pressing the powders. The optimization of the colloidal processing variables was performed using the viscosity of the suspensions as control parameter. Different one step and two step sintering schedules using as maximum dwell temperatures 1300 and 1400 °C were established from dynamic sintering experiments. Specimens cooled at 5 °C/min as well as quenched specimens were prepared and characterized in terms of crystalline phases, by X-ray diffraction, and microstructure by scanning electron microscopy of fracture surfaces.Even though homogeneous final materials were obtained in all cases, full reaction was obtained only in materials treated at 1400 °C. The microstructure of the composites obtained by quenching was formed by an alumina matrix with bimodal grain size distribution and submicrometric aluminium titanate grains located inside the largest alumina grains and at triple points. However a cooling rate of 5 °C/min led to significant decomposition of aluminium titanate. This fact is attributed to the small size of the particles and the effect of the alumina surrounding matrix.     

Investigation of hydrothermal synthesis parameters on characteristics of T type zeolite crystal structure

Hydrothermal synthesis of zeolite T in aqueous alkaline solutions without using templates was investigated. Zeolite T crystals were prepared via hydrothermal synthesis using milk-like aluminosilicate gel with a composition of aSiO₂:bAl₂O₃:cNa₂O:dK₂O:xH₂O. The effects of molar compositions including silicon module (n_RM = a/b) and relative alkalinity (α = OH/SiO₂), and crystallization conditions including crystallization temperature (T) and time (t) on the yield of T-type crystals were investigated. This research work examines changes in the yield of crystalline zeolite phases by varying the gel composition parameters (n_RM = 20-25, and α = 0.71-0.82) and crystallization process temperature and time (T = 100°−140 °C, t = 120-216 h), while keeping constant the parameters [OH] = 2.77 m, U_RM(Na/Na + K) = 0.75, stirring time = 24 h , stirring temperature = 30 °C, and drying temperature = 100 °C. The crystal species of zeolite T were characterized by XRD (X-ray diffraction) and SEM (Scanning Electron Microscope).     

Engineering grain size and electrical properties of donor-doped barium titanate ceramics

A semiconducting lanthanum-doped barium titanate ceramic has been fabricated for battery safety applications by simple means from nanoparticles prepared at room temperature by kinetically controlled vapor diffusion catalysis. The material, characterized by electron microscopy, X-ray diffraction and electrical measurements, exhibits a difficult to achieve combination of submicron grain size (∼500 nm) and attractive electrical properties of room temperature resistivity below 100 Ω cm and a 12-fold increase in resistivity through the Curie temperature (positive thermal coefficient of resistivity, PTCR). Systematic investigation of sintering conditions revealed that a short period of heating at 1350 °C under air is necessary to suppress abnormal grain growth, while precise control of the cooling rate is needed to achieve the targeted electrical properties. Cooling must be sufficiently fast to avoid complete back-oxidation, yet slow enough to facilitate oxygen adsorption at the grain boundaries to produce the thin oxide layer apparently responsible for the observed PTCR.     

Photocatalytic degradation of methylene blue with TiO2 nanoparticles prepared by a thermal decomposition process

The generation of TiO₂ nanoparticles by the thermal decomposition of titanium tetraisopropoxide (TTIP) was carried out experimentally using a tubular electric furnace at various synthesis temperatures (700-1300 °C) and TTIP heating temperatures (80-110 °C). The photocatalytic activity of the resulting TiO₂ nanoparticles was examined by measuring the rate of methylene blue decomposition. The TiO₂ nanoparticles were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) measurements and transmission electron microscopy (TEM). The crystallite size and crystallinity increased with increasing synthesis temperature and TTIP heating temperature. A TTIP heating temperature and synthesis temperature of 95 °C and 900 °C, respectively, were found to be the optimal synthesis conditions. The primary particle diameter obtained under optimum synthesis conditions was considerably smaller than the commercial photocatalyst (Degussa, P25). The specific surface areas were more than 134.4 m² g^− 1. Under the optimal conditions, the photocatalytic activity for methylene blue was higher than that of the commercial photocatalyst.     

Effect of vibro-milling time on phase formation and particle size of barium titanate nanopowders

Barium titanate (BT) nanopowder was synthesized by a solid state reaction via a rapid vibro-milling technique. The effect of milling time on phase formation and particle size of BT powder was investigated. Powder samples were characterized using XRD (X-ray diffraction) and SEM techniques. It was found that the resulting BT powders have a range of particle size depending on milling times. Production of a single-phase BT nanopowder can be successfully achieved by employing a combination of 30 h milling time and calcination conditions of 1200 °C for 2 h.     

Electrochemical lithium storage of sodium titanate nanotubes and nanorods

Layered hydrated sodium titanate nanotubes are synthesized via a hydrothermal reaction in alkaline solution. The as-prepared nanotubes are calcined at different temperatures (300-600 °C) in air. The microstructure of obtained samples is characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). It is observed that the calcined products maintain their parent tubular morphologies below 500 °C. After calcinations at 600 °C, the hollow tubular morphology could completely be converted to the short solid nanorod morphology. In the meanwhile, the monoclinic sodium hexatitanate as a main phase is formed in nanorods, coexisted with sodium trititanate as a residual phase. The electrochemical lithium storage of obtained samples is studied by galvanostatic method and cyclic voltammetry. It is demonstrated that the nanotubes calcined at 500 °C have relatively large reversible capacity, good reversibility and excellent high rate discharge capability. The lithium intercalation process is shown to have pseudocapacitive feature caused by their layered structure and open lithium insertion tunnels, which is in favor of the high rate charge/discharge capability of sodium titanate nanotubes.     

Highly active and selective Cu/SiO2 catalysts prepared by the urea hydrolysis method in dimethyl oxalate hydrogenation

Cu/SiO₂ catalysts have been successfully prepared via urea hydrolysis method. The catalysts have been systematically characterized by X-ray diffraction, high-resolution transmission electron microscopy, N₂-physisorption and H₂ temperature-programmed reduction. The results demonstrated the presence of copper nanoparticles and their high dispersion on the SiO₂ support. Catalysts with different copper loadings were prepared, and their performances in the hydrogenation of dimethyl oxalate to ethylene glycol were studied. A 100% conversion of dimethyl oxalate and maximum 98% selectivity of ethylene glycol were reached with 15.6 wt.% copper loading at 200 °C and 2 MPa. Furthermore, under the same reaction conditions, the catalyst can maintain the selectivity of 90% when the reduction temperature reduced from 350 °C to 200 °C. The high activity and selectivity over the catalyst may be ascribed to the homogenously distribution of copper nanoparticles on the large surface.     

Assessment of structurally stable cubic Bi12TiO20 as intermediate temperature solid oxide fuels electrolyte

Colloid processing and subsequent pressure filtration were used to prepare 14.3 mol% TiO₂ doped Bi₂O₃ (Bi₁₂TiO₂₀, 14BTO) as solid oxide fuel cell electrolyte. Materials characterization and electrical behaviors of 14BTO samples were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and two-point probe DC conductivity. A pure 14BTO with a cubic sillenite single phase was prepared at the sintering process of 850 °C with a high relative sintered density of 96.82%. In situ and batch-type long-term conductivity measurements at 600 °C were carried out to verify the possible reason of degradation. Additional reduction-oxidation tests under CH₄ atmosphere by thermogravimetric analysis (TGA) revealed possible application temperature of 14BTO electrolytes below 700 °C.     

Hydrothermal synthesis of carbonate-free submicron-sized barium titanate from an amorphous precursor: Synthesis and characterization

In this paper, the amorphous barium titanate precursor was prepared by the peroxo-hydroxide method and post-treated by various drying procedures, such as: room temperature drying, room temperature vacuum drying and vacuum drying at 50 °C. The objective in the latter two treatments was to increase the Ti-O-Ba bonds of the precursor. The post-treated precursors were compared with the untreated (i.e., ‘wet’) precursor. Also, a barium titanate precursor was prepared by an alkoxide route. Afterwards, the precursors were hydrothermally treated at 200 °C in a 10 M NaOH solution. Vacuum drying of the precursor seemingly promoted the formation of Ti-O-Ti bonds in the hydrothermal end-product. The low Ba:Ti ratio (0.66) of the alkoxide-route prepared precursor lead to a multi-phase hydrothermal product with BaTiO₃ as the main phase. In contrast, phase pure BaTiO₃, i.e. without BaCO₃ contamination, was obtained for the precursor which was dried at room temperature. Cube-shaped and highly crystalline BaTiO₃ particles were observed by electron microscopy for the hydrothermally treated peroxo-hydroxide-route prepared precursor.     

Formation of needle-like titanium oxynitride particles through nitridation of hydrated titanates

The process of nitridation of hydrated titanate wires was examined by thermal gravimetric (TG) analysis in an NH₃/Ar (50/50 vol.%) gas mixture, X-ray diffraction (XRD) measurement, field emission scanning electron microscope (FE-SEM) and transmission electron microscope (TEM) observations and X-ray photoelectron spectroscopic (XPS) analysis. The nitridation of the hydrated titanate nanowires was accompanied by a two-stage weight loss. In the first stage, occurring in the temperature range of 50-400 °C, the hydrated titanate wires changed to anatase-type TiO₂ nanoparticles with the releasing of H₂O molecules. In the second stage, occurring in the temperature range of 700-1000 °C, the TiO₂ nanoparticles were converted to rock-salt-type titanium oxynitride (TiN_xO_y) nanoparticles. Subsequently, the TiN_xO_y nanoparticles were sintered each other at around 1000 °C. Under a gas flow of 100% NH₃, the hydrated titanate wires were completely changed to TiN_xO_y particles at a temperature greater than 950 °C, which was maintained for 2 h. It is possible to fabricate needle-like TiN_xO_y particles by selecting thick hydrated titanate wires as the starting materials.     

X-ray absorption spectroscopy studies of nickel oxide thin film electrodes for supercapacitors

Nickel oxide films were synthesized by electrochemical precipitation of Ni(OH)₂ followed by heat-treatment in air at various temperatures (200-600 °C). Their structure and electrochemical properties were studied by cyclic voltammetry, X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). XRD results showed that the nickel oxide obtained at 250 °C or above has a crystalline NiO structure. The specific capacitance of the oxide depends on the heat-treatment temperature, showing a maximum value at 300 °C. XAS results revealed that the non-stoichiometric nickel oxide (Ni_1−xO) approached the stoichiometric NiO structure with increasing heat-treatment temperature due to the defect healing effect. The defective nature of the nickel oxide could be utilized to improve its specific capacitance for supercapacitor application.     

Effect of nanocarbon sources on microstructure and mechanical properties of MgO–C refractories

A study of microstructural evolution, mechanical and thermo-mechanical properties of MgO–C refractories, based on graphite oxide nanosheets (GONs), carbon nanotubes (CNTs) and carbon black (CB), was carried out by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDS), three-point bending and thermal shock tests. Meanwhile, these results were compared to the conventional MgO–C refractory containing 10 wt% flaky graphite prepared under the same conditions. The results showed that higher cold modulus of rupture was obtained for the composition containing GONs, and the composition containing CNTs exhibited larger displacement after coking at 1000 °C and 1400 °C. Also, the addition of nanocarbons led to an improvement of the thermal shock resistance; in particular, both compositions containing CNTs and CB had higher residual strength ratio, approaching the thermal shock resistance of the reference composition containing 10 wt% flaky graphite, as it was associated with the presence of nanocarbons and in-situ formation of ceramic phases in the matrix.     

Crystallization behavior of nano-composite based on poly(vinylidene fluoride) and organically modified layered titanate

To understand the effect of the nano-filler particles on the crystallization kinetics and crystalline structure of poly(vinylidene fluoride) (PVDF) upon nano-composite formation, we have prepared PVDF/organically modified layered titanate nano-composite via melt intercalation technique. The layer titanate (HTO) is a new nano-filler having highly surface charge density compared with conventional layered silicates. The detailed crystallization behavior and its kinetics including the conformational changes of the PVDF chain segment during crystallization of neat PVDF and HTO-based nano-composite (PVDF/HTO) have been investigated by using differential scanning calorimetric, wide-angle X-ray diffraction, light scattering, and infrared spectroscopic analyses. The neat PVDF predominantly formed α-phase in the crystallization temperature range of 110-150 °C. On the other hand, PVDF/HTO exhibited mainly α-phase crystal coexisting with γ- and β-phases at low T_c range (110-135 °C). A major γ-phase crystal coexists with β- and α-phases appeared at high T_c (=140-150 °C), owing to the dispersed layer titanate particles as a nucleating agent. The overall crystallization rate and crystalline structure of pure PVDF were strongly influenced in the presence of layered titanate particles.     

Aqueous sol–gel synthesis of zirconium titanate (ZrTiO4) nanoparticles using chloride precursors

Zirconium titanate powders were synthesized by a straightforward sol–gel method using zirconium and titanium chlorides as metal precursors, deionized water as solvent and oxygen donor, and a NaOH solution for adjusting pH to 7. According to transmission electron microscopy, amorphous particles of nearly 5 nm in size with a relatively spherical morphology were prepared. Thermogravimetry and differential scanning calorimetery analyses on the xerogel at a heating rate of 10 °C/min indicated a crystallization temperature of 690 °C, which is comparable with previous reports. Furthermore, via differential scanning calorimetery studies using the Kissinger's equation, the activation energy for ZrTiO₄ crystallization was determined to be 850 kJ/mol. Structural evaluations in the isothermal regime, using X-ray diffraction experiments, implied the onset of ZrTiO₄ crystallization at 550 °C.     

Synthesis of ZnO nanoparticles by an aerosol process

Spherical nano-sized zinc oxide (ZnO) particles were produced by a spray pyrolysis method using the aerosol technique described in this study. The effects of reaction temperatures of 600, 800 and 1000 °C and collection locations of the particles, such as the flask collector and the tube exit, on the morphology and crystal structure of the ZnO particles were investigated. X-ray diffraction (XRD) studies showed that the crystallinity of the particles was increased by increasing the reaction temperature from 600 °C to 1000 °C. Fourier transform infrared spectroscopy (FTIR) measurements revealed that the particles were pure and similar to each other. Scanning electron microscopy (SEM) revealed that the synthesized nanoparticles had sizes between 200 nm and 400 nm, with uniform morphologies. A computational fluid dynamics (CFD) model of the horizontally positioned tube reactor was developed. Simulation results provided information about the residence time and the temperature distribution along the tube, which were found to be correlated to the particle morphology.     

Titanium carbide derived nanoporous carbon for energy-related applications

High surface area nanoporous carbon has been prepared by thermo-chemical etching of titanium carbide TiC in chlorine in the temperature range 200-1200 °C. Structural analysis showed that this carbide-derived carbon (CDC) was highly disordered at all synthesis temperatures. Higher temperature resulted in increasing ordering and formation of bent graphene sheets or thin graphitic ribbons. Soft X-ray absorption near-edge structure spectroscopy demonstrated that CDC consisted mostly of sp² bonded carbon. Small-angle X-ray scattering and argon sorption measurements showed that the uniform carbon-carbon distance in cubic TiC resulted in the formation of small pores with a narrow size distribution at low synthesis temperatures; synthesis temperatures above 800 °C resulted in larger pores. CDC produced at 600-800 °C show great potential for energy-related applications. Hydrogen sorption experiments at −195.8 °C and atmospheric pressure showed a maximum gravimetric capacity of ∼330 cm³/g (3.0 wt.%). Methane sorption at 25 °C demonstrated a maximum capacity above 46 cm³/g (45 vol/vol or 3.1 wt.%) at atmospheric pressure. When tested as electrodes for supercapacitors with an organic electrolyte, the hydrogen-treated CDC showed specific capacitance up to 130 F/g with no degradation after 10 000 cycles.     

Preparation and properties of C/SiC/ZrO2 porous composites by hot isostatic pressing the pyrolyzed preforms

Three phase mixture of C/SiC/ZrO₂ porous composites were prepared from commercially available phenolic resin, Si and ZrO₂ powders. In the first step, mixed powders were pyrolyzed at 850 °C in vacuum to obtain a carbonized microporous material and then hot isostatically pressed at 1200, 1300 and 1350 °C for 10 min in an argon pressure of 50 MPa to prepare C/SiC/ZrO₂ porous composites, in second step. The hot isostatic pressing led to the increase in density from 3.28 to 3.48 g/cm³ and reduction in porosity (from 32 to 20%) of the composites. X-ray diffraction analyses revealed the existence of β-SiC and carbon might be amorphous in the composites. According to the results of scanning electron microscopy, the crystal growth of β-SiC with facets was observed at 1350 °C. In addition, the energy dispersive spectroscopy showed that carbon/silicon atomic ratio was 1:1 in the crystals. X-ray photoelectron spectroscopy of the composites suggested that evolved gaseous molecules, due to the decomposition of phenolic resin, reacted with molecules containing Si to form β-SiC. The formation and growth of β-SiC in addition to the densification of matrix by hot isostatic pressing led to the increase in hardness (max.: 13.99 GPa) at higher temperatures.