TiO2–SnO2 nanomaterials for gas sensing and photocatalysis

Nanopowders of TiO₂–SnO₂ over a full composition range extending from 100 mol% TiO₂ to 100 mol% SnO₂ are obtained by the sol–gel method from TTIP and SnCl₂·5H₂O precursors of Ti and Sn, respectively followed by calcination at 400 °C. The samples are characterized by means of BET, XRD and TEM. Optical properties of the prepared nanomaterials are studied as well. TEM images indicate that the nanoparticles are regular in shape. The specific surface area, SSA of TiO₂ is 95 m²/g while that of SnO₂ amounts to 129 m²/g. The highest SSA of 156 m²/g is achieved at 20 mol% of TiO₂. Occurrence of rutile, anatase and brookite polymorphic forms depends on the chemical composition of nanopowders. Formation of rutile-type solid solution of TiO₂–SnO₂ over the range of 0–80 mol% TiO₂ is confirmed by Vegard rule applied to lattice constants. Electronic band gap decreases with Ti content from 3.84 eV (100 mol% SnO₂) to 3.18 eV (100 mol% TiO₂).     

Platinum–tin bimetallic nanoparticles for methanol tolerant oxygen-reduction activity

Carbon-supported Pt–Sn/C bimetallic nanoparticle electrocatalysts were prepared by the simple reduction of the metal precursors using ethylene glycol. The catalysts heat-treated under argon atmosphere to improve alloying of platinum with tin. As-prepared Pt–Sn bimetallic nanoparticles exhibit a single-phase fcc structure of Pt and heat-treatment leading to fcc Pt₇₅Sn₂₅ phase and hexagonal alloy structure of the Pt₅₀Sn₅₀ phase. Transmission electron microscopy image of the as-prepared Pt–Sn/C catalyst reveals a mean particle diameter of ca. 5.8 nm with a relatively narrow size distribution and the particle size increased to ca. 20 nm when heat-treated at 500 °C due to agglomeration. The electrocatalytic activity of oxygen reduction assessed using rotating ring disk electrode technique (hydrodynamic voltammetry) indicated the order of electrocatalytic activity to be: Pt–Sn/C (as-prepared) > Pt–Sn/C (250 °C) > Pt–Sn/C (500 °C) > Pt–Sn/C (600 °C) > Pt–Sn/C (800 °C). Kinetic analysis reveals that the oxygen reduction reaction on Pt–Sn/C catalysts follows a four-electron process leading to water. Moreover, the Pt–Sn/C catalyst exhibited much higher methanol tolerance during the oxygen reduction reaction than the Pt/C catalyst, assessing that the present Pt–Sn/C bimetallic catalyst may function as a methanol-tolerant cathode catalyst in a direct methanol fuel cell.     

Luminescent and structural properties of manganese-doped zinc aluminate spinel nanocrystals

Manganese-doped zinc aluminate spinel (ZnAl₂O₄:Mn; Mn=0–6.0 mol%) phosphor nanoparticles were prepared by the sol–gel process. The effects of thermal annealing and dopant concentration on the structure, microstructure and luminescence of the powder phosphors were investigated. The X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) results confirmed that a single-phase spinel started to crystallize at around 600 °C for the investigated powders. On heating at 600–1200 °C, the powders had the average crystallite sizes of around 12–33 nm. The crystallite size and lattice constant increased as the doping level of Mn increased. FT-IR spectra exhibited only absorption bands of the AlO₆ octahedral groups, which suggested that the powder phosphors mainly crystallized in a normal spinel structure. Scanning electron microscopy (SEM) investigations showed the primary particle sizes were around 20–25 nm for the powders annealed at 1000 °C, and less than ca. 50 nm for those annealed at 1200 °C. Photoluminescence (PL) spectra under UV or visible light excitation exhibited a strong green emission band centered at 510 nm, corresponding to the typical ⁴T₁(⁴G)—⁶A₁(⁶S) transition of tetrahedral Mn²⁺ ions. The most intense PL emission was obtained by exciting at 458 nm. The PL intensity was significantly enhanced by the improved crystallinity and diminished OH^? groups. Optimum brightness occurred at a doping of 3.0 mol% Mn.     

Brookite and anatase nanomaterial polymorphs of TiO2 synthesized from TiCl3

Synthesis of anatase and brookite was achieved under mild conditions in aqueous solution. In addition, mixtures of brookite and rutile as well as mixtures of the anatase and rutile polymorphs were observed at different temperatures. It was observed that temperatures above 80 °C produced anatase and brookite phases, exclusively. The samples prepared using the acetate synthesis showed on average bandgap around 2.95–3.0 eV and brookite was observed. Whereas the samples prepared using the sulfate synthesis showed and bandgap from 3.1 to 3.2 eV and anatase was observed. In addition, the average grain size of the brookite and anatase phase synthesized at 100 °C were 9.7 and 12 nm, respectively, as determined from XRD.     

Phase stability and mechanical properties of TZP with a low mixed Nd2O3/Y2O3 stabiliser content

The phase assembly of 1.0–5.0 mol% Nd₂O₃-doped ZrO₂ sintered at 1400 °C revealed that the tetragonal ZrO₂ phase could not be completely stabilised. Co-stabilising of 0.5–2.5 mol% Nd₂O₃ with 0.5–1.0 mol% Y₂O₃, however, allowed the preparation of fully dense (Nd,Y)-TZP ceramics by pressureless sintering in air at 1450 °C. The mixed stabiliser monoclinic zirconia nanopowder starting material was synthesized from a suspension of neodymium nitrate, yttrium nitrate and monoclinic zirconia powder in an alcohol/water mixture. A HV₃₀ hardness of 10 GPa combined with an excellent indentation toughness of 13 MPa m^1/2 could be achieved for the (1.0Nd,1.0Y)- and (1.5Nd,1.0Y)-TZP ceramics. The influence of the mixed stabiliser content on the phase stability and mechanical properties are investigated and discussed.     

Potassium dodecatungstocobaltate trihydrate (K5CoW12O40 · 3H2O): A mild and efficient reusable catalyst for the synthesis of aryl-14H-dibenzo[a.j]xanthenes under conventional heating and microwave irradiation

A simple and efficient procedure has been developed for the preparation of aryl-14H-dibenzo[a.j]xanthenes by a one-pot condensation of β-naphthol and aryl aldehydes, in the presence of potassium dodecatungstocobaltate trihydrate [K₅CoW₁₂O₄₀ · 3H₂O, (0.01 mol%)] as a heterogeneous catalyst in a solvent-free media using both conventional heating and microwave irradiation. The present methodology offers several advantages such as excellent yields, simple procedure, short reaction times (1.5–2.0 h and 2.0–3.0 min) and milder conditions and the catalyst exhibited remarkable reusable activity.     

Enhanced photocatalytic activity of porous single crystal TiO2/CNT composites by annealing process

To improve the photocatalytic performance of anatase TiO₂ (a-TiO₂), it is necessary to simultaneously increase its crystallinity and surface area. Our approach to achieve the desired morphology is to develop a porous single crystal that can be transformed from its mesocrystal form via annealing. We synthesized a-TiO₂ mesocrystals onto multiwalled CNTs using a facile one-pot chemical approach, and investigated the effect of the annealing temperature (200–600 °C) on the crystallinity, morphology, chemical bonding state, and photocatalytic performance of the TiO₂/CNT composites. The as-grown sample and sample annealed at 200 °C consisted of spindle-like a-TiO₂ mesocrystals. As the annealing temperature increased to 400 °C, the morphology of a-TiO₂ changed from mesocrystals into porous single crystals and the surface area enlarged due to the thermo-decomposition of organic residues between the subunits. The chemical bonding (Ti–O–C) between TiO₂ and CNT was also strengthened with increasing annealing temperature. On the other hand, the TiO₂ was separated from the CNT at 600 °C because of the large difference in the thermal expansion coefficients. The photocatalytic performance of the TiO₂/CNT composites was the highest at 400 °C due to the increased crystallinity, removal of the by-products, and strengthened Ti–O–C bonds, resulting in an increase in the photocatalytic active sites and efficient charge separation.     

Synthesis of titanium oxide particles in supercritical CO2: Effect of operational variables in the characteristics of the final product

A new chemical precursor is proposed for the synthesis of TiO₂ anatase nanoparticles in supercritical CO₂: the organometallic diisopropoxititanium bis(acetylacetonate) (DIPBAT). DIPBAT thermohydrolysis in supercritical carbon dioxide (SC-CO₂) has been studied in the range 10.0–20.0 MPa and 200–300 °C, and compared with that of titanium tetraisopropoxide (TTIP). The proposed reaction mechanism is a thermohydrolysis, where the hydrolysis of acetylacetonate groups is the limiting step of the reaction rate. The addition of water directly to the reaction favours the growth of formed particles, whereas ethanol offers better results as hydrolysing reactant, leading to smaller particles. Experiments have been performed first in a batch process and secondly in a semi-continuous one, varying the residence time in the reactor from 30 s to 2 min. The effect of operational variables in the final product and their influence in the different steps of the process have been studied. Results have shown that product crystallinity is related with temperature, and temperatures higher than 250 °C are necessary to obtain well-crystallized TiO₂ anatase. In the same sense, area Brunauer–Emmett–Teller (BET) is connected with crystallinity, and amorphous product, Ti(OH)₄, shows the highest surface area. Particle size and particle size distribution (PSD) are controlled by instantaneously supersaturation degree, and precursor concentration together with pressure are the main responsible of particle size control. Operational conditions influence solubility of species, mass transfer, chemical reaction and nucleation and particle growth and they mark the final characteristics of the product and its application. In such a way, good crystallized TiO₂ anatase particles of about 200 nm in diameter have been obtained working at 300 °C, 20.0 MPa and residence time of 2 min, with a reaction medium composed by CO₂/ethanol (80/20, v/v). Such particles present good optical properties and specific surface area BET of around 150 m²/g. At lower working temperatures the obtained particles present worse crystallinity; however, their specific surface area increases to 350 m²/g and they are suitable as support of metal clusters in heterogeneous catalysis.     

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.     

Preparation of highly pure and crystalline carbon nanotubes and their infiltration by paraffin wax

Carbon nanotubes (CNTs) of ultrahigh purity and high crystallinity, which could be used for the encapsulation of nanoscaled materials, were fabricated by the heat treatment of disordered CNT-encapsulated In–Sn nanowires at temperatures lower than 1800 °C in H₂ under vacuum conditions (pressure of approximately 1 Pa). The results showed that nearly 100% of the encapsulated In–Sn alloy was removed at 1800 °C, and as much as 99.99% of it at 1600 °C. The prepared CNTs were also filled with paraffin wax. A vacuum-based infiltration–purification process proved effective for fabricating the CNT–paraffin hybrid structures at a high filling yield, which was confirmed by thermograms and TEM observations.     

Microwave dielectric properties of Mn-doped BaO–(Nd0.7,Sm0.3)2O3–4TiO2 ceramic sintered in a reducing atmosphere

The effect of MnCO₃ doped from 0 to 55 mol% into BaO–(Nd_0.7Sm_0.3)₂O₃–4TiO₂ (BNST) sintered in a reducing atmosphere on the microstructure and electrical properties was studied. Mn³⁺ completely substituted into Ti⁴⁺-sites of BNST to form a solid solution, so there is no second phase until 42 mol% which is the maximum solubility. Mn (<42 mol%)-doped BNST sintered in a reducing atmosphere is in a semi-conducing state because the concentration of free electron is higher than that of the acceptors. On the other hand, when Mn content doped into BNST exceeds a critical value (>43 mol%), the second Mn-rich phase due to excess of Mn³⁺ substituted into Ti⁴⁺-site, corresponding to original BaO–(Nd_0.7Sm_0.3)₂O₃–4TiO₂ (1 1 4) phase, is formed. Mn (>43 mol%)-doped BNST sintered in a reducing atmosphere is in an insulating state because the concentration of the acceptors is higher than that of liberated free electron, so the insulation resistance becomes high and tan δ becomes low. The formation of the second Mn-rich phase affects Q × f factor and temperature coefficient of capacitance (T.C.C.) of BNST significantly.     

Process-tolerant pressureless-sintered silicon carbide ceramics with alumina-yttria-calcia-strontia

Process-tolerant SiC ceramics were prepared by pressureless sintering at 1850–1950 °C for 2 h in an argon atmosphere with a new quaternary additive (Al₂O₃-Y₂O₃-CaO-SrO). The SiC ceramics can be sintered to a > 94% theoretical density at 1800–1950 °C by pressureless sintering. Toughened microstructures consisting of relatively large platelet grains and small equiaxed grains were obtained when SiC ceramics were sintered at 1850–1950 °C. The presently fabricated SiC ceramics showed little variability of the microstructure and mechanical properties with sintering within the temperature range of 1850–1950 °C, demonstrating process-tolerant behavior. The thermal conductivity of the SiC ceramics increased with increasing sintering temperature from 1800 °C to 1900 °C due to decreases of the lattice oxygen content of the SiC grains and residual porosity. The flexural strength, fracture toughness, and thermal conductivity of the SiC ceramics sintered at 1850–1950 °C were in the ranges of 444–457 MPa, 4.9–5.0 MPa m^1/2, and 76–82 Wm^?1 K^?1, respectively.     

High piezoelectricity in CuO-modified Ba(Ti0.90Sn0.10)O3 lead-free ceramics with modulated phase structure

High piezoelectricity was achieved in Ba(Ti_0.90Sn_0.10)O₃ lead-free ceramics by optimizing CuO addition and sintering temperature. The phase structure of 1.0 mol% CuO-doped Ba(Ti_0.90Sn_0.10)O₃ ceramic is coexisting rhombohedral and tetragonal phases as sintered at 1300 °C. The coexistence of rhombohedral, tetragonal and orthorhombic phases appears in 1.0 mol% CuO-doped Ba(Ti_0.90Sn_0.10)O₃ ceramics as sintered at 1350–1450 °C, which leads to highly enhanced d₃₃ up to 650pC/N. This work demonstrates that high piezoelectric property (d₃₃ = 650pC/N) can be obtained in BaTiO₃-based lead-free piezoceramics with a simple composition modification by modulating phase structures, which also indicates that Ba(Ti,Sn)O₃ is a promising candidate to replace the lead-based piezoceramics.     

Investigation on the anti-reduction mechanism of Ti4+ in high dielectric constant system Ca0.9La0.067TiO3 by doping with Al2O3

Ca_0.9La_0.067TiO₃ (abbreviated as CLT) ceramics doped with different amount of Al₂O₃ were prepared via the solid state reaction method. The anti-reduction mechanism of Ti⁴⁺ in CLT ceramics was carefully investigated. X-ray diffraction (XRD) was used to analyze the phase composition and lattice structure. Meanwhile, the Rietveld method was taken to calculate the lattice parameters. X-ray photoelectron spectroscopy (XPS) was employed to study the valence variation of Ti ions in CLT ceramics without and with Al₂O₃. The results showed that Al³⁺ substituted for Ti⁴⁺ to form solid solution and the solid solubility limit of Al³⁺ is near 1.11 mol%. Furthermore, the reduction of Ti⁴⁺ in CLT ceramics was restrained by acceptor doping process and the Q × f values of CLT ceramics were improved significantly. The CLT ceramic doped with 1.11 mol% Al₂O₃ exhibited good microwave dielectric properties: ε_r = 141, Q × f = 6848 GHz, τ_f = 576 ppm/°C.     

Effect of solid solution formation on densification of hot-pressed ZrC ceramics with MC (M = V,Nb, and Ta) additions

ZrC ceramics with additions of MC (M = V, Nb, and Ta) were prepared by hot pressing, and the effect of MC additions on densification was analyzed in terms of the solubility limit and kinetics of formation of MC solid solutions with ZrC. VC additions of 2.5–10 vol% (3.5–13.5 mol%), which is higher than its solid solubility limit of 1.3 vol% (1.8 mol%), effectively promoted the densification process and nearly fully dense ZrC ceramics were obtained by hot-pressing at 1900 °C. In contrast, both NbC and TaC additions, which can form unlimited solid solutions with ZrC, have no obvious contribution to ZrC densification. This is because formation of the solid solution of NbC and TaC with ZrC matrix requires higher temperature and longer time due to their stronger bonding energy, compared to VC. SEM observation demonstrated that the VC addition resulted in larger grains, compared to ZrC ceramics with NbC and TaC additions.     

Influence of small amounts of gallium oxide addition on ionic conductivity of La0.9Sr0.1Ga0.8Mg0.2O3-δ solid electrolyte

The effects of small amounts of gallium oxide on intragrain and intergrain conductivity of La_0.9Sr_0.1Ga_0.8Mg_0.2O_3-δ are investigated by impedance spectroscopy in the 280–420 °C range. Bulk specimens with 0.5, 1.0 and 1.5 mol% gallium oxide are prepared by solid state reaction at 1350 °C. All specimens achieved relative density values higher than 95%. The additive promotes grain growth indicating solid solution formation. A small fraction of the additive remains at grain boundaries and increases the fraction of the gallium-rich, LaSrGa₃O₇, impurity phase. The intragrain conductivity of gallium oxide containing specimens is higher than that of the parent solid electrolyte. Similar effect is found for the intergrain conductivity, which is maximum for 1 mol% gallium oxide addition.     

Salt effect on the liquid–liquid equilibrium of the ternary (water + phenol + methyl isobutyl ketone) system: Experimental data and correlation

The effects of NaCl, KCl and Na_2SO_4 on the liquid–liquid equilibrium(LLE) data for the ternary system, water+ phenol + methyl isobutyl ketone, were determined at 0.101 MPa and 333.15 K and 343.15 K.The nonrandom two-liquid(NRTL) model was used to correlate the experimental data and to yield corresponding binary interaction parameters for these salt containing systems.The Hand and Othmer–Tobias equations were used to confirm the dependability of the determined LLE data in this work.Distribution coefficient and selectivity were used to evaluate the extraction performance of methyl isobutyl ketone with the existence of salt.The magnitude of salt effect on the water + phenol + methyl isobutyl ketone(MIBK) system is in the following order: Na_2SO_4NaClKCl.     

Ytterbia–neodymia–costabilized TZP—Breaking the limits of strength–toughness correlations for zirconia?

TZP ceramics were manufactured by hot pressing of pyrogenic zirconia nanopowder which was costabilized by 1 mol% ytterbia and 2 mol% neodymia (1Yb–2Nd–TZP) via the nitrate route. The evolution of microstructure, phase composition and mechanical properties with variation of sintering temperature from 1200 °C to 1400 °C was investigated. 1Yb–2Nd–TZP consists of a bimodal microstructure of small very transformable tetragonal grains and large cubic grains. At intermediate sintering temperature the materials combine a bending strength of 1250 MPa with a fracture resistance >13 MPa √m. The high threshold stress intensity of 7 MPa √m indicates high resistance to subcritical crack growth. An increase in fracture resistance before the crack tip induced by compressive residual stress shifts the strength–toughness correlations to higher values than previously considered possible.     

The influence of the additive BaGeO3 on BaSnO3 ceramics

DTA, XRD and sintering investigations of the system BaSnO₃–BaGeO₃, prepared by a mixed-oxide method, are described herein. The melting temperature of this system is about 1270 ± 5 °C. We find a partial solubility of BaGeO₃ into BaSnO₃ of the order of 6–7 mol%. Up to 50 mol% BaGeO₃, the calcined powders (1150 °C) as well as the once-sintered samples consist of BaSnO₃ and orthorhombic BaGeO₃ at room temperature. A gradual appearance of hexagonal BaGeO₃ can be observed in calcined powders and once-sintered ceramics with a BaGeO₃ content above 50 mol%. After sintering at ≥1200 °C for more than 1 h all ceramic bodies consist of BaSnO₃ and orthorhombic BaGeO₃. The addition of BaGeO₃ leads to a considerable reduction of the sintering temperature and to a strong densification. Sintering at 1180 °C for 10 h and an addition of only 1 mol% BaGeO₃ leads to dense ceramic bodies with cubic-like grains.     

Dielectric and thermal properties of AlN ceramics

The effects of slow-cooling and annealing conditions on dielectric loss, thermal conductivity and microstructure of AlN ceramics were investigated. Y₂O₃ from 0.5 to 1.25 mol% at 0.25% increments was added as a sintering additive to AlN powder and pressureless sintering was carried out at 1900 °C for 2 h in a nitrogen flowing atmosphere. To improve the properties, AlN samples were slow-cooled at a rate of 1 °C min⁻¹ from 1900 to 1750 °C, subsequently cooled to 970 °C at a rate of 10 °C min⁻¹ and then annealed at the same temperature for 4 h. AlN and YAG (5Al₂O₃/3Y₂O₃) were the only identified phases from XRD. AlN doped with 0.5 and 0.75 mol% Y₂O₃ had a low loss of <2.0 × 10⁻³ and a high thermal conductivity of >160 W m⁻¹ °C⁻¹.