One-step flame method for the synthesis of coated composite nanoparticles

A simple in situ flame coating method has been developed by designing a new type of coflow diffusion flame burner having a sliding unit. The sliding unit was shown to be very effective in finding a right position where the precursor for coating layer should meet with core particles. SiO₂-coated TiO₂ nanoparticles were first prepared and whether most surfaces of particles were coated was examined by both direct observation of particles through a transmission electron microscope and Zeta potential measurements. Mean core sizes varied from 28 to 109 nm and mean coating thickness was about 2.4 nm for silica-coated titania particles. By simply changing chemical precursors, we demonstrated that SiO₂-coated SnO₂, SnO₂-coated TiO₂, SiO₂–SnO₂-coated TiO₂ nanoparticles could be also synthesized.     

Nanometric core-shell-shell γ-Fe2O3/SiO2/TiO2 particles

The preparation of core-shell-shell γ-Fe₂O₃/SiO₂/TiO₂ nanoparticles of few tens nanometers is performed by successively coating onto magnetic nanoparticles a SiO₂ layer and a TiO₂ layer, using sol–gel methods. The thickness of the two layers and the aggregation state of the particles can be controlled by the experimental conditions used for the two coatings. These composite nanoparticles may find application as magnetic photocatalysts, since they are characterized by their small diameters which allow a good accessibility to the TiO₂ shell. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

The hybrid photocatalyst of TiO2–SiO2 thin film prepared from rice husk silica

The TiO₂–SiO₂ thin film was prepared by self-assembly method by mixing SiO₂ precursor with titanium precursor solution and aged to obtain a co-precipitation of silica and titanium crystals. Dip coating method was applied for thin film preparation on glass slide. The X-ray diffraction (XRD) of the self-assembly thin film had no characteristic property of SiO₂ and even anatase TiO₂ but indicated new crystal structure which was determined from the Fourier Transform Infrared Spectrophotometer (FTIR) as a hybridized Ti–O–Si bonding. The surface area and surface volume of the self-assembly sample were increased when SiO₂ was incorporated into the film. The self-assembly TiO₂–SiO₂ thin film exhibited the enhanced photocatalytic decolorization of methylene blue (MB) dye. The advantages of SiO₂ are; (1) to increase the adsorbability of the film and (2) to provide the hydroxyl radical to promote the photocatalytic reaction. The self-assembly thin film with the optimum molar ratio (SiO₂:TiO₂) as 20:80 gave the best performance for photocatalytic decolorization of MB dye with the overall efficiency of 81%.     

Emulsion Combustion and Flame Spray Synthesis of Zinc Oxide/Silica Particles

Two flame spray methods, emulsion combustion method (ECM) and flame spray pyrolysis (FSP), were compared for synthesis of pure and mixed SiO₂ and ZnO nanoparticles. The effect of silicon precursor was investigated using liquid hexamethyldisiloxane (HMDSO) or SiO₂ sol, while for ZnO zinc acetate (ZA) was used. Gas phase reaction took place when using HMDSO as Si precursor, forming nanoparticles, whereas the SiO₂ sol used as Si source was not evaporated in the flame, creating large aggregates of the sol particles (e.g. 1 m). The FSP of ZA produced ZnO homogeneous nanoparticles. Lower flame temperatures in ECM than in FSP resulted in mixed gas and liquid phase reaction, forming ZnO particles with inhomogeneous sizes. The FSP of HMDSO and ZA led to intimate gas-phase mixing of Zn and Si, suppressing each other's particle growth, forming nanoparticles of 19 nm in BET-equivalent average primary particle diameter. Nucleation of ZnO and SiO₂ occurred independently by ECM of HMDSO and ZA as well as by FSP of the SiO₂ sol and ZA, creating a ZnO and SiO₂ mixture. The reaction of ZnO with SiO₂ was likely to be enhanced by ECM of the SiO₂ sol and ZA where both Zn and Si species were not evaporated completely, resulting in ZnO, -willemite and Zn_1.7SiO₄ mixed phase.     

Substrate effects on the oxygen gas sensing properties of SnO2/TiO2 thin films

In this study, SnO₂/TiO₂ thin films are fabricated on SiO₂/Si and Corning glass 1737 substrates using a R.F. magnetron sputtering process. The gas sensing properties of these films under an oxygen atmosphere with and without UV irradiation are carefully examined. The surface structure, morphology, optical transmission characteristics, and chemical compositions of the films are analyzed by atomic force microscopy, scanning electron microscopy and PL spectrometry. It is found that the oxygen sensitivity of the films deposited on Corning glass 1737 substrates is significantly lower than that of the films grown on SiO₂/Si substrates. Therefore, the results suggest that SiO₂/Si is an appropriate substrate material for oxygen gas sensors fabricated using thin SnO₂/TiO₂ films.     

Synthesis and Optical Properties of SiO2-Coated CeO2 Nanoparticles

Silica (SiO₂)-coated ceria (CeO₂) nanoparticles were prepared using water-in-oil microemulsion. Polyoxyethylene (15) cetylether and cyclohexane were used as a surfactant and organic solvent. SiO₂-coated CeO₂ nanoparticles were obtained by hydrolysis of metal alkoxide (tetraethylorthosilicate, TEOS) in the solution containing CeO₂ precursor nanoparticles. The effects of CeO₂ sources (Ce metal salt) and CeO₂ particle-forming agents on the morphology of SiO₂–CeO₂ particles were investigated. Observation via transmission electron microscopy revealed that the type of particle-forming agent affected the nanoparticles' morphology and that CeO₂ nanoparticles were spherically coated with SiO₂ when using oxalic acid ((COOH)₂) as a particle-forming agent of CeO₂. Furthermore, the transmittance of the particles was high in the visible region (above 400 nm) and decreased in the ultraviolet region.     

SnO2:Eu nanoparticles dispersed in silica: A low-temperature synthesis and photoluminescence study

SnO₂:Eu and SnO₂:Eu nanoparticles dispersed in silica matrix were prepared at a relatively low temperature of 185 °C in ethylene glycol medium. For as-prepared SnO₂:Eu nanoparticles there exists a weak energy transfer from the SnO₂ host to the Eu³⁺ ions. However, the energy transfer can be significantly improved by dispersing the Eu³⁺-doped SnO₂ nanoparticles in silica matrix. Effective shielding of surface Eu³⁺ ions in SnO₂:Eu nanoparticles from the stabilizing ligand by silica matrix is the reason for the improved extent of energy transfer. Increase in asymmetric ratio of luminescence (ratio of the intensity of the electric dipole allowed transition, ⁵D₀→⁷F₂, to magnetic dipole allowed transition, ⁵D₀→⁷F₁) for SnO₂:Eu nanoparticles dispersed in silica compared to that of SnO₂:Eu nanoparticles, has been attributed to the distorted environment around surface Eu³⁺ ions brought about by the presence of both tin and silicon structural units. ¹¹⁹Sn and ²⁹Si MAS NMR studies on this sample confirmed that there is no interaction between the tin and silicon structural units even after heating the samples at 900 °C.     

Controlled flame synthesis of αFe<Subscript>2</Subscript>O<Subscript>3</Subscript> and Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles: effect of flame configuration,flame temperature,and additive loading

Superparamagnetic iron oxide nanoparticles are used in diverse applications, including optical magnetic recording, catalysts, gas sensors, targeted drug delivery, magnetic resonance imaging, and hyperthermic malignant cell therapy. Combustion synthesis of nanoparticles has significant advantages, including improved nanoparticle property control and commercial production rate capability with minimal post-processing. In the current study, superparamagnetic iron oxide nanoparticles were produced by flame synthesis using a coflow flame. The effect of flame configuration (diffusion and inverse diffusion), flame temperature, and additive loading on the final iron oxide nanoparticle morphology, elemental composition, and particle size were analyzed by transmission electron microscopy (TEM), high-resolution TEM (HR-TEM), energy dispersive spectroscopy (EDS), and Raman spectroscopy. The synthesized nanoparticles were primarily composed of two well known forms of iron oxide, namely hematite αFe₂O₃ and magnetite Fe₃O₄. We found that the synthesized nanoparticles were smaller (6–12 nm) for an inverse diffusion flame as compared to a diffusion flame configuration (50–60 nm) when CH₄, O₂, Ar, and N₂ gas flow rates were kept constant. In order to investigate the effect of flame temperature, CH₄, O₂, Ar gas flow rates were kept constant, and N₂ gas was added as a coolant to the system. TEM analysis of iron oxide nanoparticles synthesized using an inverse diffusion flame configuration with N₂ cooling demonstrated that particles no larger than 50–60 nm in diameter can be grown, indicating that nanoparticles did not coalesce in the cooler flame. Raman spectroscopy showed that these nanoparticles were primarily magnetite, as opposed to the primarily hematite nanoparticles produced in the hot flame configuration. In order to understand the effect of additive loading on iron oxide nanoparticle morphology, an Ar stream carrying titanium-tetra-isopropoxide (TTIP) was flowed through the outer annulus along with the CH₄ in the inverse diffusion flame configuration. When particles were synthesized in the presence of the TTIP additive, larger monodispersed individual particles (50–90 nm) were synthesized as observed by TEM. In this article, we show that iron oxide nanoparticles of varied morphology, composition, and size can be synthesized and controlled by varying flame configuration, flame temperature, and additive loading.     

Energy transfer from the host to Er<Superscript>3+</Superscript> dopants in semiconductor SnO<Subscript>2</Subscript> nanocrystals segregated in sol–gel silica glasses

Undoped and Er³⁺-doped glass–ceramics of composition (100−x)SiO₂–xSnO₂, with x = 5 or 10 and with 0.4 or 0.8 mol% of Er³⁺ ions, were synthesised by thermal treatment of precursor sol–gel glasses. Structural studies were developed by X-Ray Diffraction. Wide band gap SnO₂ semiconductor quantum-dots embedded in the insulator SiO₂ glass are obtained. The mean radius of the SnO₂ nanocrystals, ranging from 2 to 3.2 nm, is comparable to the exciton Bohr radius. The luminescence properties have been analysed as a function of sample composition and thermal treatment. The results show that Er³⁺ ions are partially partitioned into the nanocrystalline phase. An efficient UV excitation of the Er³⁺ ions by energy transfer from the SnO₂ nanocrystal host is observed. The Er³⁺ ions located in the SnO₂ nanocrystals are selectively excited by this energy transfer mechanism. On the other hand, emission from the Er³⁺ ions remaining in the silica glassy phase is obtained by direct excitation of these ions.     

Effects of interface between SnO2 thin film and Si substrate on growth time

SnO₂ thin film was grown on Si substrate using the low pressure chemical vapor deposition (LPCVD) method. The SnO₂ thin film was grown in the direction of (110) as deposition time increased. The atomic ratio of O decreased by 62.4, 57.6, and 45.6%, and the thickness of the thin film increased to 0.2, 0.3, and 0.7 ? as the deposition time increased to 10, 20, and 30 min, respectively. The interface of the thin film was examined using high-resolution transmission electron microscope (HRTEM) and energy dispersive spectroscopy (EDS) analysis. The SiO₂ layer was observed at between the SnO₂ thin film and the Si substrate. This layer decreased in thickness as the deposition time increased, which indicates that the deposition time affected the interface of the thin film.     

Preparation of ZnO–Al2O3 Particles in a Premixed Flame

Zinc oxide (ZnO) and alumina (Al₂O₃) particles are synthesized by the combustion of their volatilized acetylacetonate precursors in a premixed air–methane flame reactor. The particles are characterized by XRD, transmission electron microscopy, scanning mobility particle sizing and by measurement of the BET specific surface area. Pure (-)alumina particles appear as dendritic aggregates with average mobile diameter 43–93 nm consisting of partly sintered, crystalline primary particles with diameter 7.1–8.8 nm and specific surface area 184–229 m²/g. Pure zinc oxide yields compact, crystalline particles with diameter 25–40 nm and specific surface area 27–43 m²/g. The crystallite size for both oxides, estimated from the XRD line broadening, is comparable to or slightly smaller than the primary particle diameter. The specific surface area increases and the primary particle size decreases with a decreasing flame temperature and a decreasing precursor vapour pressure. The combustion of precursor mixtures leads to composite particles consisting of zinc aluminate ZnAl₂O₄ intermixed with either ZnO or Al₂O₃ phases. The zinc aluminate particles are dendritic aggregates, resembling the alumina particles, and are evidently synthesized to the full extent allowed by the overall precursor composition. The addition of even small amounts of alumina to ZnO increases the specific surface area of the composites significantly, for example, zinc aluminate particles increases to approximately 150 m²/g. The gas-to-particle conversion is initiated by the fast nucleation of Al₂O₃ or ZnAl₂O₃, succeeded by a more gradual condensation of the excess ZnO with a rate probably controlled by the cooling rate for the flame.     

SnO2/TiO2 mixed oxide particles synthesized in doped premixed H2/O2/Ar flames

SnO₂/TiO₂ mixed oxides with primary particle size ranging between 5 nm d_p 12 nm were synthesized by doping a H₂/O₂/Ar flame with Sn(CH₃)₄ and Ti(OC₃H₇)₄ co-currently. The effects of “flow coordinate,” concentration and flame configurations were investigated with respect to particle size and morphology of the generated mixed oxides. In situ characterization of the mixed oxides was performed using the particle mass spectrometer (PMS), while XRD, TEM, BET and UV–Vis were performed ex situ. Results obtained showed that primary particle size of mixed oxides can be controlled by varying experimental parameters. The mixed oxides have interesting properties compared to those of the pure oxides of TiO₂ and SnO₂, which were also synthesized in flames earlier. Band gap tuning opportunities are possible using mixed oxides.     

Characterization of Y<Subscript>2</Subscript>BaCuO<Subscript>5</Subscript> nanoparticles synthesized by nano-emulsion method

Nanoscale yttrium–barium–copper oxide (Y₂BaCuO₅, Y211) particles were synthesized using the emulsion method and the solution method. The basic water-in-oil (w/o) emulsion system consisted of n-octane (continuous oil phase), cetyltrimethylammonium bromide (cationic surfactant), butanol (cosurfactant) and water. The composition of the emulsion system was varied and characterized by measuring the conductivity of the solutions and droplet size. The droplet size of emulsion was determined by using the dynamic light scattering method. The water content, cosurfactant content, and surfactant/n-octane ratio affected the droplet size which was in the range of 3–8 nm, and hence the w/o emulsion system was referred to as a nano-emulsion system. A model was used to verify the droplet size. The influence of salt (Y₂(NO₃)₃) content on the droplet size was investigated and the addition of salt reduced the droplet size. The effects of reaction time and temperature on the Y211 particle sizes were also investigated. The particles were characterized using the TEM, SEM, and XRD. Nanoparticles produced by the nano-emulsion method were calcined at 850°C to form the Y211 phase as compared to solid state processing temperature of 1050°C. Based on the TEM analysis, the average diameter of the Y211 particles produced using the nano-emulsion method was in the range of 30–100 nm. The effect of adding 15% Y211 nanoparticles to the superconductor YBCO-123 as flux pinning centers, was investigated, and the transition temperature was reduced by 3 K.     

Synthesis of nano-sized polycrystalline PZT powders using molecular building blocks by designed chemical route

Polycrystalline perovskite Pb(Zr _x Ti O₃ (PZT) powders in the form of particles with sizes in the range 2∼ ∼10 nm were obtained by hydrolysis of a mixed metal alkoxide precursor. The mixed metal alkoxide precursor was synthesized by refluxing Pb(OAc)₂, Zr(O– ⁿ Bu)₄ and Ti(O–ⁱPr)₄ in anhydrous ethanol. After it was hydrolyzed in a solution with a pH of 3 and dried at 423 K, nano-sized polycrystalline perovskite PZT was obtained. This temperature of formation of the PZT perovskite phase is noticeably lower than those reported elsewhere. The sizes of the freshly dried polycrystalline perovskite PZT particles are within the range of 2–5 nm.     

Flame Temperature Effect on the Structure of SiC Nanoparticles Grown by Laser Pyrolysis

Small SiC nanoparticles (10 nm diameter) have been grown in a flow reactor by CO₂ laser pyrolysis from a C₂H₂ and SiH₄ mixture. The laser radiation is strongly absorbed by SiH₄ vibration. The energy is transferred to the reactive medium and leads to the dissociation of molecules and the subsequent growth of the nanoparticles. The reaction happens with a flame. The purpose of the experiments reported in this paper is to limit the size of the growing particles to the nanometric scale for which specific properties are expected to appear. Therefore the effects of experimental parameters on the structure and chemical composition of nanoparticles have been investigated. For a given reactive mixture and gas velocity, the flame temperature is governed by the laser power. In this study, the temperature was varied from 875°C to 1100°C. The chemical analysis of the products indicate that their composition is a function of the temperature. For the same C/Si atomic ratio in the gaseous phase, the C/Si ratio in the powder increases from 0.7 at 875°C up to 1.02 at 1100°C, indicating a growth mechanism limited by C₂H₂ dissociation. As expected, X-ray diffraction has shown an improved crystallisation with increasing temperature. Transmission electron microscopy observations have revealed the formation of 10 nm grains for all values of laser power (or flame temperature). These grains appear amorphous at low temperature, whereas they contain an increasing number of nanocrystals (2 nm diameter) when the temperature increases. These results pave the way to a better control of the structure and chemical composition of laser synthesised SiC nanoparticles in the 10 nm range.     

Preparation, structures and photoluminescent enhancement effect of PbWO4–TiO2 composite nanofilms

A novel route for preparing PbWO₄–TiO₂ nanofilms on a glass substrate is firstly proposed. The collodion is used as a dispersant and film-forming agent. The nanofilms are characterized through SEM, XRD, TG/DTA, PL and IR, respectively. The results of XRD indicate PbWO₄ particles with tetragonal scheelite structure and TiO₂ particles with Anatase phase, and SEM shows they are well dispersed in the substrate. Compared with nanoparticles, when TiO₂ nanoparticles are added in 5% ratio, the PL intensities at 395 nm of PbWO₄ nanofilms are enhanced obviously. IR spectrum reveals a large absorption band between 750 and 870 cm⁻¹, which is the W–O stretching vibration in WO₄ tetrahedron.     

Fabrication and characterization of Au/SiO2 nanocomposite films grown by radio-frequency cosputtering

Au/SiO₂ nanocomposite films were prepared on Si wafers by cosputtering of SiO₂ and gold wires. Au/Si atomic ratios in Au/SiO₂ nanocomposite films were varied from 0.53 to 0.92 by controlling the length of gold wire to study the evolution of the crystallization of gold, the size of Au/SiO₂ nanocomposite particles, and the optical properties of as-deposited Au/SiO₂ nanocomposite films. An X-ray photoelectron spectroscopy reveals that Au exists as a metallic phase in the bulk of SiO₂ matrix. Dome-shaped Au/SiO₂ nanocomposite particles and both Au (1 1 1) and (2 0 0) planes were observed in a field-emission scanning electron microscopy and X-ray diffraction studies respectively. With an ultraviolet-visible, absorption peaks of Au/SiO₂ nanocomposite films were observed at 525 nm.     

Electron beam-physical vapor deposition of SiC/SiO2 high emissivity thin film

When heated by high-energy electron beam (EB), SiC can decompose into C and Si vapor. Subsequently, Si vapor reacts with metal oxide thin film on substrate surface and formats dense SiO₂ thin film at high substrate temperature. By means of the two reactions, SiC/SiO₂ composite thin film was prepared on the pre-oxidized 316 stainless steel (SS) substrate by electron beam-physical vapor deposition (EB-PVD) only using β-SiC target at 1000 °C. The thin film was examined by energy dispersive spectroscopy (EDS), grazing incidence X-ray asymmetry diffraction (GIAXD), scanning electron microscopy (SEM), atomic force microscopy (AFM), backscattered electron image (BSE), electron probe microanalysis (EPMA), X-ray photoelectron spectroscopy (XPS) and Fourier transformed infra-red (FT-IR) spectroscopy. The analysis results show that the thin film is mainly composed of imperfect nano-crystalline phases of 3C-SiC and SiO₂, especially, SiO₂ phase is nearly amorphous. Moreover, the smooth and dense thin film surface consists of nano-sized particles, and the interface between SiC/SiO₂ composite thin film and SS substrate is perfect. At last, the emissivity of SS substrate is improved by the SiC/SiO₂ composite thin film.     

Gd-doped SnO2 nanoparticles: Structure and magnetism

Gd-doped SnO₂ nanoparticles were chemically prepared doping 0-12.5% Gd into SnO₂ and calcined at 600 °C. X-ray diffraction and Fourier transformed infrared spectroscopy measurements show the formation of single phase of Sn_1−xGd_xO₂ up to x=0.0625 while at x=0.125, an additional secondary phase of tetragonal GdO₂ (not cubic Gd₂O₃) is detected. The transmission electron microscopy studies show that the individual particles are single crystalline with an average size in the range of 10-12 nm. Magnetization measurements show the absence of ferromagnetic and antiferromagnetic ordering in all samples; however surface spin effects and enhanced Gd-O-Gd interactions are proposed to account for the observed magnetic properties of the samples.     

Structure and photoluminescence properties of Er3+-doped TiO2-SiO2 powders prepared by sol-gel method

Er 3+-doped TiO 2-SiO 2 powders are prepared by the sol-gel method,and they are characterized by high resolution transmission electron microscopy (HR-TEM),X-ray diffraction (XRD) spectra,and Raman spectra of the samples.It is shown that the TiO 2 nanocrystals are surrounded by an SiO 2 glass matrix.The photoluminescence (PL) spectra are recorded at room temperature.A strong green luminescence and less intense red emission are observed in the samples when they are excited at 325 nm.The intensity of the emission,which is related to the defect states,is strongest at the annealing temperature of 800 C.The PL intensity of Er 3+ ions increases with increasing Ti/Si ratio due to energy transfer between nano-TiO 2 particles and Er 3+ ions.