Preparation Method and Cation Dopant Effects on the Particle Size and Properties of BaCeO3 Perovskites

Perovskite-type BaCeO₃ has been investigated to study the effects of preparation method and cation doping on the particle size and sintering in the fabrication of dense perovskite membranes. A variety of preparation methods including solid-state reactions, coprecipitation, microemulsion, and molten salt reactions have been studied. In coprecipitation and microemulsion preparations, perovskites were formed at significantly lower temperatures than that required in a solid-state preparation. The pH of the reactant solutions has been found to greatly affect the particle size and agglomeration of BaCeO₃ perovskites. Smallest perovskite particles with sizes of 40–60 nm were obtained by the microemulsion preparation with minimal agglomeration. Transition metal dopants such as neodymium and manganese cations were doped into BaCeO₃ and their effects on the particle size and agglomeration of perovskite particles investigated. Both small particle size and cation doping significantly helped the sintering of perovskites.     

Exploitation of inline photon density wave spectroscopy for titania particle syntheses

In this work, inline (or in-situ) monitoring of titania particle formation with photon density wave spectroscopy is shown to provide helpful information for process optimization for higher particle yields. Titania particles have been synthesized by the controlled hydrolysis of tetraethyl orthotitanate. Without calibration or dilution, photon density wave spectroscopy provides access to dispersions' reduced scattering coefficient μ_s'. Hence, information can be obtained inline about processes that are otherwise challenging for established particle characterization methods. Photon density wave spectroscopy results suggest that the titania particles disintegrate over time after their formation. Consistent with that hypothesis, a decreasing particle yield with reaction time has been observed. The disintegration can be hindered by adding a sufficient amount of hexadecylamine, such that the particle yield after 24 h can be increased by 44% for the given syntheses.     

Characterization of spherical silica–titania mixed oxide particles synthesized by using a dry process

Silica–titania mixed oxides have excellent properties, such as a low thermal expansion coefficient and a refractive index that can be adjusted by changing the Ti content. However, when the Ti content increases, silica and titania phases in silica–titania mixed oxides can separate. This phase separation leads to the precipitation of the titania component as rutile or anatase crystals. When silica–titania mixed oxides undergo phase separation, their properties become unstable; for example, the refractive index of the particles becomes non-uniform. Therefore, it is preferable to synthesize silica–titania mixed oxides in an amorphous state without causing phase separation. Based on our previous studies on particle size control in silica synthesis, we employed a dry process using organosilicon compounds to synthesize silica–titania mixed oxides. In this study, spherical amorphous silica–titania mixed oxide particles were obtained via flame synthesis using organosilicon and organotitanium compounds. The purpose of this study was to characterize the obtained powder and explore the possibility of controlling particle size during synthesis. By studying the dry process synthesis of spherical silica–titania mixed oxide particles, we confirmed the relationships: between the Si/Ti molar ratio and the obtained crystal structure and between the adiabatic flame temperature and the particle size.     

Nanosize Polyacrylamide/SiO2 Composites by Inverse Microemulsion Polymerization

Nanosize polyacrylamide/silica (PAM/SiO₂) composites were prepared by water- in-oil (W/O) microemulsion process. In this system, aqueous solution of acrylamide containing disperse 10 nm size silicon dioxide was used as the dispersed phase of the microemulsion while the dispersion medium was sodium bis (2-ethylhexyl) sulfosuccinate (AOT)/toluene solution. The size of the synthesized PAM/SiO₂ nanocomposites was 38–76 nm as determined by dynamic light scattering (DLS). The incorporation of nanosize silica filler reduces the particle size of PAM latex. It had also been found that the size of composite particles decreases with increasing filler loading along with better polydispersity. The presence of silica particles in the polymer latex particles and interaction of polymer chains with silica particles in hybrid nanocomposites were characterized by Fourier transform infra red spectrophotometry (FTIR), thermogravimetry analysis (TGA) and differential scanning calorimetry (DSC). The TGA results showed improved thermoresistance and high thermal stability behavior of hybrid composites. The DSC measurements revealed that the incorporation of filler favors crystallization, increases the enthalpy of melting and thermal stabilization of the synthesized composite particles. A scanning electron microscope (SEM) was used to study the morphology and topography of the prepared nanocomposites.     

Distinguishing between aggregates and agglomerates of flame-made TiO2 by high-pressure dispersion

The potential of high-pressure dispersion (HPD) and dynamic light scattering (DLS) is explored for rapid and quantitative estimation of the extent of particle aggregation and agglomeration by analyzing the entire particle size distribution. Commercially available and tailor-made TiO₂ particles by flame spray pyrolysis (FSP) were characterized by X-ray diffraction, nitrogen adsorption and transmission electron microscopy (TEM). Volume distributions of these titania particles were obtained by DLS of their electrostatically stabilized (with Na₄P₂O₇) aqueous suspensions. Dispersing these suspensions through a nozzle at 200 to 1400 bar reduced the size of agglomerates (particles bonded by weak physical forces) resulting in bimodal size distributions composed of their constituent primary particles and aggregates (particles bonded by strong chemical or sinter forces). Sintering FSP-made particles from 200 to 800 °C for 4 h progressively increased the minimum primary particle size (by grain growth) and aggregate size (by neck growth and phase transformation).     

Size dependent photocatalytic activity of hydrothermally crystallized titania nanoparticles on poorly adsorbing phenol in absence and presence of fluoride ion

The photocatalytic degradation of phenol has been performed by adopting nanosized titanium dioxide, prepared with the sol–gel method, both in presence and absence of fluoride ions. Several catalyst treatments, that is hydrothermal heat treatment and calcination, have been applied in order to increase the crystallinity of the particles. A close relationship was found between the rate of phenol disappearance and the particle size, with an efficiency that becomes maximum when the combination of large particle size (7.8 nm) and surficial sites covered by fluoride is fulfilled. Intermediates profiles have been also evaluated, in order to verify if the surficial process occurring in the diverse materials still remains the same. It is accomplished in the case of the fluorinated titania, where both the rate of disappearance and the intermediates formation closely resemble those seen on Degussa P25, while a different formation ratio between catechol and hydroquinone was observed in the case of naked titania.     

Improvement in photocatalytic activity of morphologically controlled Pd-supporting TiO2 particles via sol–gel process using inkjet nozzle

The purpose of the present study is to prepare palladium-supporting porous titania particles via a sol–gel process using an inkjet nozzle and to improve the photocatalytic activity of the particles. The morphology of titania particles produced by the sol–gel process using an inkjet nozzle was evaluated by scanning electron microscopy and nitrogen physisorption measurements. The photocatalytic activity of the obtained titania particles was evaluated using the changes in the concentration of a methylene blue solution under UVC light irradiation and the effect of palladium supported on the inner and outer surfaces of the titania particles on the photocatalytic activity was investigated.The titania particles prepared by inkjet processing exhibited spherical porous structures. The particle and pore size distributions of the obtained titania particles were more uniform than those of the titania particles prepared using the non-inkjet nozzle. The titania particles supporting palladium on the inner and outer surfaces exhibited a faster rate of photocatalytic degradation than the titania particles supporting palladium on only the outer surface, with anatase titania particles exhibiting the highest rate of photocatalytic degradation. Thus, we have successfully improved the photocatalytic activity of titania particles by supporting palladium on the inner and outer titania surfaces. This sol–gel process using an inkjet nozzle is an effective method for the preparation of porous titania particles supporting palladium on their inner and outer surfaces.     

Preparation of high solid loading titania suspension in gelcasting using modified boiling rice extract (MBRE) as binder

Preparation of high solid loading homogeneous titania suspension using modified boiling rice extract (BRE) as consolidator (network-former)/binder for gelcasting application has been investigated. To achieve in situ consolidation forming of TiO₂ ceramic, the gel network formed by swelling and gelatinization of the modified BRE (MBRE) with 2-hydroxyethylmethacrylate was studied. The dispersion behaviour of the titania powder and rheology of the suspension under the influence of binder content, dispersant (Darvan 821A) concentration and pH of the dispersing media have been discussed. The present process of gel casting deals with 50-80 weight% solid loading of titania particles with MBRE (2-10 weight% to that of total solid loading) in presence of dispersant (ammonium salt of polyacrylic acid [(C₄H₅O₂-NH₄⁺)n]). The influence of BRE concentration and solid particle loading on rheological properties of aqueous titania suspensions has been analyzed under steady and oscillatory shear conditions. Thermogravimetry (TG) and differential thermal analysis (DTA) on gelcast green body has been evaluated and analyzed. The characterization of green and sintered body has been done with respect to density, porosity and microstructure.     

Gas-to-Particle Conversion in the Particle Precipitation–Aided Chemical Vapor Deposition Process II. Synthesis of the Perovskite Oxide Yttrium Chromite

In the particle precipitation-aided chemical vapor deposition process, an aerosol is formed in the gas phase at elevated temperatures. The particles are deposited on a cooled substrate. Coherent layers with a controlled porosity can be obtained by a simultaneous heterogeneous reaction, which interconnects the deposited particles. The synthesis of submicrometer powder of the perovskite oxide yttrium chromite (YCrO₃) by gas to particle conversion, which is the first step of the PP-CVD process, has been investigated, and preliminary results are shown. The powders have been synthesized using yttrium trichloride vapor (YCl₃), chromium trichloride vapor (CrCl₃), and steam and oxygen as reactants. The influence of the input molar ratio of the elements on the composition and characteristics of the powders has been investigated. Phase composition has been determined by X-ray diffraction (XRD). The powders have been characterized by transmission electron microscopy (TEM) and sedimentation field flow fractionation (SF³). At a reaction temperature of 1283 K the powders consist of chromium sesquioxide (Cr₂O₃), or a mixture of Cr₂O₃ and YCrO₃. At stoichiometric input amounts of metal chlorides and steam the formation of YCrO₃ seems to be favored. Two typical particle size distributions have been observed. The primary particle size ranges from 5 to 30 nm for small particles, and from 40 to 250 nm for large particles, depending on the process conditions. The particles tend to be agglomerated. The weight of the agglomerates is independent of the primary particle diameter.     

Microemulsion polymerization of styrene in the presence of macroinimer

The kinetics of o/w electrostatically and sterically-stabilized microemulsion polymerization of styrene with and without macromonomeric azoinitiator (macroinimer; MIM) have been investigated. The microemulsion polymerization stabilized by the ionic emulsifier sodium dodecyl sulfate (SDS) or the non-ionic emulsifier Tween 20 (Tw 20) was initiated by ammonium peroxodisulfate (APS)/sodium thiosulfate (STS) redox system. The rate of polymerization vs. conversion curve shows the two non-stationary rate intervals. This behavior is a result of two opposing effects, the continuous particle nucleation and the decrease of monomer concentration at the reaction loci. The addition of MIM favors the additional particle nucleation. The sterically (Tw 20)-stabilized microemulsion polymerization is much faster than that of the electrostatically (SDS)-stabilized microemulsion polymerization. This was attributed to the higher Tw 20 concentration and increased solubilization of MIM and comonomer concentration in the polymer particles. The formation of initial large polymer particles is attributed to the intensive agglomeration polymer particles with monomer droplets. The continuous decrease in the average size is mainly attributed to the additional particle nucleation.     

Flame synthesis of titania particles from titanium tetraisopropoxide in premixed flames

An experimental investigation of flame synthesis of titania particles was conducted in premixed flames. The titanium precursor and silicon dopant used in this study were titanium tetraisopropoxide (TTIP) and hexamethyldisiloxane (HMDS), respectively. The objective of this study was to investigate the influence of flame condition, TTIP concentration, and HMDS on the phase composition and particle morphology of titania synthesized in flames. It was found that the anatase content of titania particles made in flames was appreciably increased by the increase of oxygen concentration in the oxidizer. The increase of flame temperature results in the decrease of anatase content. A significant increase in rutile content of titania particles was observed by increasing the particle residence time at high temperatures. The doping of HMDS in flames inhibits the transformation of anatase to rutile phase and, therefore, reduces the rutile content of product particles. Under the flame doped with low concentrations of HMDS, titania particles with SiO₂ particle agglomerates attached were produced. Further increase of the HMDS concentration up to the Si to Ti molar ratio equal to 0.375 results in the formation of a large amount of SiO₂ agglomerates in the product.     

Interfacial sol–gel processing for preparation of porous titania particles using a piezoelectric inkjet nozzle

The aim of the present work is to apply the liquid–liquid interfacial crystallization using a piezoelectric inkjet nozzle to the sol–gel processing. The instillation process was compared with the batch process to elucidate the effectiveness of the inkjet technique on the liquid–liquid interfacial sol–gel processing. The effect of frequency and water concentration in titanium tetraisopoxide (TTIP) solution on titania particle properties was investigated for sol–gel processing with a piezoelectric inkjet nozzle. Titania particles produced by each process were calcined at 500 °C. The crystal structure, morphology, pore size distribution and specific surface area of titania particles were evaluated by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen physisorption measurement. The photocatalytic activity of titania particles was evaluated by the photodegradation of methylene blue solution under UVC light irradiation.     

Particle kinetics and physical mechanism of microemulsion polymerization of octamethylcyclotetrasiloxane

In the present study, the particle kinetics and physical mechanism of microemulsion polymerization of octamethylcyclotetrasiloxane (D₄) were investigated by using dodecyldimethylbenzyl ammonium bromide (DBDA) as a surfactant and n-pentane as a cosurfactant. The light transparence of the emulsion, oil-water interfacial tension and the polymerization conversion as functions of the polymerization time were recorded. Furthermore, the particle sizes and their distributions in the process were measured by using dynamic light scattering technique (DLS). The results show that there does not exist constant-rate reaction period during the polymerization. The results of DLS show that the microemulsion polymerization can be distinguished as four steps, namely (I) the dispersion period, (II) the colloid formation and reaction period, (III) the colloid reaction period, and (IV) the agglomeration period. Corresponding physical models for each period were discussed. It has been found that the nucleation occurs mostly in the swollen-micelles and the polymerization occurs mostly in the new microlatex particles for the microemulsion polymerization of D₄.     

Comparison of gold supported catalysts obtained by using different allotropic forms of titanium dioxide

Gold catalysts were prepared on different allotropic phases of TiO₂ using the colloidal deposition method. The supports were chosen in order to study the influence of the support structure on the catalytic activity of the final material. Furthermore, for the same allotropic modification of titania, materials with a different particle size distributions have been used to study the influence of the grain size of the support on the deposition of the colloid. Our results indicate that the activity of the final catalyst is not much affected by the variation of the titania structure, though the situation becomes different when the catalyst is calcined at different temperatures. In this case, pure anatase and rutile supported catalysts showed a lower thermostability than the one prepared using P25 titanium oxide (Degussa). Concerning the colloid immobilization on the support it was found that the most important parameter is the grain size of the support. In particular, the deposition of the colloidal gold particles is greatly enhanced in the case of supports composed of particles of few nanometers in size.     

Production of titania nanoparticles by a green process route

The manufacture of heterogeneous catalysts and catalyst supports produces substantial amounts of nitrate containing aqueous effluent. The use of nitrate free precursors and an environmentally friendly process would change the manufacture so that the entire process of catalyst synthesis and use can be considered green. In this work the precipitation of titania acetylacetonate nanoparticles for use as catalytic supports using a supercritical carbon dioxide anti-solvent process was investigated over a range of conditions. The effects of 1) pressure, 2) temperature, 3) solution flowrate, 4) solution concentration of TiO(acac)₂ in methanol, 5) nozzle diameter and 6) CO₂/methanol flow ratio on the mean particle size and morphology were studied. Particle sizes between 27 and 78 nm were obtained and were generally string and branch-like with an amorphous nature. Pressure and temperature had little effect on the mean particle size. A decrease in the velocity of the solution flow rate led to an increase in mean particle size and to particles that exhibited greater interconnectivity. It was also observed that an increase in concentration of TiO(acac)₂ in methanol led to an increase in mean particle size. The process shows promise for the production of catalysts by an environmentally acceptable route.     

Effect of particle size on the mechanical properties of polystyrene and poly(butyl acrylate) core/shell polymers

The effects of particle size and polymer location (core or shell) on the mechanical properties of core/shell materials composed of polystyrene (PST) and poly(butyl acrylate) (PBA) made by a two-stage emulsion or microemulsion polymerization process are reported. Low-seed content (LSC) latexes were made by batch polymerization in microemulsions stabilized with DTAB in the presence of an organic salt (dibutyl phosphite). High-seed content (HSC) latexes were produced by microemulsion or emulsion polymerization in semi-continuous process. These latexes were subsequently used to form core/shell particles of PST/PBA or PBA/PST and their mechanical properties were examined and compared. Our results indicate that core/shell particle size and the location of the polymers have important effects on the mechanical properties.     

Synthesis of non-aggregated titania nanoparticles in atmospheric pressure diffusion flames

Flame aerosol synthesis has been employed to synthesize nanoscale titania (TiO₂) particles by oxidation of titanium tetraisopropoxide (TTIP) vapor. The influence of reactant mixing and flow rates on particle morphology, size and phase composition has been studied for two different diffusion flame configurations using transmission electron microscopy, X-ray diffraction and photon correlation spectroscopy. Spherical, loosely agglomerated powders with a minimum secondary particle size of 90 nm and a rutile content of up to 35 w % were obtained at low oxygen flow rates in the double diffusion flame, while large anatase-rich aggregates formed at high oxygen flow rates. It is shown that the degree of aggregation of the as-synthesized particles is represented better by the ratio of d_PCS³/d_TEM³, than by the ratio of d_BET³/d_XRD³ commonly used in literature. The differences observed in particle morphology and phase composition can be explained by considering their time-temperature history as a function of flame configuration and gas flow rates.     

Promoting Photocatalytic Cleaning Efficiency of Textile Finishing Solutions with Nanoboron as a p-Type Dopant

Boron is a commonly used p-type dopant for semiconductor and photonic applications. In this study, standard photocatalytic titanium dioxide (TiO₂) particles were doped with nanosized boron particles and coated on textiles to bring the photocatalytic light intensity closer to the visible light range. Boron/titania nanoparticle composites were initially prepared in DI water solutions and studied for their photocatalytic response through a statistical central composite design. To determine the most effective titania and nanoboron particle blend for photocatalytic textile coating, absorbance and stain bleach analyses were performed by UV light exposure. The performance of the composite particles at the optimal concentration has also been evaluated in the finishing solution and compared with the performances of the pure titania particles. It was found that the textiles coated with 0.08 wt% anatase doped with 0.16 wt% nanoboron as a p-type dopant provided improvement in self-cleaning ability under the visible light range in the DI water environment. Energy band gap calculations further verified the nanoboron-doped titania blend to have a lower energy barrier as compared with the 0.1 wt% anatase in agreement with the photocatalytic activity improvements. Nanoboron is shown to be a strong candidate as a p-type dopant to titania for photocatalytic textile coatings.     

反胶束法纳米TiO_2的UV-vis和TEM研究

用石油醚为溶剂的反胶束体系溶胶-凝胶法合成了纳米TiO2,采用UV-vis光谱跟踪纳米TiO2粒子粒径的变化,研究了影响纳米TiO2溶胶粒子大小的因素,采用TEM表征了纳米TiO2的粒子大小及其粒径分布。结果表明,合成的反胶束纳米TiO2的UV-vis光谱吸收边λonset为344.8~363.2 nm,与锐钛型纳米TiO2的吸收边λonset=385 nm相比,紫外可见光谱发生“蓝移”,反胶束纳米TiO2粒子的半径为5~6.5 nm;TEM表明,纳米TiO2粒子的粒径为15~55 nm,粒径分布较窄,粒径分布指数SD I为1.19~1.29;FTIR谱图表明,TiO2粒子为表面具有一定数量钛羟基的水合TiO2。     

The preparation of small polystyrene latex particles

The effects of several variables in the preparation of small-sized polystyrene latex particles are described. A semicontinuous preparation using microlatexes obtained by microemulsion polymerization as a seed is compared with a batchwise preparation employing the same ingredients. The particles in the batch products prove to be slightly larger in size but are more narrowly distributed. Furthermore, the effects of both the surfactant type and the ionic strength on the particle size in the batchwise emulision polymerization of styrene are reported. The systems do not obey the linear Smith–Ewart relationship with respect to the micellar surfactant concentration, although in the microemulsion polymerization of styrene the Smith–Ewart relationship is found to be valid with respect to the initiator concentration. Surfactants with a low critical micelle concentration increasingly promote the formation of smaller particle sizes. Salt is found to decrease the particle size when using a strong adsorbing surfactant. However, in the case of a weak adsorbing surfactant, an increase in particle size has been observed above a certain salt concentration.