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Factors for controlling sizes of silica particles formed in the hydrolysis and condensation of silicon alkoxides were examined in batch and semi-batch processes with our model previously proposed. Particle sizes in the particle formation were simulated for buffer systems to reduce time-variation in pH. Effectiveness of the buffer system to suppress time-variation in ionic strength was experimentally verified in a silicon alkoxide concentration range of 0.01-0.1 M. Comparison of experimental particle sizes with calculated ones showed that the addition of electrolytes slightly decreased surface potential of silica particles in both batch and semi-batch processes, and the surface potential values estimated for the semi-batch process were lower than that for batch process. In simulation of the number of particles formed in the processes, the particle number had strong dependences on surface potential and Debye-Hückel parameter. The simulated number of particles formed in semi-batch process was smaller than that in batch process under the same surface potential and Debye-Hückel parameter. The combination of the low surface potential and the small number of particles revealed that the semi-batch process was suitable for producing a small number of particles, which provides enlargement of size range of silica particles formed in the method., (Copyright © 2012 Elsevier Inc. All rights reserved.)

A methanol oxidation catalyst with improved durability in acidic environments is reported. The catalyst consists of PtRu alloy nanoparticles on a carbon support that were stabilized with a silane-coupling agent. The catalyst was prepared by reducing ions of Pt and Ru in the presence of a carbon support and the silane-coupling agent. The careful choice of preparatory conditions such as the concentration of the silane-coupling agent and solution pH resulted in the preparation of catalyst in which the PtRu nanoparticles were dispersively adsorbed onto the carbon support. The catalytic activity was similar to that of a commercial catalyst and was unchanged after immersion in sulfuric acid solution for 1000 h, suggesting the high durability of the PtRu catalyst for the anode of direct methanol fuel cells., (Copyright © 2010 Elsevier Inc. All rights reserved.)

Entry of direct methanol fuel cells into the market requires anode catalyst with stable activity. This paper presents a novel method for stabilizing the activity by immobilizing silica on the catalytic PtRu nanoparticles. Characterization was performed by STEM-EDX, XRD, and ICP. The silica-immobilized PtRu nanoparticles showed high and stable activity toward methanol oxidation. The activity was maintained for 1000 h in sulfuric acidic solution, while the activity of the catalyst with "bare" PtRu nanoparticles decayed after 100 h, showing high durability of the silica-immobilized PtRu nanoparticles catalyst in quasi-anodic acidic environment.

Soap-free emulsion polymerization was extended to preparation of monodisperse poly(methyl methacrylate) (PMMA) particles incorporating rhodamine 6G (R6G) fluorescent molecules. The polymerization was conducted in the presence of an anionic monomer, p-styrenesulfonate (NaSS), which improved dispersion stability of the polymer particles. NaSS concentrations was ranged up to 2 mol/m3 H2O in the polymerization at 0.5 kmol/m3 H2O methyl methacrylate (MMA) monomer and 5 mol/m3 H2O potassium persulfate (KPS) initiator for R6G concentrations from 0.1 to 10 mol/m3-polymer. At R6G concentrations lower than 1.0 mol/m3-polymer, PMMA particles were highly monodisperse and incorporated most R6G molecules. The average sizes of PMMA particles were in a rage of 160-300 nm, and decreased with the concentration of NaSS. The high monodispersity of the particles enabled the fabrication of colloidal crystals of the particles with a vertical deposition method.

A synthetic method for platinum-ruthenium (PtRu) nanoparticles in aqueous media is proposed. This method employs citric acid as a capping agent and NaBH(4) as a reducing agent with the aid of pH control. The number-averaged size of the PtRu nanoparticles was ca. 2 nm. The crystal phase and chemical composition of the nanoparticles was investigated by X-ray diffraction measurement and scanning transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy analysis, which indicated that the nanoparticles mainly consisted of an alloy of Pt and Ru. Electrochemical measurement showed that the PtRu nanoparticles had catalytic activity for methanol oxidation.

A synthetic method for preparing submicrometer-sized titania particles is proposed, which is based on hydrolysis of titanium alkoxide with the use of a cosolvent and an amine catalyst for alkoxide hydrolysis. The preparation was performed with different amines of ammonia, methylamine (MA), and dimethylamine (DMA) in different solvents of ethanol/acetonitrile, ethanol/methanol, ethanol/acetone, ethanol/acetonitrile, and ethanol/formamide for 0.1-0.3 M water and 0.03 M titanium tetraisopropoxide (TTIP) at temperatures of 10-50 degrees C. The use of the ethanol/acetonitrile solvent with MA was required for preparing monodispersed, spherical particles. The number average of the titania particle sizes and their coefficient of variation were varied from 143 to 551 nm and from 5.7 to 20.6%, respectively, with reaction temperature and concentrations of water and MA. Colloidal crystals of titania particles fabricated with a sedimentation method revealed reflection peaks attributed to Bragg's diffraction. Annealing at 100-1000 degrees C led to shrinkage and crystallization of titania particles followed by an increase in the refractive index of titania particles.

A previously proposed method was examined for producing monodisperse, submicrometer-sized magnetic polymer particles. The method applies soap-free emulsion polymerization during which Fe3O4 magnetic nanoparticles are heterocoagulated onto precipitated polymer nuclei. To chemically fix the magnetic particles to the polymer nuclei, vinyl groups were introduced on the Fe3O4 particles in a preliminary surface modification reaction with methacryloxypropyltrimethoxysilane, and methacryloxypropyldimethoxysilane (MPDMS) was added to reaction systems of the soap-free emulsion polymerization. The colloidal dispersion stability of magnetic polymer particles was improved by the addition of an ionic monomer, sodium p-styrenesulfonate (NaSS), during the polymerization. The polymerizations were carried out with styrene monomer and potassium persulfate initiator in ranges of NaSS concentrations (0-2.4 x 10(-3) M), NaSS addition times (60-80 min), and monomer concentrations (0.3-0.6 M) at fixed concentrations of 1.6 x 10(-2) M initiator and 1.3 x 10(-2) M MPDMS for pH 4.5 adjusted with a buffer system of [CH3COOH]/[NaOH]. The addition of NaSS during the polymerization could maintain the dispersion stability of magnetic polymer particles during the polymerization. Selection of the reaction conditions enabled the preparation of colloidally stable, submicrometer-sized magnetic polymer particles that had coefficients of variation of distribution smaller than the standard criterion for monodispersity, 10%.

A previously proposed method for metal deposition with silver [Kobayashi et al., Chem. Mater. 13 (2001) 1630] was extended to uniform deposition of gold nanoparticles on submicrometer-sized silica spheres. The present method consisted of three steps: (1) the adsorption of Sn(2+) ions took place on surface of silica particles, (2) Ag(+) ions added were reduced and simultaneously adsorbed to the surface, while Sn(2+) was oxidized to Sn(4+), and (3) Au(+) ions added were reduced and deposited on the Ag surface. TEM observation, X-ray diffractometry, and UV-vis absorption spectroscopy revealed that gold metal nanoparticles with an average particle size of 13 nm and a crystal size of 5.1 nm were formed on the silica spheres with a size of 273 nm at an Au concentration of 0.77 M.

Silver nanoparticles prepared through a borohydride-reduction method were directly coated with silica by means of a seeded polymerization technique based on the Stober method. Various amine catalysts were used for initialization of a sol-gel reaction of TEOS with no need for a prior surface modification. Use of dimethylamine (DMA) as a catalyst was found to be necessary to obtain a proper coating. The silica shell thickness was varied from 28 to 76 nm for TEOS concentrations of 1-15 mM at 11.1 M water and 0.8 M DMA. The optical spectra of the core-shell silver-silica composite particles show a qualitative agreement with predictions by Mie theory.

A soap-free emulsion polymerization method with the use of an amphoteric initiator, currently proposed by the authors for producing highly monodisperse, micrometer-sized polymer particles, was examined in the polymerization of styrene with a 2,2'-azobis [N-(2-carboxyethyl)-2-2-methylpropionamidine] hydrate initiator and an NH(4)OH/NH(4)Cl pH buffer. The pH buffer was used to control the electric surface potential of particles to maintain a stable dispersion of particles and to prevent generation of new particles during the polymerization. Addition of monomer to the reaction system during polymerization could enlarge the average size of polymer particles to 5.7 microm with a coefficient of variation of 1.5%, which is much less than the standard criteria of monodispersity, 10%.

Particle formation in the hydrolysis and condensation of tetraethyl orthosilicate (TEOS) was studied by varying pH (9.5-11) with the basic catalysts NH3, methylamine (MA), and dimethylamine (DMA) in the presence of 5 mol/m3 CH3COOH, which was chosen to suppress time variations of pH and ionic strength during the reaction. Spherical particles were formed for MA and DMA at catalyst concentrations of 0.02-0.2 kmol/m3 and for NH3 at catalyst concentrations of 0.1-1.5 kmol/m3. In a common range of catalyst concentrations for spherical particle formation, average particle size was largest for DMA and smallest for NH3. Hydrolysis rate of TEOS could be quantified by the use of buffer systems as a function of TEOS and OH- concentrations. A specific relation was not found between the hydrolysis and the particle size. The zeta potential of silica particles measured in the reaction solvent was in the order DMA < MA < NH3, and ionic strength, estimated from pH in the reactions, was in the order DMA approximately equal to MA > NH3. This suggested that the particle sizes were controlled by electrostatic particle interactions.

Jingle bell-shaped hollow spheres were fabricated starting from multilayered particles composed of a silica core, a polystyrene inner shell, and a titania outer shell. Composite particles of silica core-polystyrene shell, synthesized by coating a 339-nm-sized silica core with a polystyrene shell of thickness 238 nm in emulsion polymerization, were used as core particles for a succeeding titania-coating. A sol-gel method was employed to form the titania outer shell with a thickness of 37 nm. The inner polystyrene shell in the multilayered particles was removed by immersing them in tetrahydrofuran. These successive procedures could produce jingle bell-shaped hollow spheres that contained a silica core in the titania shell.

A preparation method for multilayered gold-silica-polystyrene core-shell composite particles is proposed. The gold-silica core-shell particles of 192-nm-sized, synthesized by coating the 18-nm-sized gold particles with silica by a seeded growth technique, were used as cores for succeeding polystyrene coating. After surface modification of gold-silica composite particles by methacryloxypropyltrimethoxysilane (MPTMS), polymerizations of styrene (0.16-0.4 M) were conducted with 8 x 10(-3) M of potassium persulfate initiator in the presence of 1 x 10(-3) M of sodium p-styrenesulfonate anionic monomer. Multilayered core-shell gold-silica-polystyrene particles that contained a single core could be obtained. The coefficient of variation of size distribution (CV) of the composite particles was less than 7%, and polystyrene shell thickness was in a range of 193 to 281 nm.

A method for producing silica-core composite particles with a polystyrene shell is proposed. Silica particles were prepared by the Stöber method through condensation and hydrolysis of tetraethyl orthosilicate in a water-ethanol-ammonia solution. The silica particles were the surface-modified with a coupling reagent, methacryloxypropyltrimethoxysilane (MPTMS), to introduce vinyl groups onto the particle surfaces. Polymerization of styrene was conducted with an initiator, potassium persulfate (KPS), and an anionic monomer, sodium p-styrenesulfonate (NaSS), in the presence of the silica particles. In these coating experiments, the average size of the silica particles was varied from 339 to 1210 nm with the concentration ranges of MPTMS (0-10 mmol/l), NaSS (0-10 mmol/l), KPS (4-12 mmol/l), and styrene (0.12-0.4 mol/l). Selection of reaction conditions enabled the preparation of composite particles that contained one core of silica. The coefficient of variance of size distribution of the composite particles was less than 7%, and shell thickness was in the range 125 to 410 nm.

Gold nanoparticles prepared through a conventional citrate-reduction method were directly coated with silica by means of a seeded polymerization technique based on the Stöber method. The method required no surface modification. The addition of tetraethylorthosilicate and water prior to ammonia was found to be critical to obtain a proper coating. The silica shell thickness was varied from 30 to 90 nm for TEOS concentrations of 0.0005-0.02 M at 10.9 M of water and 0.4 M of ammonia. The optical spectra of the core-shell gold-silica composite particles agreed with predictions of Mie theory.

The electrorheological response and structure growth of colloidal silica suspension was studied with in situ measurements of the shear stress, electric conductivity, and dielectric permittivity of the suspension. The measurements were carried out under steady and sweep shears after the application of an electric field of alternative current (100 Hz) using silica particles with a diameter of 630 nm and a water content of 4.5 wt%. The measurements of the conductivity enabled the detection of structure growth formed by particle aggregation and clarified that the development of the particle aggregation enlarged the dielectric permittivity and the shear stress. Hysteretic behavior observed in the electrorheological response was explained by considering structure growth of the particle aggregation. The correlation equation for the shear stress and the dielectric permittivity obtained in our previous work (1) was found to be applicable to the present results. Copyright 2001 Academic Press.

A generalized model considering reaction and diffusion processes as rate determining steps is proposed for the formation of particles from hydrolysis and condensation of tetraethyl orthosilicate (TEOS). Reaction rate constant is assumed to be proportional to contact-surface area of two particles. Diffusion rate constant is given by Fuchs' stability theory with interparticle potential containing van der Waals attraction and electrostatic repulsion. To examine the validity of the model, ammonia-catalyzed reactions of TEOS were carried out in an ethanol-water solution at a water concentration of 11 mol/dm(3), an ammonia concentration of 1.0 mol/dm(3), and TEOS concentrations of 0.2 and 0.4 mol/dm(3) in the presence and in the absence of electrolytes. The experiments included competitive particle growth and seeded and nonseeded reactions. The model quantitatively expressed the results of the competitive growth experiments in which particles with different sizes grew at the same rate. The model gave the expected trend for the effect of ionic strength on particle sizes in the nonseeded reaction and the suppression of secondary particles in the seeded reaction by the addition of an electrolyte KCl. Good estimation was also obtained for transient particle size distributions in the nonseeded reaction and the seeded reaction in which secondary particles were generated. Copyright 2000 Academic Press.

A method was developed for producing micrometer-sized, highly monodisperse polystyrene particles in single stage polymerization in aqueous media. The method employs an amphoteric surfactant, dimethyldodecylbetaine, that is added to the reaction system of styrene/K(2)S(2)O(8)/water in early stage of reaction. Polymerizations were carried out over a range of initiator concentrations (4-8 mmol/dm(3) H(2)O). The polymerization procedure could produce particles with an average diameter of 3.4 µm with a coefficient of variation of particle size distribution of 4.0%. Copyright 2000 Academic Press.

Electrorheological response was experimentally studied by the use of silicone oil suspensions containing submicrometer-sized and supermicrometer-sized silica particles with different amounts of adsorbed water. The simultaneous measurements of dielectric permittivity and shear stress of the suspensions were carried out after the application of alternating current voltage under steady shear in ranges of shear rate (150-1400 s(-1)), electric field strength (0-4 kV/mm), its frequency (30-1000 Hz), and particle volume fraction (0.1-0.3). For the particles with small amounts of adsorbed water, steady shear stress was attained within several minutes after the application of electric field. The steady-state data for both the particles at each electric field strength showed that the shear stress generated by the application of electric field, Deltatau, varied correlatively with the generated permittivity, Deltaepsilon(r) (= epsilon(r) - epsilon(r,oil)), where epsilon(r) and epsilon(r,oil) are the permittivities of the suspension and the silicon oil, respectively. Under a wide variety of experimental conditions, the steady-state data for both the particle sizes could be correlated with a simple relationship, Deltatau ~ (Deltaepsilon(r)E)(2), where E is electric field strength. For the particles with large amounts of adsorbed water, steady state was not attained, and the evolutions of shear stress and permittivity of the suspensions were measured after the application of electric field. Remarkably, the transient values of Deltatau varied with (Deltaepsilon(r)E)(2) and fell along the same correlation line as the steady-state data. Copyright 1999 Academic Press.

A single-stage polymerization technique, proposed for producing micron-sized polymer particles in aqueous media by Gu and Konno, was examined. Styrene was used for the monomer, potassium persulfate for the initiator, and cetyltrimethylammonium bromide and sodium dodecyl sulfate were used for the ionic surfactants to control the aggregation of the particles during the reaction. Particle-size distributions and monomer-to-polymer conversions were measured over a range of initiator concentration (2-8 mmol/dm3 H2O), stirring speed (200-400 rpm), surfactant addition time and monomer concentration (1.1-2.2 mol/dm3 H2O). Changes in the initiator concentration and stirring speed did not bring about significant effect on the particle-size distributions. On the other hand, the addition of time affected the coefficient of variation of the particle-size distribution, but it had no significant effect on the average diameter of the particles. An increase in the monomer concentration enlarged the average size without lowering the coefficient of variation of particle-size distribution. Monodisperse polystyrene particles with an average diameter of 3.3 µm and a coefficient of variation of particle size distribution 7% could be prepared with the present technique. Copyright 1998 Academic Press.