Low Temperature One Step Synthesis of Barium Titanate: Particle Formation Mechanism and Large-scale Synthesis

The formation of BaTiO3 nanoparticles via the reaction of BaCl2, TiCl4 and NaOH in aqueous solution has been systematically studied. The formation of BaTiO3 from the ionic precursors has been elucidated to be a very rapid process, occurring at temperature higher than 60℃. Furthermore, the particle size could be controlled by the proper selection of the synthesis conditions (e.g. reactant concentration of 0.5—1.0mol·L-1, temperature of 80— 95℃ and pH≥13). A two-step precipitation mechanism was proposed. The first stage of the synthesis involved the formation of amorphous Ti-rich gel phase. The second stage of the synthesis was the reaction between the amor-phous phase and the solution-based Ba2+ ions, which led to the crystallization of BaTiO3. Based on the particle for-mation mechanism, a novel method, high gravity reactive precipitation, was proposed and used to mass production of BaTiO3 of average particle size of about 60 nm and with narrow particle size distribution. Because it could break up the amorphous Ti-rich gel into small pieces, intensify mass transfer, promote the reaction rate of amorphous Ti-rich gel with Ba2+ ions.

STUDY ON THE FORMATION MECHANISM OF MONODISPERSE PARTICLES IN THE EMULSIFIER-FREE EMULSION POLYMEAIZATION OF METHYL METHACRYLATE AND BUTYL ACRYLATE

The formation mechanism of monodisperse polymer latex particles in the emulsifier-free emulsion polymerizationof methyl methacrylate and butyl acrylate with potassium persulfate as initiator was investigated. A multi-step formationmechanism for the monodisperse polymer particles was proposed. The nucleation mechanism is considered to be thecoagulation of the precursor particles by homogeneous nucleation when the primary particles reach a critical size with highsurface charge density and sufficient stability. It had been proved by a special experiment that the early latex particles formedby the coagulation were stable. The primary particles grow by absorbing monomers and radicals in the polymerization systemand then become colloidally unstable again due to the understandable decrease of particle surface charge density, which leadsto the aggregation of the growing particles and the formation of larger latex pedicles therefrom. Aner the nucleation period,the preferential aggregation of the smaller particles in the propagation process leads to the change of the particles towards auniform size and narrower particle size distribution. The coexistence and competition of homogeneous nucleation,coagulation, propagation and aggregation result in the increase of the polydispersity index (U = D_(43)/D_(10)) in the first Stage,then its decrease in the later stage because of the competition of propagation and aggregation, and the gradual formation ofthe monodisperse particles.

PARTICLE MORPHOLOGY OF POLY(VINYL CHLORIDE)RESIN PREPARED BY SUSPENDED EMULSION POLYMERIZATION

Suspended emulsion polymerization was used to prepare poly(vinyl chloride) (PVC) resin. Fine PVC particleswere formed at low polymerization conversions. The amount of fine panicles decreases as conversion increases anddisappears at conversions greater than 30%. Scanning electron micrographs show that PVC grains are composed of looselycoalesced primary particles, especially for PVC resins prepared in the presence of poly(vinyl alcohol) dispersant. The size ofprimary particles increases and porosity decreases with the increase of conversion. In view of the particle features of PVCresin, a particle formation mechanism including the formation of primary particles and grains is proposed. The formationprocess of primary particles includes the formation of particle nuclei, coalescence of particle nuclei to form primary particles,and growth of primary particles. PVC grains are formed by the coagulation of primary particles. The loose coalescence ofprimary particles is caused by the colloidal stability of primary particles and the low swelling degree of vinyl chloride in the primary particles.

Occurrence,evolution and degradation of heavy haze events in Beijing traced by iodine-127 and iodine-129 in aerosols

Heavy haze events have become a serious environment and health problem in China and many developing countries,especially in big cities,like Beijing.However,the factors and processes triggered the formation of secondary particles from the gaseous pollutants are still not clear,and the processes driving evolution and degradation of heavy haze events are not well understood.Iodine isotopes(127Ⅰand129Ⅰ)as tracers were analyzed in time series aerosol samples collected from Beijing.It was observed that the127Ⅰconcentrations in aerosols peaked during the heavy haze events.The conversion of gaseous iodine to particular iodine oxides through photochemical reactions provides primary nuclei in nucleation and formation of secondary air particles,which was strengthened as the external iodine input from the fossil fuel burning in the south/southeast industrial cities and consequentially induced heavy haze events.Anthropogenic ^(129)Ⅰconcentrations peaked during clean air conditions and showed high levels in spring and later autumn compared to that in summer.^(129)Ⅰoriginated from the direct air discharges and re-emissions from contaminated seawaters by the European nuclear fuel reprocessing plants was transported to Beijing by the interaction of Westerlies and East Asian winter monsoon.Three types of mechanisms were found in the formation and evolution of heavy haze events in Beijing by the variation of ^(127)Ⅰand ^(129)Ⅰ,i.e.,iodine oxides intermediated secondary air particles,dust storm and mixed mode by both secondary air particles and dust storm induced processes.