Synthesis of submicron-sized composite particles with unique morphology by emulsifier-free seeded emulsion copolymerization

Polystyrene (PSt) microspheres with diameter of 375 nm to be used as the seeds for seeded emulsion polymerization were prepared via emulsion polymerization using potassium persulfate (KPS) as initiator in ethanol-water mixed solvents.Emulsifier-free seeded emulsion copolymerization of styrene (St) with acrylonitrile (AN) was carried out in the presence of poly(ethylene glycol) monomethoxymonomethacrylate (PEGm)macromonomer as reactive stabilizer and 2,2'-azobisisobutyronitrile (AIBN) as initiator to obtain submicron-sized PEGm graft poly(styrene-co-acrylonitrile) (PEGm-g-PSAN) composite particles with unique morphology.Scanning electron microscopy (SEM) indicated that St and AN together contributed to forming the unusual morphology.The concentration of St and AN,total monomer concentration,initiator type and the monomer adding method remarkably affected the morphology of the composite polymer particles.     

Improved performance of aluminum pigments encapsulated in hybrid inorganic–organic films

An organic silane acrylate resin (PMBK) was synthesized by free-radical solution polymerization using methyl methacrylate, butyl acrylate and (3-methacryloxypropyl)trimethoxysilane as monomers. Aluminum (Al) particles were then encapsulated in inorganic–organic hybrid films that were prepared by hydrolysis and condensation of PMBK and tetraethyl orthosilicate (TEOS) on the surface of Al pigments. Characterization results showed that PMBK and TEOS could simultaneously hydrolyze and condense with hydroxyl groups on the surface of the Al particles to form composite Al particles coated with inorganic–organic hybrid films. Compared with raw Al particles, the corrosion resistance and adhesive properties of paint films containing the composite Al particles were improved greatly, while the glossiness of the paint films decreased slightly, from 48.6° to 47.0°. In alkaline media (pH 11), the volume of evolved H₂ of composite Al particles was only 3.5 mL, whereas that of raw Al was 83.5 mL. The glossiness of paint films containing composite Al particles decreased by 1.66% after immersion in alkaline media for 24 h, whereas that of raw Al decreased by 14.82%. Peel-off tests of the paint films showed that the composite particles moved slightly away from the paint films. In contrast, the raw Al particles were seriously desquamated, suggesting encapsulation of hybrid films can greatly improve the adhesive properties of Al particles in paint films.     

Enhanced wettability and thermal stability of nano-SiO2/poly(vinyl alcohol)-coated polypropylene composite separators for lithium-ion batteries

To improve the electrolyte wettability and thermal stability of polypropylene (PP) separators, nano-SiO₂/poly(vinyl alcohol)-coated PP composite separators were prepared using a simple but efficient sol–gel and dip-coating method. The effects of the tetraethoxysilane (TEOS) dosage on the morphology, wettability, and thermal stability of the composite separators were investigated using Fourier-transform infrared spectroscopy, scanning electron microscopy, and contact-angle measurements. All the composite separators gave a smaller contact angle, higher electrolyte uptake, and lower thermal shrinkage compared with the PP separator, indicating enhanced wettability and thermal stability. Unlike the case for a traditional physical mixture, SiOC covalent bonds were formed in the coating layer. The composite separator with a TEOS dosage of 7.5 wt% had a unique porous structure combining hierarchical pores with interstitial voids, and gave the best wettability and thermal stability. The ionic conductivity of the composite separator containing 7.5 wt% TEOS was 1.26 mS/cm, which is much higher than that of the PP separator (0.74 mS/cm). The C-rate and cycling performances of batteries assembled with the composite separator containing 7.5 wt% TEOS were better than those of batteries containing PP separators.     

Synthesis and characterization of PMMA/Al2O3 composite particles by in situ emulsion polymerization

In order to improve its dispersibility, superfine alumina (Al2O3) was encapsulated with poly (methyl methacrylate) (PMMA) by in situ emulsion polymerization. It was found that only when the concentration of sodium dodecyl sulfate (SDS) was much higher than its critical micelle concentration, could PMMA/Al2O3 composite particles with high percentage of grafting (PG) be prepared. The same results were obtained between the experimental and stoichiometric amounts of tris (dodecylbenzenesulfonate) isopropoxide (NDZ), indicating that single-molecule-layer adsorption had taken place between NDZ and Al2O3. Analysis using FTIR. TEM and XPS showed that PMMA/Al2O3 composite particles with core-shell structure had been successfully synthesized by in sire emulsion polymerization. Compared to Al2O3, thermal stability and dispersibility of the composite particles showed marked improvement.     

Dynamics of disk-like particles in turbulent vertical channel flow

The dynamical behavior of inertial disk-like particles in turbulent vertical channel flow is investigated by an Eulerian–Lagrangian point-particle approach. Gravity effects on distribution, translation, rotation and orientation statistics of non-spherical particles modeled as oblate spheroids have been studied both in an upward and a downward flow and compared with results obtained in the absence of gravity. Altogether 12 different particle classes have been studied, with inertia and shape parameterized by means of Stokes number St and aspect ratio λ ≤ 1. The St = 5 disk-like particles distribute more evenly across the channel in upward than in downward flow. The gravity effect on the particle concentration diminishes with large inertia and the spheroid shape has only a modest influence. Although the gravity significantly affects the streamwise and wall-normal mean slip velocities with increasing inertia, the particle shape rarely has any impact on the translational motion, except for the mean wall-normal velocity. The fluctuations of the velocity of disk-like particles are mainly ascribed to inertia, whereas the gravity and shape only have marginal effects. The presence of gravity is moreover found to have a negligible effect on the particles’ orientation and rotation, in spite of the striking effect of λ on the orientation and rotation seen in the near-wall region. The tendency of the disks to align their symmetry axis orthogonal to the fluid vorticity in the channel center is stronger for particles with modest inertia. In the near-wall region, however, oblate spheroids preferentially align with the fluid vorticity for St >> 1. The observed behavior is believed to be caused by the influence of the gravity force on the turbophoresis; i.e. that inertial particles move towards low-turbulence regions.     

Technique for quantitative mapping of three-dimensional liquid–gas phase boundaries in microchannel flows

A diagnostic technique capable of characterizing interfaces between transparent, immiscible fluids is developed and demonstrated by investigating the morphology of liquid–gas interfaces in an adiabatic two-phase flow through a microchannel of 500 μm × 500 μm square cross section. Water seeded with 0.5 μm-diameter fluorescent polystyrene particles is pumped through the channel, and the desired adiabatic two-phase flow regime is achieved through controlled air injection. The diagnostic technique relies on obtaining particle position data through epifluorescent imaging of the flow at excitation and emission wavelengths of 532 nm and 620 nm, respectively. The particle position data are then used to resolve interface locations to within ±1 μm in the focal plane. By mapping the interface within individual focal planes at various depths within the channel, it is possible to determine the complete liquid–gas interface geometry across the channel cross section in a dynamic flow environment. Utilizing this approach, the liquid–gas phase boundaries of annular flows within a microchannel have been successfully characterized.     

Modification of silica with PMMA via ultrasonic irradiation and its application for reinforcement of polyacrylates

Polymethyl methacrylate （PMMA） encapsulated silica nanocomposite particles were prepared by ultra- sonically induced in situ polymerization of methyl methacrylate （MMA） on the surface of silica sol. The nanoparticles were characterized by Fourier transform infrared spectroscopy （FFIR）, transmission electron microscopy （TEM）, thermogravimetry （TG）, scanning electron microscopy （SEM）. The results showed that core-shell structure nanocomposite particles with an average size of 36 nm were obtained, and the thickness of polymer encapsulating layer was about 8 nm. The pretreatment of silica sol with tert-butyl hydroperoxide （TBHP） and the addition of ~-methacryloxypropyl trimethoxysilane （MAPTS） significantly enhanced the encapsulation effect. Modified by the polymer layer, the silica particles could be well dispersed in matrices and utilized to improve the mechanical performance of polyacrylates.     

Novel synthesis with an atomized microemulsion technique and characterization of nano-calcium carbonate （CaCO3）/poly（methyl methacrylate） core-shell nanoparticles

The synthesis of hard-core/soft-shell calcium carbonate （CaCO3）/poly（methyl methacrylate） （PMMA） hybrid structured nanoparticles （〈100nm） by an atomized microemulsion polymerization process is reported. The polymer chains were anchored onto the surface of nano-CaCO3 through use of a cou- pling agent, triethoxyvinyl silane （TEVS）. Ammonium persulfate （APS）, sodium dodecyl sulfate （SDS） and n-pentanol were used as the initiator, surfactant and cosurfactant, respectively. The polymeriza- tion mechanism of the core-shell latex particles is discussed. The encapsulation of nano-CaCO3 by PMMA was confirmed using a transmission electron microscope （TEM）. The grafting percentage of the core-shell particles was investigated by thermogravimetric analysis （TGA）. The nano-CaCO3/PMMA core-shell par- ticles were characterized by Fourier transform infrared （FTIR） spectroscopy and differential scanning calorimetry （DSC）. The FTIR results revealed the existence of a strong interaction at the interface of the nano-CaCO3 particle and the PMMA, which implies that the polymer chains were successfully grafted onto the surface of the nano-CaCO3 particles through the link of the coupling agent, In addition, the TGA and DSC results indicated an enhancement of the thermal stability of the core-shell materials compared with that of the pure nano-PMMA, The nano-CaCO3/PMMA particles were blended into a polypropylene （PP） matrix by melt processing. It can also be observed using scanning electron microscopy （SEM） that the PMMA chains grafted onto the CaCO3 nanoparticles interfere with the aggregation of CaCO3 in the polymer matrix （PP matrix） and thus improve the compatibility of the CaCO3 nanoparticles with the PP matrix.     

Synthesis and characterization of PMMA/Al2O3 composite particles by in situ emulsion polymerization

In order to improve its dispersibility, superfine alumina （A1203） was encapsulated with poly（methyl methacrylate） （PMMA） by in situ emulsion polymerization. It was found that only when the concentration of sodium dodecyl sulfate （SDS） was much higher than its critical micelle concentration, could PMMA/Al2O3 composite particles with high percentage of grafting （PG） be prepared. The same results were obtained between the experimental and stoichiometric amounts of tris（dodecylbenzenesulfonate） isopropoxide （NDZ）, indicating that single-molecule-layer adsorption had taken place between NDZ and Al2O3. Analysis using FTIR, TEM and XPS showed that PMMA/Al2O3 composite particles with core-shell structure had been successfully synthesized by in situ emulsion polymerization. Compared to Al2O3, thermal stability and dispersibility of the composite particles showed marked improvement.     

A solids mixing rate correlation for small scale fluidized beds

A new first degree solids mixing rate is proposed to evaluate the mixing of solids in small scale fluidized beds. Particle mixing experiments were carried out in a 2D fluidized bed with a cross-section of 0.02 m × 0.2 m and a height of 1 m. White and black particles with average diameters of 850 and 450 μm were used in our experiments. Image processing was used to measure the concentration of the tracers at different times. The effects of four representative operating parameters (superficial gas velocity, ratio of tracer particles to bed particles, tracer particle position, and particle size) on mixing are discussed with reference to the mixing index. We found that the Lacey index depends on the concentration of the tracers. The position of the tracers affects the initial mixing rate but not the final degree of mixing. However, the new mixing rate equation does not depend on the initial configuration of the particles because this situation is considered to be the initial condition. Using the data obtained in this work and that found in literature, an empirical correlation is proposed to evaluate the mixing rate constant as a function of dimensionless numbers (Archimedes, Reynolds, and Froude) in small scale fluidized beds. This correlation allows for an estimation of the mixing rate under different operating conditions and for the detection of the end point and/or the time of mixing.     

Particle number size distribution and new particle formation （NPF） in Lanzhou,Western China

Particle number size distribution from 10 to 10,000 nm was measured by a wide-range particle spectrometer (WPS-1000XP) at a downwind site north of downtown Lanzhou, western China, from 25 June to 19 July 2006. We first report the pollution level, diurnal variation of particle concentration in different size ranges and then introduce the characteristics of the particle formation processes, to show that the number concentration of ultrafine particles was lower than the values measured in other urban or suburban areas in previous studies. However, the fraction of ultrafine particles in total aerosol number concentration was found to be much higher. Furthermore, sharp increase of ultrafine particle concentration was frequently observed at noon. An examination of the diurnal pattern suggests that the burst of the ultrafine particles was mainly due to nucleation process. During the 25-day observation, new particle formation (NPF) from homogeneous nucleation was observed during 33% of the study period. The average growth rate of the newly formed particles was 4.4 nm/h, varying from 1.3 to 16.9 nm/h. The needed concentration of condensable vapor was 6.1 × 10⁷ cm^?3, and its source rate was 1.1 × 10⁶ cm^?3 s^?1. Further calculation on the source rate of sulphuric acid vapor indicated that the average participation of sulphuric acid to particle growth rate was 68.3%.     

Experimental investigation on flow asymmetry in solid entrance region of a square circulating fluidized bed

To study the influence of back feeding particles on gas-solid flow in the riser, this paper investigated the flow asymmetry in the solid entrance region of a fluidized bed by particle concentration/velocity measurements in a cold square circulating fluidized beds （CFB）. The pressure drop distribution along the riser and the saturation carrying capacity of gas for Geldart-B type particles were first analyzed. Under the condition of u0 = 4 m/s and Gs = 21 kg/（m^2 s）, the back feeding particles were found to penetrate the lean gas-solid flow near the entrance （rear） wall before reaching the opposite （front） wall, thus leading to a relatively denser region near the front wall in the bottom bed. Higher solid circulation rate （u0 =4 m/s, Gs = 33 kg/（m^2 s）） resulted in a higher particle concentration in the riser. However the back feeding particles with higher momentum increased the asymmetry of the particle concentration/velocity profile in the solid entrance region. Lower air velocity （u0 =3.2 m/s） and Gs =21 kg/（m2 s）, beyond the saturation carrying capacity of gas, induced an S-shaped axial solid distribution with a denser bottom zone. This limited the penetration of the back feeding particles and forced the flnidizing air to flow in the central region, thus leading to a higher solid holdup near the rear wall. Under the conditions of uo = 4 m/s and Gs = 21 kg/（m^2 s）, addition of coarse particles （dp= 1145 μm） into the bed made the radial distribution of solids more symmetrical.     

Preparation of photoluminescent carbon dots-embedded polyelectrolyte microcapsules

Two types of photoluminescent carbon dots (CDs)-embedded polyelectrolyte (PE) microcapsules were successfully prepared via the layer-by-layer (LbL) assembly approach on sacrificial templates. For the first type, the PE microcapsules with CDs embedded in the cavity were produced from assembly of five pairs of poly(sodium 4-styrensulfonate) (PSS) and poly(allylamine hydrochloride) (PAH) on CDs-pre-loaded meso-porous silica. For the second type, the PE microcapsules with CDs embedded in the wall were made of CDs and PAH, which were derived from SiO₂ particles as templates. Microscope images confirmed the introduction of CDs into the two CDs-embedded microcapsules. These two microcapsules also retained the optical properties of free CDs. Photoluminescence spectra revealed that the two types of microcapsules had excitation-dependent photoluminescence behavior. When the excitation wavelength changed from 280 to 340 nm, photoluminescence emission peak of the PE microcapsules with CDs embedded in the cavity shifts from 369 to 377 nm, while for microcapsules with CDs embedded in the wall, emission peak shifts from 367 to 390 nm. Due to low toxicity, good hydrophilicity and photoluminescence properties of CDs, these two kinds of photo-luminescent microcapsules have competitive potential for application in carriers for imaging, drug delivery and biosensors.     

MONODISPERSED AND NANOSIZED DENDRIMER／POLYSTYRENE LATEX PARTICLES

Emulsion polymerization of styrene was carried out using dendrimer DAB-dendr-(NH2)64 as seed. The size and size distribution of the emulsion particles were characterized by transmission electron microscopy (TEM) and dynamic light scattering (DLS), and the effects o.f emulsion polymerization conditions on the preparation of emulsion particle were investigated. It has been found that the nanosized dendrimer/polystyrene polymer emulsion particles obtained were in the range of 26～64nm in diameter, and were monodisperse; the size and size distribution of emulsion particles were influenced by the contents of dendrimer DAB-dendr-(NH2)64, emulsifier and initiator, as well as the pH value.     

Oil emulsion separation with fluidic oscillator generated microbubbles

Surfactants stabilise oil droplets in water, forming a dispersed oil–water emulsion. Treatment of oily effluents is a serious challenge owing to the high stability and colloidal nature of the oil droplets. In many applications, microbubbles are employed for separation purposes due to their buoyancy and increased surface area to volume ratio. This property has been exploited in the water treatment industry for separation in a process known as dissolved air flotation (DAF). Though practically efficient, the process is energy intensive operating at >5 bars and consequently consuming ∼90% of the total energy required in water purification plants. In this study microbubbles were produced by fluidic oscillation via a no-moving part diverter valve to cut down the energy consumption considerably. Microbubbles are applied for the separation of emulsified oil in a process known as microflotation. The mean bubble size generated by fluidic oscillation from the 50 μm pore diffuser was ∼100 μm, otherwise coarse bubbles were produced under steady flow. The effect of surfactant concentration on oil droplet size was investigated. It was found that oil droplet size varied inversely proportional to surfactant concentration. In addition, it was found that the oil removal efficiency also depends on the surfactant concentration. The maximum oil removal efficiency by Microflotation was found to be 91% under lowest surfactant concentration tested (0.3 wt%) whilst at highest surfactant concentration used (10 wt%); lowest recovery efficiency (19.4%) was recorded.     

Chemically modified magnetic chitosan microspheres for Cr(VI) removal from acidic aqueous solution

A bioadsorbent composed of magnetic silica nanoparticles encapsulated by chitosan microspheres was prepared by the emulsion cross-linking method, and it was then modified with quaternary ammonium groups by reaction with ethylenediamine and glycidyl trimethylammonium chloride. Characterization of the bioadsorbent indicated that it was highly acid resistant and magnetically responsive. The bioadsorbent was then used to remove Cr(VI) from acidic aqueous solution. The results of batch experiments indicated that the optimal pH value was 2.5, and the adsorbent exhibited low pH dependence. The maximum adsorption capacity was 233.1 mg/g at pH 2.5 and 25 °C, and the equilibrium time was determined to be 40–120 min depending on the initial Cr(VI) concentration. The adsorbent could be effectively regenerated using a mixture of 0.3 mol/L NaOH and 0.3 mol/L NaCl with a desorption efficiency of 95.6%, indicating high reusability. In conclusion, the bioadsorbent shows potential for Cr(VI) removal from acidic wastewater.     

Analysis of the causes of heavy aerosol pollution in Beijing,China: A case study with the WRF-Chem model

The causes and variability of a heavy haze episode in the Beijing region was analyzed. During the episode, the PM_2.5 concentration reached a peak value of 450 μg/kg on January 18, 2013 and rapidly decreased to 100 μg/kg on January 19, 2013, characterizing a large variability in a very short period. This strong variability provides a good opportunity to study the causes of the haze formation. The in situ measurements (including surface meteorological data and vertical structures of the winds, temperature, humidity, and planetary boundary layer (PBL)) together with a chemical/dynamical regional model (WRF-Chem) were used for the analysis. In order to understand the rapid variability of the PM_2.5 concentration in the episode, the correlation between the measured meteorological data (including wind speed, PBL height, relative humidity, etc.) and the measured particle concentration (PM_2.5 concentration) was studied. In addition, two sensitive model experiments were performed to study the effect of individual contribution from local emissions and regional surrounding emissions to the heavy haze formation. The results suggest that there were two major meteorological factors in controlling the variability of the PM_2.5 concentration, namely, surface wind speed and PBL height. During high wind periods, the horizontal transport of aerosol particles played an important role, and the heavy haze was formed when the wind speeds were very weak (less than 1 m/s). Under weak wind conditions, the horizontal transport of aerosol particles was also weak, and the vertical mixing of aerosol particles played an important role. As a result, the PBL height was a major factor in controlling the variability of the PM_2.5 concentration. Under the shallow PBL height, aerosol particles were strongly confined near the surface, producing a high surface PM_2.5 concentration. The sensitivity model study suggests that the local emissions (emissions from the Beijing region only) were the major cause for the heavy haze events. With only local emissions, the calculated peak value of the PM_2.5 concentration was 350 μg/kg, which accounted for 78% of the measured peak value (450 μg/kg). In contrast, without the local emissions, the calculated peak value of the PM_2.5 concentration was only 100 μg/kg, which accounted for 22% of the measured peak value.     

Set up of an experimental apparatus for the study of fragmentation of solid fuels upon severe heating

An experimental apparatus has been developed in order to perform tests of primary fragmentation of solid fuels under severe heating conditions. The device is a modified heated strip reactor, capable to reach 2000 °C in less than 0.2 s. Particles are laid on the strip and pyrolysed under inert or moderately oxidizing conditions. The char particles and their fragments, generated upon pyrolysis, can be recovered and analysed to assess the fragmentation propensity of the fuel.Some preliminary experiments have been carried out on two biomass samples in order to assess the time-temperature history of particles in the experimental apparatus. In particular biomass particles of approximately 2–3 mm have been used. The temperature of the heated strip reactor in such preliminary tests was varied between 1000 and 1600 °C, while the strip nominal heating rate was kept at 10⁴ °C/s and the holding time was set at the value of 10 s. A near infrared fast camera (38,000 frames/s) has been used to measure the temperature of the heated strip and of the particles during the tests. A heat up model was developed and validated against experimental results. The model was then used to estimate the temperature gradients across particles of biomass and of coal as well.Results show that the strip of the reactor reaches the set temperature in less than 0.2 s. When particles are laid on the strip, their bottom surface, which is in physical contact with the strip, immediately reaches the set temperature value. For 1 mm coal particles the upper surface can be considered at the same temperature as well. Under the most severe conditions tested (strip temperature of 1600 °C , biomass particles of 2 mm thickness) the temperature difference between the bottom and the upper face is 200 °C after 3 s and drops to 100 °C after 10 s. On the whole the experimental apparatus simulates uniform heating of the particles with reasonable approximation. In the next future the apparatus will be further upgraded to operate at pressures up to 20 bars.     

Flow of mono-dispersed particles through horizontal bend

Pipeline slurry flow of mono-dispersed particles through horizontal bend is numerically simulated by implementing Eulerian two-phase model in FLUENT software. A hexagonal shape and Cooper type non-uniform three-dimensional grid is chosen to discretize the entire computational domain, and a control volume finite difference method is used to solve the governing equations. The modeling results are compared with the experimental data collected in 53.0 mm diameter horizontal bend with radius of 148.4 mm for concentration profiles and pressure drops. Experiments are performed on narrow-sized silica sand with mean diameter of 450 μm and for flow velocity up to 3.56 m/s (namely, 1.78, 2.67 and 3.56 m/s) and four efflux concentrations up to 16.28% (namely, 0%, 3.94%, 8.82% and 16.28%) by volume for each velocity. Eulerian model gives fairly accurate predictions for both the pressure drop and concentration profiles at all efflux concentrations and flow velocities.     

Synthesis of PS/Ag asymmetric hybrid particles via phase separation and self-assembly

This article presents a facile approach to preparation of polystyrene/silver （PS/Ag） asymmetric hybrid par- ticles. In this method, polystyrene/polyglycidyl methacrylate （PS/PGMA） Janus particles were synthesized via internal phase separation triggered by evaporation of dichloromethane （DCM） from PS/PGMA/DCM- in water emulsion droplets. Then, the Janus particles were aminated and sequentially carboxylated to obtain PS/PGMA-NH2 and PS/PGMA-COOH particles. Ag＋ self-assembled on the surface of PGMA hemi- sphere of the functionalized PS/PGMA particles by coordinating with amine/carboxyl. PS/Ag asymmetric hybrid particles with 7.29 wt% of Ag were obtained by reduction of Ag＋, Scanning electron microscopy, energy-dispersive X-ray spectroscopy and transmission electron microscopy results confirmed that Ag was asymmetrically distributed on the surface of polymer particles.