The removal of arsenic from (ground)-water by adsorbent loaded in polymeric microspheres

Arsenic is a natural tasteless and odourless element,existing in the earth's crust at average levels of between two and five thousands micrograms per liter (parts per million) . Arsenic is highly toxic to humans, who are exposed to it primarily from air,food and water. The occurrence of arsenic in groundwater is due to geological composition of soil. High concentrations of arsenic in water are the result of dissolution or desorption of ferric oxides and the oxidation of mineral arsenopyrites. Arsenic in drinking water has an important impact on the human health,especially in the less developed countries. Different methods exist to remove arsenic from aquatic media,and one of them is by adsorption. In this work,the adsorption of both As(III) and As(V) by means of novel microspheres has been investigated. In particular,TiO2 has been embedded into polymeric microspheres PES (PolyEtherSulphone) and PEEK-WC (PolyEtherEther-Ketone) . The main advantages of this encapsulation adsorption material are: no loss of adsorbents into the water stream,easy to be used and scaled-up.

An efficient preparation of porous polymeric microspheres by solvent evaporation in foam phase

This paper reports an efficient method of preparing porous polymeric microspheres by solvent evaporation in foam phase,in which phase separation between polymer and porogen occurs in foam phase instead of that in water phase by using the traditional solvent eva poration method.The method provides outstanding features,including being time-saving,of high-yield and able for continuous production,in which formation of porous polymeric microspheres finished within 3 min with a high production yield up to approximate 95 wt% and the process was able to be developed into a continuous process for production of porous polymeric microspheres.It was also universal to non-crosslinked polymers since the method is a development on the traditional emulsion solvent evaporation method.The new method is efficient and can be used potentially on the industrial scale for continuous production of porous polymeric microsphere s.

Polymeric microsphere injection in large pore-size porous media

High water-cut has become a worldwide challenge for oil production.It requires extensive efforts to process and dispose.This entails expanding water handling facilities and incurring high power consumption costs.Polymeric microsphere injection is a cost-effective way to deal with excessive water production from subterranean formations.This study reports a laboratory investigation on polymeric microsphere injection in a large volume to identify its in-depth fluid diversion capacity in a porous media with large pore/particle size ratio.The performance of polymeric microsphere injection was evaluated using etched glass micromodels based on the pore network of a natural carbonate rock,which were treated as water-wet or oil-wet micromodels.Waterflooding was conducted to displace oil at reservoir temperature of 95°C,followed by one pore volume of polymeric microsphere injection.Three polymeric microsphere samples with median particle size of 0.05,0.3,and 20μm were used to investigate the impact of particle size of the polymeric microspheres on incremental oil production capacity.Although the polymeric microspheres were much smaller than the pores,additional oil production was observed.The incremental oil production increased with increasing polymeric microsphere concentration and particle size.As a comparison,polymeric microsphere solutions were injected into oil-wet and water-wet micromodels after waterflooding.It was observed that the oil production in oil-wet micromodel was much higher than that in water-wet micromodel.The wettability of micromodels affected the distribution patterns of the remaining oil after waterflooding and further dominated the performance of the microsphere injection.The study supports the applicability of microsphere injection in oil-wet heterogeneous carbonates.

SYNTHESIS OF MONODISPERSE HOLLOW POLYMER MICROSPHERES WITH FUNCTIONAL GROUPS BY DISTILLATION PRECIPITATION POLYMERIZATION

Monodisperse hollow polymer microspheres having various functional groups on the shell-layer, such as carboxylic acid, pyridyl and amide, were prepared by two-stage distillation precipitation polymerization in neat acetonitrile in the absence of any stabilizer or additive, during which monodisperse poly（methacrylic acid） （PMAA） afforded from the first-stage polymerization was utilized as the seeds for the second-stage polymerization. The shell layer with different functional groups was formed during the second-stage copolymerization of either divinylbenzene （DVB） or ethyleneglycol dimethacrylate （EGDMA） as crosslinker and the functional comonomers, in which the hydrogen-bonding interaction between the carboxylic acid group of PMAA core and the functional groups of the corresponding comonomers, including carboxylic acid, amide and pyridyl, played an essential role for the formation of monodisperse core-shell functional microspheres. The hollow polymer microspheres were then developed after the subsequent removal of PMAA cores by dissolution in ethanol under basic condition. Transmission electron microscopy （TEM） and scanning electron microscopy （SEM） were used to determine the morphology of the resultant PMAA core, functional core-shell microspheres and the corresponding hollow polymer microspheres with different functional groups. FT-IR spectra confirmed the successful incorporation of the various functional groups on the shell layer of the hollow polymer microspheres.

A review of recent progress in preparation of hollow polymer microspheres

The preparation methods of hollow polymer microspheres both at home and abroad are summarized, and their preparation mechanisms and developmental states are presented. These methods include the liquid droplet method, dried-gel droplet method, self-assembly method, microencapsulation method, emulsion polymerization method and the template method. Hollow polystyrene microspheres are the most extensively studied in the research of hollow polymer microspheres. Through comparison of the advantages and disadvantages of different preparation methods, it is concluded that microencapsulation method is most suitable for preparing polystyrene hollow microspheres.

Preparation of Dysprosium Ferrite/Polyacrylamide Magnetic Composite Microsphere and Its Characterization

Using the technique of microemulsion polymerization with nano-reactor, dysprosium ferrite/polyacrylamide magnetic composite microsphere was prepared by one-step method in a single inverse microemulsion. The structure, average particle size, morphology of composite microsphere were characterized by FTIR, XRD, TEM and TGA. The magnetic responsibility of composite microsphere was also investigated. The results indicate that the magnetic composite microsphere possess high magnetic responsibility and suspension stability.

PREPARATION OF MONODISPERSE CROSSLINKED POLYMER MICROSPHERES HAVING CHLOROMETHYL GROUP BY DISTILLATIONPRECIPITATION POLYMERIZATION

Monodisperse crosslinked poly(chloromethylstyrene-co-divinylbenzene)(poly(CMSt-co-DVB))microsphereswere prepared by distillation-precipitation copolymerization of chloromethylstyrene(CMSt)and divinylbenzene(DVB)inneat acetonitrile.The polymer particles had clean surfaces due to the absence of any added stabilizer.The size of the particlesranges from 2.59 μm to 3.19 μm and with mono-dispersity around 1.002-1.014.The effects of monomer feed incopolymerization on the microsphere formation were described.The polymer microspheres were characterized by SEM andchlorinity elemental analysis.

PREPARATION OF POLYMER MICROSPHERES WITH PYRIDYL GROUP AND THEIR STABILIZED GOLD METALLIC COLLOIDS

Narrow disperse poly（ethyleneglycol dimethacrylate-co-4-vinylpyridine） （poly（EGDMA-co-4-VPy）） microspheres were prepared by distillation-precipitation copolymerization of ethyleneglycol dimethacrylate （EGDMA） and 4-vinylpyridine （4-VPy） with 2,2＇-azobisisobutyronitrile （AIBN） as initiator in neat acetonitrile. The polymer microspheres containing pyridyl group were then utilized as stabilizer for gold metallic colloids with the diameter around 7 nm, which were prepared by the in situ reduction of gold chloride trihydrate with sodium borohydride through the coordination of the pyridyl group on the gel layer and surface of the microsphere with the gold metallic nano-particles. The catalytic properties of the pyridyl- functionalized microsphere-stabilized gold metallic colloids and the behavior of the stabilized-catalyst for the recycling were investigated with reduction of 4-nitrophenol to 4-aminophenol as a model reaction.

Preparation and performance of fluorescent polyacrylamide microspheres as a profile control and tracer agent

Polyacrylamide microspheres have been suc- cessfully used to reduce water production in reservoirs, but it is impossible to distinguish polyacrylamide microspheres from polyacrylamide that is used to enhance oil recovery and is already present in production fluids. In order to detect polyacrylamide microspheres in the reservoir pro- duced fluid, fluorescent polyacrylamide microspheres P（AM-BA-AMCO）, which fluoresce under ultraviolet irradiation, were synthesized via an inverse suspension polymerization. In order to keep the particle size distribu- tion in a narrow range, the synthesis conditions of the polymerization were studied, including the stirring speed and the concentrations of initiator, NaaCO3, and dispersant. The bonding characteristics of microspheres were deter- mined by Fourier transform infrared spectroscopy. The surface morphology of these microspheres was observed under ultraviolet irradiation with an inverse fluorescence microscope. A laboratory evaluation test showed that the fluorescent polymer microspheres had good water swelling capability, thus they had the ability to plug and migrate in a sand pack. The plugging rate was 99.8 % and the residual resistance coefficient was 800 after microsphere treatment in the sand pack. Furthermore, the fluorescent microspheres and their fragments were accurately detected under ultra- violet irradiation in the produced fluid, even though theyhad experienced extrusion and deformation in the sand pack.

Local immunotherapy with interleukin - 2 delivered from biodegradable polymer microspheres combined with interstitial chemotherapy: a novel treatment for experimental malignant glioma.

OBJECTIVE:Local delivery of carmustine(BCNU)from biodegradablepolymers prolongs survival against experi-mental brain tumors.Moreover,paracrine administration of interleukin-2(IL-2)has been shown to elicit apotent antitumor immune response and to improve survival in animal brain tumor models.We report the use of anovel polymeric microsphere delivery vehicle to release IL-2.We demonstrate both in vitro release of cytokinefrom the microspheres and histological evidence of the inflammatory response elicited by IL-2 released from themicrospheres in the rat brain.Thees microspheres are used to deliver IL-2,and biodegradable polymer wafers

An efficient synthesis of ampicillin on magnetically separable immobilized penicillin G acylase

Penicillin G acylase(PGA) was immobilized on the magnetic hydrophilic polymer microspheres with average pore size of 17.1 nm,specific surface area of 128.2 m2/g and saturate magnetization of 6.4 emu/g.The 96.7%ampicillin yield with 1.60 of the synthesis/hydrolysis(S/H) ratio from 6-aminopenicillanic acid(6-APA) and D-(-)-alpha-phenylglycine methyl ester(D-PGME) can be achieved using the resultant magnetic biocatalyst in ethylene glycol,where only 82.1%yield with 1.40 of the S/H ratio was obtained using the free PGA under the identical reaction conditions.The immobilized PGA can be separated magnetically and recycled for five times without obvious loss of its catalytic activity.

Photo-induced fusion of monodisperse polymer microspheres:A novel strategy for constructing topological microsphere clusters with improved stability

The preparation of monodisperse azobenzene(Azo)polymer microspheres by dispersion polymerization was reported.The photo-induced fusion of Azo polymer microspheres was successfully achieved during the process of reversible trans-cistrans photoisomerization of Azo units,and induced various unique“microsphere molecular”clusters or“microsphere polymers”.Encouraged by this interesting phenomenon,microsphere clusters of different topological structures were stabilized by the in situ acetal cross-linking chemistry.The photo-induced fusion polymerization of monodisperse polymer microspheres provides a new strategy for designing photo-responsive clusters and allows for control over the mechanical properties of microspheres with high spatiotemporal resolution.

Influence of surface modification of SrFe12O19 particles with oleic acid on magnetic microsphere preparation

Oleic acid was used as surface modification agent to improve the hydrophobicity of magnetic strontium hexaferrite particles. The structure and properties of treated magnetic particles were characterized by scanning electronic microscopy （SEM）, Fourier transform infrared spectra （FTIR）, powder X-ray diffraction （XRD） and magnetic property measurement system （MPMS）. The results show that oleic acid is chemically enwrapped on the surface of SrFe12O19 particles. Magnetic particles modified by oleic acid are highly dispersible and strongly responsive to magnetism but with slight decrease in saturated magnetization. The affinity between magnetic particles and monomers is improved by surface modification, resulting in increased particle incorporation in magnetic polymeric microspheres. The surface modification mechanism of magnetic particles by oleic acid is addressed in this work.

MAGNETIC POLYMER MICROSPHERE STABILIZED GOLD NANOCOLLOIDS AS A FACILELY RECOVERABLE CATALYST

Magnetically responsive hierarchical magnetite/silica/poly（ethyleneglycol dimethacrylate-co-4-vinylpyridine） （Fe3O4/SiO2/P（EGDMA-co-VPy）） tri-layer microspheres were used as stabilizers for gold metallic nanoeolloids as a facilely recoverable catalyst with the reduction of 4-nitrophenol to 4-aminophenol as a model reaction. The magnetic microsphere stabilized gold metallic nanocolloids were prepared by in situ reduction of gold chloride trihydrate with borohydride as reductant via the stabilization effect of the pyridyl groups to gold nanoparticles on the surface of the outer shell-layer of the inorganic/polymer tri-layer microspheres.

Preparation and Properties of Magnetic-fluorescent Microporous Polymer Microspheres

Microporous microspheres can be used as functional nanomaterial carriers for their microporous structure and higher specific surface area. In this study, magnetic fluorescent polymer microspheres were prepared by incorporating Fe304 nanoparticles and CdSe/ZnS quantum dots（QDs） into hyper-crosslinked microporous polymer micro- spheres（HCMPs） via the in situ coprecipitation method and swelling-diffusion. The HCMPs predominantly have mi- cropores, and their specific surface area is as high as 703.4 m2/g. The magnetic-fluorescent microspheres maintain the superparamagnetic behavior of Fe304, and the saturation magnetization reaches 38.6 A.m2/kg. Moreover, the composite microspheres exhibit an intense emission peak at 530 nm and achieve good fluorescence.

Whispering-gallery mode lasing from polymer microsphere for humidity sensing

Microlasers based on high quality （Q） whispering-gallery mode （WGM） resonance are pronfising low threshold laser sources for bio-sensing and imaging applications. In this Letter, dye-doped polymer microspheres were fabricated by a controlling emulsion solvent evaporation method. WGM lasing with low threshold and high Q factors was realized in an individual microsphere under femtosecond laser pumping. The slight change of environmental relative humidity （RH） can be monitored by measuring the shift of the lasing modes at tile ex- posure of water molecules, which dcmonstrates the sensitivity is as high as 6 pm/RH%. The results would offer an insight into employing microlasers as sensors.

Preparation and characterization of conducting polymer-coated thermally expandable microspheres

The thermally expandable microspheres（TEMs） were prepared via suspension polymerization with acrylonitrile（AN）, methyl methacrylate（MMA） and methyl acrylate（MA） as monomers and n-hexane as the blowing agent. Meanwhile, a novel type of functional and conductive thermal expandable microsphere was obtained through strongly covering the surface of microsphere by conductive polymers with the mass loading of 1.5%. The optimal conditions to prepare high foaming ratio and equally distributed microcapsules were investigated with AN-MMA-MA in the proportion of 70%/20%/10%（m/m/m）, and 25 wt% of n-hexane in oil phase. The further investigation results showed that the unexpanded TEMs were about 30 μm in diameter and the maximum expansion ratio was nearly 125 times of original volume. The polypyrrole（PPy） was smoothly coated on the surface of the TEMs and the expansion property of PPy-coated TEMs was almost the same as the uncoated TEMs. Moreover, the structure and expanding performance of TEMs and PPy-coated TEMs were characterized by scanning electron microscopy（SEM）, laser particle size analyzer and dilatometer（DIL）.

PREPARATION OF SILICA/POLY(METHACRYLIC ACID)/POLY(DIVINYLBENZENE-CO-METHACRYLIC ACID) TRI-LAYER MICROSPHERES AND THE CORRESPONDING HOLLOW POLYMER MICROSPHERES WITH MOVABLE SILICA CORE

Hollow poly（divinylbenzene-co-methacrylic acid） （P（DVB-co-MAA）） microspheres were prepared by the selective dissolution of the non-crosslinked poly（methacrylic acid） （PMAA） mid-layer in ethanol from the corresponding silica/PMAA/P（DVB-co-MAA） tri-layer hybrid microspheres, which were afforded by a three-stage reaction. Silica/PMAA core-shell hybrid microspheres were prepared by the second-stage distillation polymerization of methacrylic acid （MAA） via the capture of the oligomers and monomers with the aid of the vinyl groups on the surface of 3-（methacryloxy）propyl trimethoxysilane （MPS）-modified silica core, which was prepared by the Stober hydrolysis as the first stage reaction. The tri-layer hybrid microspheres were synthesized by the third-stage distillation precipitation copolymerization of functional MAA monomer and divinylbenzene （DVB） crosslinker in presence of silica/PMAA particles as seeds, in which the efficient hydrogen-bonding interaction between the carboxylic acid groups played as a driving force for the construction of monodisperse hybrid microspheres with tri-layer structure. The morphology and the structure of silica core, silica/PMAA core-shell particles, the tri-layer hybrid microspheres and the corresponding hollow polymer microspheres with movable silica cores were characterized by transmission electron microscopy （TEM）, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy （XPS）.

Preparation of porous polyimide microspheres by thermal degradation of block copolymers

A new preparation method has been developed for thermally stable porous polyimide microspheres. Porous polyimide microspheres were prepared using trib]ock copolymers that consisted of a thermally stable polyimide derived from pyromellitic dianhydride/4,4＇-oxydianiline as the continuous phase and a thermally labile polyether as the dispersed phase. Spheres of copolymers were generated in a nonaqueous emulsion and then gradually heated to complete the imidization to form a microphase-separated structure. Subsequently, thermal treatment at a slightly reduced pressure removed the labile blocks and produced pores. Under suitable decomposition conditions, the pore size of the porous polyimide was in the range of 200-400nm.

Effects of Shell Composition, Dosage and Alkali Type on the Morphology of Polymer Hollow Microspheres

Polymer hollow microspheres were prepared by performing alkali treatment on the multilayer core/shell polymer latex particles containing carboxyl groups. Effects of the shell composition and dosage as well as alkali type on the morphology of the microspheres were investigated. Results showed that in comparison with acrylonitrile（AN） and methacrylic acid（MAA）, using butyl acrylate（BA） as the shell co-monomer decreased the glass transition temperature（T_g） of shell effectively and was beneficial to the formation of uniform and big hollow structure. Along with the increase of the shell dosage, the alkali-treated microspheres sequentially presented porous and hollow morphology, and the size of microspheres increased, while the hollow diameter increased first and then decreased, and the maximum hollow ratio reached 39.5%. Furthermore, the multilayer core/shell microspheres had better tolerance to NH_3·H_2O than to NaOH. When the molar ratio of alkali to methacrylic acid（MR_（alkali/acid）） for Na OH ranged from 1.15 to 1.30 or MRalkali/acid for NH_3·H_2O ranged from 1.30 to 2.00, the regular polymer hollow microspheres could be obtained.