DESIGN AND CONTROL OF SOAP-FREE HYDROPHILIC-HYDROPHOBIC CORE-SHELL LATEX PARTICLES WITH HIGH CARBOXYL CONTENT IN THE CORE OF THE PARTICLES

Soap-flee hydrophilic-hydrophobic core-shell latex particles with high carboxyl content in the core of the particles were synthesized via the seeded emulsion polymerization using methyl methacrylate （MMA）, butyl acrylate （BA）, methacrylic acid （MAA）, styrene （St） and ethylene glycol dimethacrylate （EGDMA） as monomers, and the influences of MMA content used in the core preparation on polymerization, particle size and morphology were investigated by transmission electron microscopy, dynamic light scattering and conductometric titration. The results showed that the seeded emulsion polymerization could be carried out smoothly using ＂starved monomer feeding process＂ when MAA content in the core preparation was equal to or less than 24 wt%, and the encapsulating efficiency of the hydrophilic P（MMA-BA-MAA- EGDMA） core with the hydrophobic PSt shell decreased with the increase in MAA content. When an interlayer of P（MMA- MAA-St） with moderate polarity was inserted between the P（MMA-BA-MAA-EGDMA） core and the PSt shell, well designed soap-free hydrophilic-hydrophobic core-shell latex particles with 24 wt% MAA content in the core preparation were obtained.

THE PREPARATION AND CHARACTERIZATION OF SBR/PS CORE-SHELL PARTICLES BY GAMMA IRRADIATION

A kind of core(SBR)-shell(PS)particles was synthesized by using SBR latex and grafting with St under gammairradiation.The influences of absorbed dose and dose rate on the grafting yield of PS on SBR seed latex have beeninvestigated.Results show there was a transition layer which contained the SBR/PS graft copolymer between the SBR coreand PS shell.Dynamic laser scattering(DLS)and differential scanning calorimetry(DSC)results confirm the existence ofgrafted polystyrene,and transmission electron microscope(TEM)observation verifies the core-shell structure of SBR-g-PSlatex.Such SBR/PS core-shell latex could be processed easily to ultrafine rubber powders by using spray drying andexpected to be used as an impact modifier for PS.

TOUGHENING OF POLYCARBONATE WITH PBA-PMMA CORE-SHELL PARTICLES

The miscibility,mechanical properties,morphology and toughening mechanism of PC/PBA-PMMA blends wereinvestigated.The dynamic mechanical results show that PC/PBA-PMMA blend has good miscibility and strong interfacialadhesion.The Izod impact strength of blend PC/PBA-PMMA with 4%(volume fraction)PBA-PMMA core-shell modifier is16 times higher than that of pure PC.The core-shell volume fraction and thickness of the PMMA shell have effect on thetoughness of PC/PBA-PMMA blends.As PMMA volume fraction increases,the toughness of PC/PBA-PMMA blendincreases,and reaches a maximum value at 30% volume fraction of PMMA or so.The tensile properties of PC/PBA-PMMAblend with a minimum amount of PBA-PMMA modifier show that brittle-tough transition has no significant variance incomparison with that of pure PC.The scanning electron microscopic(SEM)observation indicates that the tougheningmechanism of the blend with the pseudo-ductile matrix modified by small core-shell latex polymer particles is the synergeticeffect of cavitation and shear yielding of the matrix.

Polybutylacrylate/poly (methyl methacrylate) Core-Shell Elastic Particles as Epoxy Resin Toughener: Part Ⅱ Toughness on DGEBA/DDM system

Mechanlcal properties of epoxy resin were investigated by adding core-shell elastic particles (CSEP). The results indicated that optimized core-shell ratio was 60/40 and the loading volume of CSEP was 10 phr (per hundred parts of epoxy resin by weight). The impact strength of modified systems increased apparently with the decrease of core sizes. However, the shearing strength changed gently with the particle sizes. CSEP with lightly crosslinked rubbery core showed more effectiveness on toughness than others. With solution blending, CSEP could be dispersed in epoxy matrix well, and the morphologies of dispersed rubber domains were controlled perfectly by CSEP whose structure was predesigned. A cavitation-shearing band toughness mechanism was observed from the SEM micrographs of fracture surface. It also was found that the deforming temperature (DT) of modified epoxy did not decline apparently.

Controlling Shell Thickness of PS/SiO_2 Core-Shell Particles and Their Crystallization into 3-D Ordered Thin Film

PS/SiO2 particles with core-shell structure were synthesized by coating silica on surface of polystyrene(PS) colloidal particles.The reaction parameters,such as initial tetraethyl orthosilicate(TEOS) concentration,water concentration and reaction temperature,have been investigated to control the thickness of silica shells.The shell thickness was prepositional to the square root of the initial concentration of TEOS and first increased with increasing water concentration,reached a maximum at about 2.0 mol/L and then started decreasing beyond that concentration.It was also found that the shell thickness decreased firstly with the reaction temperature added,then tended to a constant.The so-synthesized PS/SiO2 core-shell particles were directly crystallized into 3-D ordered thin film,then sintered at 570℃ into the ordered macroporous thin film.Compared with the conditional method,the present approach avoids repeatedly filling the precursor in the templetes and save time more.

Optimized high performance liquid chromatography–ultraviolet detection method using core-shell particles for the therapeutic monitoring of methotrexate

Methotrexate （MTX） is an antineoplastic drug, and due to its high toxicity, the therapeutic drug mon- itoring is strictly conducted in the clinical practice. The chemometric optimization and validation of a high performance liquid chromatography （HPLC） method using core-shell particles is presented for the determination of MTX in plasma during therapeutic monitoring. Experimental design and response surface methodology （RSM） were applied for the optimization of the chromatographic system and the analyte extraction step. A Poroshel1120 EC-C18 （3.0 mm × 75 mm, 2.7 μm） column was used to obtain a fast and efficient separation in a complete run time of 4 min. The optimum conditions for the chroma- tographic system resulted in a mobile phase consisting of acetic acid/sodium acetate buffer solution （85.0 mM, pH =4.00） and 11.2% of acetonitrile at a flow rate of 0.4 mL/min. Selectivity, linearity, accuracy and precision were demonstrated in a range of 0.10-6.0 μM of MTX. The application of the optimized method required only 150μL of patient plasma and a low consumption of solvent to provide rapid re- sults.

Review:Progress in Core-shell Rubber Particles for Efficiently Toughening Resins

Core-shell toughening particles are structured composite particles consisting of generally two different components, one at the center as a rubbery elastic core and surrounding by the second as a glassy inelastic shell. The design, preparation, and application of core-shell polymer particles have been briefly reviewed. Morphological characteristics of the core-shell particles by transmission electron microscopy(TEM) and scanning electron microscopy(SEM) are focused. The vital factors that are useful to control core-shell morphology and toughening properties including core-shell monomer species, polymerization conditions, cross-linking reagents, synthetic method, and post-processing techniques are analyzed. Distinguished properties are mainly considered as the most desirable features that endow core-shell polymer particles with various applicabilities, particularly as effectively toughening components in brittle epoxy resin and polylactide that are substrate of copper clad laminate widely used in the modern electronic world and environmentally friendly materials that are useful as packaging films, disposable tableware, biomedical equipment, and new energy vehicles.

Preparation of Core-shell Structured Particles and Their Nucleation in Polyester:I. Preparation of Monodisperse SiO_2/PS Core-shell Composite Particles

To enhance the nucleation and crystallization properties of polyester (e.g., polyethylene terephthalate, PET), core-shell structured particles are used to improve these properties by controlling the inorganic dispersion properties in the polymers. In the paper, monodisperse particles of silica/polystyrene (PS) are prepared with both dispersion and emulsion polymerization techniques. The monodisperse silicon dioxide particles are first prepared with the seed growth method and modified by the coupling agents. Silica is properly modified with KH-570, and its size deviation is 3.0% or so. The modified silica then reacts with the mixture of ethanol, water medium, and monomer of styrene under dispersion polymerization. Results show that the dispersion polymerization technique is more suitable for monodisperse core-shell SiO2/PS particles than that of the emulsion. The morphology and molecular structure of the core-shell particles are investigated with the transmission electron microscope (TEM), and fourier transform infra-red spectroscopy (FTIR). The results show that the modified silica particles are successfully encapsulated with polystyrene. The average number of silica particles encapsulated into each polystyrene sphere decreases when the size of silica particles increases from 50 nm to 600 nm, and will approach one when the silica is greater than 380nm in size. The mass ratio for silica/PS particles in emulsion polymerization is 4.7/1, lower than that of 6.8/1 for dispersion polymerization, which is the first reported optimized data for preparing the similar monodisperse composite particles. Thus, the PS shell in the former is thinner than that in the latter.

Superfast and solvent-free core-shell assembly of sulfur/carbon active particles by hail-inspired nanostorm technology for high-energy-density Li-S batteries

The demand on low-carbon emission fabrication technologies for energy storage materials is increasing dramatically with the global interest on carbon neutrality.As a promising active material for metal-sulfur batteries,sulfur is of great interest due to its high-energy-density and abundance.However,there is a lack of industry-friendly and low-carbon fabrication strategies for high-performance sulfur-based active particles,which,however,is in critical need by their practical success.Herein,based on a hail-inspired sulfur nano-storm(HSN)technology developed in our lab,we report an energy-saving,solvent-free strategy for producing core-shell sulfur/carbon electrode particles(CNT@AC-S)in minutes.The fabrication of the CNT@AC-S electrode particles only involves low-cost sulfur blocks,commercial carbon nanotubes(CNT)and activated carbon(AC)micro-particles with high specific surface area.Based on the above core-shell CNT@AC-S particles,sulfur cathode with a high sulfur-loading of 9.2 mg cm^(-2) delivers a stable area capacity of 6.6 mAh cm^(-2) over 100 cycles.Furthermore,even for sulfur cathode with a super-high sulfur content(72 wt%over the whole electrode),it still delivers a high area capacity of 9 mAh cm^(-2) over50 cycles in a quasi-lean electrolyte condition.In a nutshell,this study brings a green and industryfriendly fabrication strategy for cost-effective production of rationally designed S-rich electrode particles.

The Growth of Latex Particles during the VAc/BA Copolymerization

The semi-continuous seeded emulsion eopolymerization of vinyl acetate and butyl acrylate was carried out with hydroxyethyl cellulose as a colloid stabilizer. The morphology of the latex particle and the relationship between the reaction time and the average particle diameter and/or the conversion ratio during the polymerization were invstiguted. The experimental results shaw that the morphology of the latex particle possesses the stable sterie construction. In the seeded polymerizution, the average particle diameter of latex decreased while the conversion ratio increased. At the second term of the emulsion copolymerization （the growth stage of particle size）, the latex particle average diameter increased with copolymerization continuously, but the instantaneous conversation ratio was not large, so it was very necessaO to properly prolong the time during the holding temperature stage.

A New Kind of Void Soap-free P(MMA-EA-MAA) Latex Particles

Soap-free P(MMA-EA-MAA) particles with narrow size distribution were synthesized by seeded emulsion polymerization of methyl methacrylate (MMA), ethyl acrylate (EA) and methacrylic acid (MAA), and large voids inside the particles were generated by alkali posttreatment in the presence of 2-butanone. Results indicated that the size of void and the particle volume were related with the amount of 2-butanone. The generation mechanism of voids was proposed.

THE PREPARATION AND CHARACTERIZATION OF ZnO-Ag CORE-SHELL ULTRAFINE PARTICLE

The ZnO-Ag core-shell ultrafine particle in ethanol was prepared by photoreduction and colloidal methods. The experimental results obtained from aboorption spectroscopy. fluorescence sopectroscopy and electron microscopy revealed that the structure of the hybrid wide ig ZnO core covered with Ag shell. The thickness of the silver layer can ho controlled by the concentration of Ag+ ions and the time of UV irradiation. The structure of the electric double layer of the ZnO seed greatly affects the formation of ZnO-Ag hybtid particle.

Preparation of multihollow P(St-MAA) particles by sequence soap-free/soap emulsion polymerization and followed by stepwise alkali/acid posttreatment

The effects of ionic emulsifier, sodium dodecylbenzene sulfate (SDBS), on the formation of the multihollow structures in sub-micron sized polymer particles produced by alkali/acid posttreatment were investigated. The original latex particles with narrow size distribution were synthesized by a new sequence emulsifier-free/emulsifier emulsion copolymerization of styrene (St) and methacrylic acid (MAA). Results indicated that the pore size decreased and the pore number increased with the increase of SDBS amount, and the morphology of the posttreated latex particles was also significantly influenced by the introducing time of SDBS in the preparation of the original latex particles, and a suitable introducing time was 3 h of polymerization. (c) 2007 Cheng You Kan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Structural response of aluminum core–shell particles in detonation environment

Natural aluminum particles have the core-shell structure.The structure response refers to the mechanical behavior of the aluminum particle structure caused by external influences.The dynamic behavior of the structural response of aluminum core-shell particles before combustion is of great importance for the aluminum powder burning mechanism and its applications.In this paper,an aluminum particle combustion experiment in a detonation environment is conducted and analyzed;the breakage factors of aluminum particles shell in detonation environment are analyzed.The experiment results show that the aluminum particle burns in a gaseous state and condenses into a sub-micron particle cluster.The calculation and simulation demonstrate that the rupture of aluminum particle shell in the detonation environment is mainly caused by the impact of the detonation wave.The detonation wave impacts the aluminum particles,resulting in shell cracking,and due to the shrinkage-expansion of the aluminum core and stripping of the detonation product,the cracked shell is fractured and peeled with the aluminum reacting with the detonation product.

Synthesis and Structure Control of A New Kind of Inelastomer Impact Modifier with Core-shell Structure and Impact Modification to PVC/CPE

A new kind of inelastomer impact modifier with a coreshell structure was synthesized by employing a multistep composite emulsion polymerization technique, the size and morphology structure of the coreshell particles could be controlled by the multistep composite emulsion polymerization technique. The study of the impact strength and the elongation at break of the PVC/CPE blend with different contents of coreshell particles(CS) indicated that the mechanical properties of PVC/CPE/CS composite were the best when the concentration of the particle was 25%(mass fraction) which showed the different regularities and characteristics of elastomer toughening plastic.

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.

EFFECT OF PARTICLE SIZE ON THE FILMING PROCESS OF POLYSTYRENE LATEX STUDIED BY AFM

The film formation process of micro-PS particles (diameter 742 nm) and nano-PS particles (diameter 29 nm) was studied by atomic force microscopy and differential scanning calorimetry. During a step heating process, the particles were annealed for 0.5 h at each selected temperature. It was found that the deformation and interdiffusion temperatures of the micro-PS particles are ca. 120-130degreesC and 140-150degreesC, that of the nano-PS particles are 90degreesC and 100-110degreesC respectively. The DSC traces of nano-PS particles showed that there was an exothermic peak near T-g after annealing for 0.5 h at the selected temperatures below 90degreesC; otherwise, the exothermic peak disappeared after annealing at 100degreesC or above. Compared with the micro-PS particles, the sintering process of nano-PS particles occurs at much lower temperature determined by the confined state of polymer chains with higher conformational energy in nano-particles, and completes in a much narrower temperature range driven mainly by the larger total surface energy.

Determination of Size Distribution of Nano-particles by Capillary Zone Electrophoresis

A new method was developed for the determination of the size distribution of nano-particles by capillary zone electrophoresis (CZE). Scattering effect of nanoparticles was studied . This method for the determination of size distribution was statistical.

Electrorheological Properties of Suspensions of PAn-PEO-PAn Triblock Copolymer Particles

The PAn-PEO-PAn triblock copolymer with the PEG chain length of 400 was synthesized by chemical oxidation copolymerization of aniline and α,ω-bis（p-aminophenyl）poly（ethylene glycol）and characterized by FT-IR and TEM.The experimental results show that the copolymer particles are of μtypical core-shell structure after the self-assembly process in water.Its conductivity is much lower than that of the pure PAn.The suspension containing 20 vol% PAn-PEO-PAn tiblock copolymer in silicone oil exhibits.a typical electrorheological （ER） effect in DC electric field.while it shows a lower leakage current density than that of the pure PAn-based ER fluids.Therefore,the PEO shell hinders the electric hop among PANI chains and decreases the current density of ER fluids in an external electric field.at the same time the interface polarity improves the ER effects.

The structure and properties of Fe_3O_4/P (NaUA-St-BA) magnetic composite nano particles

Fe3O4/P （NaUA-St-BA） core-shell composite micro spheres were in situ prepared by soapless polymerization of styrene and butyl acrylate, with Fe3O4magnetic colloidal particles coated with NaUA. The results of IR and XRD analysis demonstrated that the desired polymer chains have been covalently bonded to the surface of Fe3O4 nano particles. The morphology analysis by TEM confirmed that the composite particles have the core-shell structure and a relatively uniform diameter of about 100nm. The magnetic properties of the obtained composite latex particles were measured by VSM and found that they exhibited super paramagnetic properties. Finally, the prepared magnetic composite particles latex is stable for several months.