Synthesis of PS and PDMAEMA mixed polymer brushes on the surface of layered silicate and their application in pickering suspension polymerization

An ammonium free radical initiator was ion exchanged onto the surface of clay layers. Polystyrene (PS) and poly(2‐(dimethylamino)ethyl methacrylate) (PDMAEMA) mixed polymer brushes on the surface of clay layers were prepared by in situ free radical polymerization. PS colloid particles armored by clay layers with mixed polymer brushes were prepared by Pickering suspension polymerization. Transmission electron microscopy (TEM), atomic force microscopy (AFM), and scanning electron microscopy (SEM) were used to characterize the structure and morphology of the colloid particles. Clay layers on the surface of PS colloid particles can be observed. Because of the cationic nature of the PDMAEMA brushes the colloid particles have positive zeta potentials at low pH values. X‐ray photoelectron spectroscopy (XPS) was used to analyze the surface of the colloid particles. N_1s binding energy of PDMAEMA chains on the surface of clay layers was detected by XPS. The two peaks of the N_1s binding energy indicate two different nitrogen environments on the surface of clay layers. The peak with a lower binding energy is characteristic of neutral nitrogen on PDMAEMA chains, and the peak with a higher binding energy is attributed to protonated nitrogen on PDMAEMA chains. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5759–5769, 2007     

Silica nanorings on the surfaces of layered silicate

A simple approach to the synthesis of clay-silica nanocomposites is presented. Silica nanorings on the edges of clay sheets were synthesized by using a modified St?ber method. Transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy, and fluorescence spectroscopy were employed to characterize the prepared nanocomposites. TEM results show that the average size of the nanorings increases with the growth of silica. XRD results indicate that the layered structures of clay can be found in the nanocomposite and the growth of silica nanorings expands the d spacing of clay platelets. The mechanism of the formation of the nanorings is discussed. The preparation of polystyrene (PS) brushes on the surfaces of silica nanorings by atom-transfer radical polymerization is also reported. The polymer nanocomposite with negatively charged clay surfaces and hydrophobic polymer brushes on the silica nanorings can be used in Pickering emulsions, and PS colloidal particles with clay-silica on the surfaces were prepared.     

Functional colloidal particles stabilized by layered silicate with hydrophilic face and hydrophobic polymer brushes

In this study, we describe a new strategy for producing narrowly dispersed functional colloidal particles stabilized by a nanocomposite with hydrophilic clay faces and hydrophobic polystyrene (PS) brushes on the edges. This method involves preparation of polymer brushes on the edges of clay layers and Pickering suspension polymerization of styrene in the presence of the nanocomposites. PS brushes on the edges of clay layers were prepared by atom transfer radical polymerization. X‐ray diffraction and thermogravimetric analysis results indicated that PS chains were grafted to the edges of clay platelets. Transmission electron microscope results showed that different morphologies of clay‐PS particles could be obtained in different solvents. In water, clay‐PS particles aggregated together, in which PS chains collapsed forming nanosized hydrophobic domains and hydrophilic clay faces stayed in aqueous phase. In toluene, clay‐PS particles formed face‐to‐face structure. Narrowly dispersed PS colloidal particles stabilized by clay‐PS were prepared by suspension polymerization. Because of the negatively charged clay particles on the surface, the zeta potential of the PS colloidal particles was negative. Positively charged poly(2‐vinyl pyridine) (P2VP) chains were adsorbed to the surface of PS colloidal particles in aqueous solution at a low pH value, and gold nanoparticles were prepared in P2VP brushes. Such colloidal particles may find important applications in a variety of fields including waterborne adhesives, paints, catalysis of chemical reactions, and protein separation. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1535–1543, 2009     

Pickering emulsion polymerization of graphene oxide-stabilized styrene

Polystyrene (PS) particles were prepared via Pickering emulsion polymerization using graphene oxide (GO) as the stabilizer. The results show that pH is an important factor in the stability of Pickering emulsions. The effects of two different phase initiators, the water phase initiator potassium persulfate and the oil phase initiator azobisisobutyronitrile, on the morphology of PS particles in Pickering emulsion polymerization had been investigated in detail. Wrinkled particles were prepared using the water phase initiator, and spherical particles were prepared using the oil phase initiator. In addition, hexadecane was used as the auxiliary stabilizer in the polymerization, which narrowed the diameter distribution of the PS spheres, and the hollow PS spheres were fabricated. The size of the GO particles also influenced the final morphology of the particles. Nano-sized polymer particles were grafted onto the surface of micro-sized GO. Small GO particles were suitable for Pickering emulsion polymerization to prepare the composite particles. The thermogravimetric analysis of the prepared particles confirmed that they were PS/GO composite particles, which could have a wide range of potential applications, such as in catalysts, sensors, environmental remediation, and energy storage.     

Synthesis of polystyrene nanoparticles “armoured” with nanodimensional graphene oxide sheets by miniemulsion polymerization

Polystyrene particles “armoured” with nanosized graphene oxide (GO) sheets have been prepared by aqueous miniemulsion polymerization of styrene, exploiting the amphiphilic properties of GO in the absence of conventional surfactants. The nanoscale GO sheets were prepared from graphite nanofibers of diameter approximately 100 nm based on a novel procedure, thus effectively ensuring the absence of larger sheets. Polymerization proceeded to high conversion with minor coagulation, with final number‐average particle diameters of approximately 500 nm, but relatively broad particle size distributions. Scanning electron microscopy analysis revealed particles with a textured surface, consistent with the expected morphology. Interestingly, analysis of GO sheets recovered from the polymerization revealed that the GO sheets are partially reduced during the polymerization—approximately 50% of the initial carboxyl groups of the GO were lost, consistent with some loss in colloidal stability at high conversion. The overall approach offers a convenient and attractive synthetic route to novel graphene‐based polymeric nanostructures. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis,characterization and optical properties of graphene oxide–polystyrene nanocomposites

The synthesis of graphene oxide (GO)–polystyrene (PS) Pickering emulsions, as environment‐friendly nanostructures suitable for novel applications, has received significant attention in recent years. In this work, the synthesis and characterization of GO–PS nanocomposites through seeded emulsion polymerization and the selective light reflection properties of dry films have been reported. Amphiphilic molecule sulfonated 3‐pentadecyl phenol was used as a co‐surfactant to stabilize GO dispersions during the emulsion polymerization process. The particle size of the dispersions as measured by dynamic light scattering decreases from 540 nm, for PS without any GO, to 88 nm with 1 wt% GO content. Scanning electron microscopy studies show a uniform size distribution of the composite particles prepared with GO. The dried films show a structural color that varies with the GO content. The self‐assembly behavior of the dried film was further studied using reflectance spectroscopy, which shows a red shift of the reflectance maximum from 440 to 538 nm as the GO loading was increased from 0.2 to 0.5 wt%, respectively, indicating a different microstructure. X‐ray diffraction, transmission electron microscopy (TEM) and atomic force microscopy (AFM) were used to study the morphology and structure of the composite particles on drying. The AFM study confirms the non‐spherical shape of the particles. Thermogravimetric analysis shows improved thermal decomposition characteristics of the nanocomposite films. Copyright © 2015 John Wiley & Sons, Ltd.     

Silica-graphene oxide hybrid composite particles and their electroresponsive characteristics

Silica-graphene oxide (Si-GO) hybrid composite particles were prepared by the hydrolysis of tetraethyl orthosilicate (TEOS) in the presence of hydrophilic GO obtained from a modified Hummers method. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images provided visible evidence of the silica nanoparticles grafted on the surface of GO, resulting in Si-GO hybrid composite particles. Energy dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD) spectra indicated the coexistence of silica and GO in the composite particles. The Si-GO hybrid composite particles showed better thermal stability than that of GO according to thermogravimetric analysis (TGA). The electrorheological (ER) characteristics of the Si-GO hybrid composite based ER fluid were examined further by optical microscopy and a rotational rheometer in controlled shear rate mode under various electric field strengths. Shear stress curves were fitted using both conventional Bingham model and a constitutive Cho-Choi-Jhon model. The polarizability and relaxation time of the ER fluid from dielectric spectra measured using an LCR meter showed a good correlation with its ER characteristics.     

Synthesis and characterization of positively charged,alumina‐coated silica/polystyrene hybrid nanoparticles via pickering miniemulsion polymerization

Positively charged, raspberry‐like hybrid nanoparticles, consisting of a polystyrene core and an alumina‐coated silica shell were successfully prepared in a surfactant free system via the radical copolymerization of styrene (St) and different comonomers (acrylic acid, methacrylic acid, and acrylamide) by using a cationic silica sol as the sole emulsifier in Pickering miniemulsion polymerization. The influence of different parameters like pH of the dispersion, comonomer content, and the amount and size of silica nanoparticles on the colloidal stability of the systems, prepared with different comonomers, was examined. The particles' morphology was observed via high‐resolution scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The removal of free silica particles via centrifugation was proved by TEM and SEM, and the content of free and adsorbed silica was quantified via thermogravimetric analysis (TGA). © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Preparation and characterization of emulsifier-free core–shell interpenetrating polymer network-fluorinated polyacrylate latex particles

The emulsifier-free core–shell interpenetrating polymer network (IPN) fluorinated polyacrylate latex particles with fluorine rich in shell were prepared by emulsifier-free seeded emulsion polymerization with water as the reaction medium. The fluorinated copolymer could be fixed on the particle surface due to the formation of interpenetrating polymer network. The resultant core–shell particles were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic light scattering (DLS) analysis, Fourier transform infrared (FTIR) spectrometry, X-ray photoelectron spectroscopy (XPS) analysis and thermogravimetric analysis (TGA). The core–shell particles possessed very narrow monomodal particle size distributions. XPS analysis of the latex film displayed that perfluoroalkyl groups had the tendency to enrich at surface and there was a gradient concentration of fluorine in the structure of the latex film from the film–air interface to the film–glass interface. In addition, compared with the latex film of crosslinked polyacrylate prepared under the same condition, the emulsifier-free core–shell IPN-fluorinated polyacrylate latex film showed better thermal stability, higher contact angle and lower water uptake.     

Synthesis of raspberry‐like organic–inorganic hybrid nanocapsules via pickering miniemulsion polymerization: Colloidal stability and morphology

Raspberry‐like hybrid nanocapsules with a hydrophobic liquid core were successfully prepared via the copolymerization of styrene, divinylbenzene (DVB), and 4‐vinyl pyridine (4‐VP) in Pickering‐stabilized miniemulsions by using silica particles as the sole emulsifier and hexadecane (HD) as liquid template. When compared with conventional Pickering miniemulsions and Pickering suspensions, the colloidal stability of the current systems is much more sensitive to the variation of reaction parameters such as pH, size, amount of silica particles, and content of 4‐VP. The systems without coagulum were only obtained in a narrow pH range at around 9.5 and by using 12 nm silica particles as emulsifier. The formation of well‐defined raspberry‐like capsules was confirmed by transmission electron microscopy (TEM) and high‐resolution scanning electron microscopy (HRSEM). The stable attachment of silica particles on the surface of hybrid particles was verified by centrifugation and subsequent characterizations, such as Fourier transform infrared spectroscopy, TEM, and HRSEM. The influence of pH and weight content of HD, DVB, and 4‐VP on the particle morphology was extensively investigated. Interestingly, the particle morphology strongly depends on the particle size. When compared with the organic surface‐active surfactant, the formation of capsule morphology could be promoted by the application of silica particles taking advantage of their surface inactivity. The formation mechanisms of capsules/solid particles are discussed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis of worm-like superparamagnetic P(St-AA)@Fe3O4/SiO2 Janus composite particles

Novel Janus nanocomposite particles with superparamagnetic P(St-AA)@Fe₃O₄ seed microspheres as head and worm-like SiO₂ as body were successfully prepared. The effects of different variables such as the amount of cetyltrimethyl ammonium bromide (CTAB), tetraethyl orthosilicate (TEOS), and ammonia and the composition of inorganic precursors and surfactants on the morphologies of final particles were studied by transmission electron microscopy (TEM) and field-emission scanning electron microscopy (SEM). Due to the amphiphilic difference between the two parts as well as their special morphologies, the fabricated worm-like particles could be applied to stabilize oil/water mixtures even if owing relative hydrophilic properties that might provide a new category of functional solid surfactants in Pickering emulsions and the fabrication of hierarchical materials.     

The Formation of Large‐Area Conducting Graphene‐Like Platelets

The treatment of a suspension of graphite oxide (GO) with sodium azide leads to a material that, after reduction, features amino groups at the top and bottom of the sheets. These groups react through microcontact printing with an isothiocyanate monolayer on a silicon oxide substrate to form covalent bonds that strongly attach to the particles on the surface. With ultrasonication it is possible to obtain exfoliation of the sheets that are not covalently bound to the surface leaving single‐layer platelets attached to the substrate. The azido derivative can be also used to functionalize the graphene oxide with long alkylic chains through a click chemistry approach. This functionalization results in the exfoliation of this material in dimethylformamide. The novel materials were fully characterized by different techniques including IR spectroscopy, thermogravimetric analysis (TGA), scanning and transmission electron microscopy (SEM and TEM), X‐Ray photoelectron spectroscopy (XPS), and solid state NMR spectroscopy. The material with amino groups, after the reduction step, is conductive with a resistivity only approximately seven times larger than that of unprocessed graphite. This implies that after reduction of the GO, the conjugated sp² network is largely restored. We consider this to be an important step towards a chemical approach for forming conducting large‐area platelet films of single‐layer graphene.     

颗粒模板法制备大孔Al2O3材料

采用颗粒模板法制备了大孔氧化铝(Al2O3)材料. 扫描电子显微镜(SEM)结果显示, 大孔Al2O3结构中的大孔呈“囊泡状”且孔道的贯通性较差. Zeta电位测量表明, 共沉积条件下聚苯乙烯(PS)和Al2O3两种胶体颗粒带有相反的电荷, 在静电引力作用下先发生了吸附, 再沉积在一起. 吸附在PS微球表面的Al2O3纳米颗粒形成的吸附层是导致大孔呈“囊泡状”和孔道不贯通的主要原因. 采用聚二烯丙基二甲基氯化铵(PD)溶液对PS胶体微球带电性质进行了改性, PS微球的Zeta电位由−44.36 mV变成了+37.41 mV, 进而消除了沉积过程中二元颗粒间的吸附现象. 扫描电子显微镜显示, 大孔样品中“囊泡状”大孔消失, 同时孔道贯通性得到改善.     

改性聚苯乙烯微球的制备及其胶体晶体的组装

采用甲基丙烯酸改性的无皂乳液聚合方法制备了尺寸为210 nm、含羧基的聚苯乙烯(PS)微球，用红外光谱、透射电子显微镜和粒度分析仪对其形状和结构进行分析，结果表明，经甲基丙烯酸改性后得到了表面为高密度电荷的单分散性PS微球.用垂直沉积法快速制备出在较大范围(大于1 cm2)呈现很好有序性的密排结构聚苯乙烯胶体晶体薄膜，其在590 nm波长处存在光子带隙.在电子显微镜下，观察到这种胶体晶体是面心立方(fcc)密排结构.     

pH-responsive aqueous foams stabilized by hairy latex particles

Polystyrene (PS) latex particles carrying pH-responsive poly[2-(diethylamino)ethyl methacrylate] (PDEA) hair (PDEA-PS particles) were synthesized by dispersion polymerization and characterized in terms of diameter, diameter distribution, morphology, chemical composition, surface chemistry, and pH-response using scanning electron microscopy (SEM), elemental microanalysis, (1)H nuclear magnetic resonance spectroscopy, the laser diffraction method, and zeta potential measurements. The hairy particles can act as pH-responsive stabilizers of aqueous foams by adsorption at the air-water surface. Above pH 8.0, where particles have nonprotonated PDEA hair, which is relatively hydrophobic, particle-stabilized foams are stable for at least 1 month. Optical microscopy and SEM confirmed that flocculated PDEA-PS latex particles were adsorbed at the air-water interface and stabilized the aqueous foams. At pH 6.1 and 7.1, relatively stable foams can be prepared that remain stable for at least 24 h. SEM studies indicated that the PDEA-PS particles were adsorbed at the air-water interface as a monolayer at pH 6.1. At pH 5.1 and 3.1, where the particles have cationic water-soluble PDEA hairs with hydrophilic character, no foam was formed. Rapid defoamation can be induced by lowering the solution pH; the addition of acid caused the in situ protonation of 2-(diethylamino)ethyl methacrylate residues, which impart water-soluble hydrophilic character to the PDEA hair, and the PDEA-PS particles desorbed from the air-water interface. The foaming and defoaming cycles could be repeated at least five times.     

Synthesis and characterization of emulsifier-free trilayer core–shell polysilsesquioxane/polyacrylate/poly(fluorinated acrylate) hybrid latex particles

The trilayer core–shell polysilsesquioxane/polyacrylate/poly(fluorinated acrylate) (PSQ/PA/PFA) hybrid latex particles are successfully prepared, using functional PSQ latex particles with reactive methacryloxypropyl groups synthesized by the hydrolysis and polycondensation of (3-methacryloxypropyl)trimethoxysilane in the presence of a reactive emulsifier as seeds. Transmission electron microscopy (TEM), scanning electron microscopy (SEM) and dynamic light scattering (DLS) confirm that the resultant hybrid latex particles have evident trilayer core–shell structure and a narrow size distribution. The Fourier transform infrared (FTIR) spectra show that fluorinated acrylate monomers are effectively involved in the emulsion copolymerization and formed the fluorine-containing hybrid latex particles. XPS analysis of the obtained hybrid latex film reveals that the intensity of fluorine signal in the film–air interface is higher than that in the film–glass interface. In addition, compared with pure polyacrylate latex film, the obtained fluorine-containing hybrid film shows higher hydrophobicity and thermal stability, and lower surface free energy.     

Preparation of uniform silica/polypyrrole core/shell microspheres and polypyrrole hollow microspheres by the template of modified silica particles using different modified agents

Silica/polypyrrole (PPY) core/shell microspheres and PPY hollow microspheres were prepared by the template of silica particles whose surface character was modified with different modified agents. The morphology and structure of the particles were characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Elemental analysis and X-ray photoelectron spectroscopy (XPS) were carried out to characterize the structure of PPY hollow microspheres. We investigated the effect of different modified agents on the surface character of silica particles and the effect of surface character of silica particles on the morphology of PPY hollow microspheres. The effect of reaction conditions on the size of core/shell particles and hollow particles was also studied.     

Fabrication of core/shell hybrid organic–inorganic polymer microspheres via Pickering emulsion polymerization using laponite nanoparticles

Oil-in-water (o/w) emulsions of styrene, as monomer oil in water, were achieved successfully via Pickering emulsification with laponite nanoparticles as the sole inorganic stabilizers. The formed emulsions showed excellent stability not only against droplets coalescence (before polymerization) but also against microparticles coagulation (after polymerization). Generally, the number of composite polystyrene microparticles (PS) increased and their sizes decreased with the content of solid nanoparticles used in stabilizing the precursor o/w emulsions. This is consistent with the formation of rigid layer(s) of the inorganic nanoparticles around the PS microparticles thus a better stability was achieved. The composite microparticles were characterized using various techniques such as surface charge, stability, transmission electron microscope (TEM), scanning electron microscope (SEM) and Fourier transform infra-red (FT-IR). Coating films of the prepared latexes were applied to flat glass surfaces and showed reasonable adhesion compared to PS latex particles prepared with conventional surfactants. The effect of employed conditions on the features of the resulting emulsions in terms of stability and particle size has been discussed.     

Latex and hollow particles of reactive polypyrrole: preparation, properties, and decoration by gold nanospheres

Polypyrrole-coated polystyrene latex particles bearing reactive N-amino functional groups (PS-PPyNH2) were prepared by the in-situ copolymerization of pyrrole (Py) and the active amino-functionalized pyrrole (PyNH2) in the presence of 1.33 microm-diameter polystyrene (PS) latex particles. These particles were prepared by dispersion polymerization of styrene using poly(N-vinylpyrrolidone), PNVP, as a steric stabilizer. The functionalized polypyrrole-coated PS particles (PS-PPyNH2) were characterized in terms of their particle size and surface morphology using transmission electron microscopy (TEM). Infrared and X-ray photoelectron spectroscopy (XPS) detected pyrrole-NH2 repeat units at the surface of the latex particles, indicating that this monomer had indeed copolymerized with pyrrole. The core-shell structure of the PS-PPyNH2 particles was confirmed by etching the polystyrene core in THF, leading to the formation of hollow conducting polymer capsules. The PS-PPyNH2 particles were then decorated with citrate-stabilized gold nanoparticles via electrostatic interactions. Furthermore, etching of the polystyrene core resulted in the formation of gold-decorated PPyNH2 hollow capsules.     

Selective surface reactions for Janus ORMOSIL particles with multiple functional groups using an ordered monolayer film at liquid-liquid interface

Monodispersed, submicron-sized Janus ORMOSIL particles with multiple functional groups were prepared by the selective surface reaction of a monolayer film formed at a hexane-water interface. A well-ordered monolayer film was obtained by self-assembly of ORMOSIL particles with multiple functional groups at hexane-water interface. The photopolymerization of an ordered monolayer containing ORMOSIL particles yields a rigid film strong enough to maintain its integrity for transfer and further chemical reaction. The chemical reaction of this ordered film with organic and inorganic functional groups produced Janus ORMOSIL particles with multiple functional groups. The morphologies, structures, and chemical compositions of monolayer films and Janus ORMOSIL particles were characterized by FT-IR, solid state NMR, X-ray diffraction (XRD), optical microscopy (OM), electron microscopies (SEM and TEM), and confocal laser scanning microscopy.