Preparation of polyacrylamide/silica composite capsules by inverse Pickering emulsion polymerization

Polyacrylamide/silica(PAM/SiO_2) composite capsules were synthesized by inverse Pickering emulsion polymerization.Silica nanoparticles modified with methacryloxypropyltrimethoxysilane(MPS) were used as a stabilizer.Transmission electron microscopy(TEM),scanning electron microscopy(SEM),Fourier transform infrared(FT1R) spectroscopy,and thermal gravimetric analysis(TGA) were used to characterize the morphology and composition of the composite capsules.SEM and TEM images showed that capsules consisted of a particle shell and a polymer inner layer.The capsule size depends on the nanoparticle concentration in the continuous phase.The composite rigidity largely depends on the acrylamide concentration.FTIR and TGA results indicated the existence of polyacrylamide and SiO_2 in the composite particles.Aqueous Hg(Ⅱ) removal testing by the PAM/SiO_2 composite capsules indicated promising potential for removing heavy metal ions from wastewater.     

Preparation and characterization of LiAl_xCo_yNi_1-x-yO₂ particles

Lithium-aluminum-cobalt-nickel oxide LiAlxCoyNi1xyO2 particles, generally used as cathode of lithium battery, were prepared by chemical coprecipitation from an aqueous solution of LiOH, Al(NO3)3, Co(NO3)2 and Ni(NO3)2 with NH4OH. XRD, SEM and FTIR were used to examine the effect of nickel content on the product. FTIR patterns showed that increase in nickel content decreased the absorption strength of the peak of spinel structure of the product, attributed to the occupation by nickel in the aluminum sites. Particle size and electrical properties of the lithium-aluminum-cobalt-nickel oxide (abbreviated as LACNO) particles were also determined.     

Preparation of polyacrylamide/silica composite capsules by inverse Picketing emulsion polymerization

Polyacrylamide/silica （PAM/SiO2） composite capsules were synthesized by inverse Pickering emulsion polymerization. Silica nanoparticles modified with methacryloxypropyltrimethoxysilane （MPS） were used as a stabilizer. Transmission electron microscopy （TEM）, scanning electron microscopy （SEM）. Fourier transform infrared （FTIR） spectroscopy, and thermal gravimetric analysis （TGA） were used to characterize the morphology and composition of the composite capsules. SEM and TEM images showed that capsules consisted of a particle shell and a polymer inner layer. The capsule size depends on the nanoparticle concentration in the continuous phase. The composite rigidity largely depends on the acrylamide concentration. FTIR and TGA results indicated the existence of polyacrylamide and SiO2 in the composite particles. Aqueous Hg（ll） removal testing by the PAM/SiO2 composite capsules indicated promising potential for removing heavy metal ions from wastewater.     

MULTI-SCALE STRUCTURES IN EMULSION AND MICROSPHERE COMPLEX SYSTEMS

Multi-scale structures involved in emulsion and microsphere complex systems are presented and discussed. The stability and spatio-temporal structures of emulsions, as well as nano-structures formed on the surface of microspheres after polymerization, are affected by the molecular emulsifier/stabilizer structures and the adsorbed emul-sifier/stabilizer nano-structures on the oil/water interface. The broad size distribution and variation of surface features of droplets are responsible for variations of the adsorbed emulsifier/stabilizer structures and the stability of the emulsions. On the other hand, preparation of a uniformly sized emulsion and employment of a combined emulsifier/stabilizer system can preserve the stability of the emulsions and microspheres. The above phenomena should be modeled by a multi-scale method, In order to maintain the stability of individual emulsion systems and realize the desired nano-structures of microspheres by choosing adequate emulsifier/stabilizer and experimental parameters.     

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-coacrylonitrile） （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.     

Key synthesis of magnetic Janus nanoparticles using a modified facile method

Inorganic/organic poly（methylmethacrylate-acrylic acid-divinylbenzene） iron oxide Janus magnetic nanoparticles（P（MMA-AA-DVB）/Fe3O4） with strong magnetic domains and unique surface functionalities were prepared using a solvothermal process.The P（MMA-AA-DVB） nanoparticles were prepared via soapfree emulsion polymerization and used as a precursor for preparing Janus nanoparticles.The morphology and magnetic properties of the magnetic Janus nanoparticles formed were characterized using a laser particle size analyzer,transmission electron microscopy,Fourier transform infrared spectroscopy,vibrating sample magnetometry,and thermogravimetric analysis.The synthesized P（MMA-AA-DVB）/Fe3O4 magnetic Janus nanoparticles were characterized by a Janus structure and possessed a stable asymmetric morphology after being dually functionalized.The particle size,magnetic content,and magnetic domain of the P（MMA-AA-DVB）/Fe3O4 magnetic Janus nanoparticles were 200 nm,40%,and 25 emu/g,respectively.The formation mechanism of the Janus nanoparticles was also investigated,and the results revealed that the reduction of Fe3＋ ions and growth of Fe3O4 took place on the surface of the P（MMA-AA-DVB） polymeric precursor particles.The size of the Janus particles could be controlled by narrowing the size distribution of the P（MMA-AA-DVB） precursor nanoparticles.     

EFFECTS OF SURFACTANT AND ACID TYPE ON PREPARATION OF CHITOSAN MICROCAPSULES

Chitosan microcapsules were prepared by a method involving emulsification and crosslinking. The effectsof surfactants and acid type for dissolving chitosan on the characteristics of chitosan microcapsules were investigated.The results showed that the mixed surfactant consisting of Span80 and Tween60 had an obvious effect on reducing the size of the microcapsules. The two-surfactant complex, formed on the basis of hydrogen bonding, strengthened the interfacial membrane in the emulsion, thus decreasing not only the size of the microcapsules but also the coalescence of dispersed chitosan liquid drops. In the case of monoacid such as hydrochloric acid or acetic acid for dissolving chitosan,the chitosan microcapsules obtained were spherical in shape with smooth surfaces. For diacids or triacid, the chitosanmicrocapsules obtained were also spherical, but their surfaces were covered by folds and crinkles. The number of carboxyl groups in the acids used influenced the chemical crosslinking between chitosan and the crosslinker (glutaraldehyde) as well as the morphology of the particles. For diacids or triacid, physical crosslinking occured due to electrostatic force, accompanied by substantial decrease of covalent crosslinking, leading to decreased strength of the microcapsules as shown by the collapse of microcapsule walls and the formation of multiple folds and cnnkles on their surfaces.     

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.     

Fabrication of submicron barium sulfate aggregates in the presence of ethylenediaminetetraacetic acid anions

Barium sulfate aggregates with an average size of 0.5 μm were synthesized at pH 7,directed by ethylenediaminetetraacetic acid(EDTA) anions.The particle morphology,chemical composition,and size distribution of the BaSO_4 aggregates were characterized.The as-synthesized BaSO_4 particles were spherical and comprised many interconnected nanoballs,of which the surface properties were affected by the EDTA anions.The adsorption of EDTA anions reversed the charge and weakened the surface polarity of BaSO_4,instigating the formation of aggregates by a self-assembly and transformation process.The resulting BaSO_4 particles at pH 9-10 were ellipsoidal and featured smooth surfaces.Based on the zeta potential of BaSO_4,variations in the morphology induced by changes in pH were closely related to the adsorption of mono- and multi-valent anions onto the electrical double layer of BaSO_4.     

SYNTHESIS OF MESOPOROUS TiO_2 MATERIALS WITH HIGH SPECIFIC AREA USING INORGANIC ACIDS AS CATALYSTS

This paper presents a synthesis process for preparing mesoporous titanium dioxide materials in the absence of any templates and using inorganic acids as catalysts. Tetrabutyl titanate was used as the precursor at ambient temperature, and four different inorganic acids, i.e., hydrochloric, nitric, sulfuric and phosphoric, were used as catalysts. The as-prepared mesoporous TiO2 materials were characterized by SEM, XRD and nitrogen adsorption/desorption measurements. The influences of different inorganic acids on the properties of TiO2 were discussed and compared in details. Experiments showed that the inorganic acids have significant effects on the surface area, pore volume, pore size, and pore size distribution of the products. The mesoporous TiO2 materials catalyzed by phosphoric acid exhibited the largest specific surface area and largest pore volume with narrow pore size distribution. Vacuum and infrared drying methods tested in the process were found to have subtle impact on the structure of the TiO2 materials prepared.     

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.     

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.     

PTFE@SiO2核壳型添加剂在不同实验条件下的水润滑性能

采用原位聚合法制备了聚四氟乙烯@二氧化硅(PTFE@SiO₂)复合粒子. 利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、粒径分布仪以及傅立叶红外光谱仪(FTIR)对复合粒子的形貌、粒径分布和组成结构进行了分析. 结果表明:所制备的复合粒子呈核壳型复合结构,粒子尺寸处于亚微米级别. 分散性试验表明:该粒子在水中具有良好的分散性和稳定性. 利用LSR-2M往复式摩擦磨损试验机测试了不同试验条件下复合粒子在水环境中的摩擦学性能,结果表明:在常温、0.019 m/s滑动速率以及0.2 μm的钢盘粗糙度下,PTFE@SiO₂润滑剂具有最佳的摩擦学性能;相比于纯水和添加了PTFE/SiO₂的润滑剂,其摩擦系数降低了近80%,磨损体积减小了1~2个数量级. 分析表明:PTFE@SiO₂复合粒子优异的水润滑性能主要与核壳结构的存在以及在摩擦过程中形成的高质量转移膜密切相关.      

Polymer nanoparticles with dendrimer-Ag shell and its application in catalysis

Polymer nanoparticles with dendrimer-Ag shell were prepared and their application in catalytic reduction of 4-nitrophenol (4-NP) was investigated. Cross-linked polystyrene (PS) microspheres were prepared through dispersion copolymerization of styrene, acrylic acid and crosslinking monomer 1, 2-divinylbenzene. PS microspheres with average size of 450 nm and narrow size distribution were used as support for the immobilization of dendrimer-Ag shell. The polyamidoamine (PAMAM) dendrimer shell was successively grafted onto the surface of PS microspheres through repetitive Michael addition reaction of methyl acrylate (MA) and amidation of the obtained esters with large excess of ethylenediamine (EDA). Silver nanoparticles were formed directly inside the PAMAM shell through reduction with NaBH₄. The resulting PS@PAMAM-Ag nanoparticles were packed in a stainless steel column and used successfully for catalytic reduction of 4-NP. This technique for packing catalytic polymer particles in a column could improve the efficiency of using the metal catalyst and the tedious separation in catalytic reaction.     

Alginate-gelatin emulsion droplets for encapsulation of vitamin A by 3D printed microfluidics

Microfluidics is characterized by the manipulation of fluids in submillimeter channels and has great application potential in encapsulation. To further extend the application of microfluidics in food industries, a 3D printed microfluidic device is used to encapsulate vitamin A and improve its stability. Two natural macromolecules, sodium alginate and gelatin, are added to water as the continuous phase to generate monodisperse emulsion. Under different flow rate ratios, the diameter of droplets decreases with the increase of continuous flow rate. However, at the same flow rate ratio, varying the dispersed and continuous flow rates does not significantly change the diameter and size distribution of emulsion collected. The prepared O/W (oil/water) single emulsion can form microgel particles and avoid degradation of vitamin A by simulated gastric acid; the encapsulated vitamin A will not be released until particles reach simulated intestinal tract. In the simulated digestion in vitro, no vitamin A is released for 2 h in the acidic environment; under an alkaline or neutral environment such as those in intestinal fluids, vitamin A can be released from the microgel particles within 2.5 h. Using the presented approach, emulsions encapsulating vitamin A have been prepared and can potentially be applied to encapsulate other oil-soluble substances in the food industry.     

Preparation and characterization of LiAlxCoyNi1-x-yO2 particles

Lithium-aluminum-cobalt-nickel oxide (LiAlxCoyNi1-x-yO2) particles, generally used as cathode of lithium battery, were prepared by chemical coprecipitation from an aqueous solution of LiOH, AI(NO3)3, Co(NO3)2 and Ni(NO3)2 with NH4OH. XRD, SEM and FTIR were used to examine the effect of nickel content on the product. FHR patterns showed that increase in nickel content decreased the absorption strength of the peak of spinel structure of the product, attributed to the occupation by nickel in the aluminum sites. Particle size and electrical properties of the lithium-aluminum-cobalt-nickel oxide (abbreviated as LACNO) particles were also determined.     

High-throughput generation of uniform droplets from parallel microchannel droplet generators and the preparation of polystyrene microsphere material

To prepare uniform polystyrene particles with ten microns of diameter, a parallel scaling-up strategy for the capillary-assembled stepwise microchannel was developed, which created uniform droplets with high-throughput and formed a large amount of emulsion templates for the polymerization of styrene and cross-linker. The microchannel droplet generator was robust for the flow rate deviation of the continuous phase in the jetting flow, and droplet generation frequency up to 2.8 × 10⁴ Hz was achieved with only four parallel droplet generators, which were much more efficient than the parallelly scaled microfluidic devices working in dripping flow. 32–52 μm average diameter droplets with 4.5%–8.4% diameter variation coefficients were successfully prepared from the microchannel device fabricated by low-cost 3D-print method, and the droplets were subsequently turned to solid particles via a two-step polymerization in the platform. The polystyrene particles were further reduced to 16.9–23.5 μm with 5.0%–8.6% diameter variation coefficients due to the accompanying emulsion polymerization, and the working capacity of the platform reached hundred milligrams of particles per hour.