溶胶-凝胶模板法制备三维有序大孔TiO_2微球

采用无皂乳液聚合方法自制的单分散聚苯乙烯(PS)微球乳液为原料,并以PS微球自组装制备了有序胶体晶体模板("蛋白石"),采用溶胶-凝胶模板法制备了三维有序大孔TiO2微球("反蛋白石"),其孔呈六边形,孔径分布均一,约为200 nm,运用SEM,XRD对其形貌特征及晶型进行表征。结果表明,采用表面含有羧基的单分散聚苯乙烯微球及高的硅油粘度制得的模板有序度高;控制煅烧温度可以改变有序大孔TiO2微球的晶型,当煅烧温度为500℃时,其晶型为锐钛型,当煅烧温度为700℃时,其晶型则为金红石型。     

聚苯乙烯胶体晶体模板制备及在3DOM-SiO_2材料制备中应用

通过创新的方法制备聚苯乙烯（PS）胶体晶体,成功的制备出粒径在255nm左右的PS胶体晶体,并阐述了乳化剂用量对PS胶体晶体有序性排列的影响。用此PS胶体晶体为模板制备3DOM-SiO2材料,通过扫描电镜与透射电镜观察,SiO2大孔材料的孔径收缩率为10%左右,并且大孔SiO2在大面积范围内排列整齐有序,孔壁均匀致密光滑,是典型的三维有序大孔结构,3DOM-SiO2材料整体上呈面心立方体结构。     

单分散胶体颗粒的有序组装及其应用研究进展

本文综述了近1～2年来课题组在单分散胶体微球有序组装及其应用方面的研究进展.其中包括250～1300 nm宽尺寸范围单分散二氧化硅胶体微球的重力沉降自组织;旨在提高光子晶体折射率反差的TiO2/SiO2复合胶体微球的有序组装;硬模板与催化材料一步复合的二元胶体体系颗粒的有序自组装;一种高效的聚苯乙烯胶体颗粒的批量组装技术;低体积分数聚苯乙烯胶体晶体的制备;以及聚苯乙烯胶粒晶体作为可调谐三维非线性光子晶体在高开关对比的光子晶体光开关方面的应用,和作为制备有序大孔材料硬模板在大分子催化方面的应用等.     

等离子体增强化学气相沉积技术制备锗反蛋白石三维光子晶体

采用溶剂蒸发对流自组装法将单分散二氧化硅(SiO2)微球组装形成三维有序胶体晶体模板,以锗烷(GeH4)为先驱体气用等离子增强化学气相沉积法在350℃填充高折射率材料锗.获得了锗反蛋白石光子晶体.通过扫描电镜、X射线衍射仪对锗反蛋白石的形貌、成分、结构进行了表征.结果表明:锗在SiO2微球空隙内填充均匀,得到的锗为多晶态.锗反蛋白石光子晶体为三维有序多孔结构.等离子体增强化学气相沉积的潜在优势在于可实现材料的低温填充,从而以高分子材料为模板进行复型,得到多种结构的三维光子晶体.     

油性介质中组装二氧化硅胶体晶体薄膜

报道厂一种由粒径大于700nm的SiO2微球组装胶体晶体薄膜的方法。以一种密度较大的疏水性有机物替代水或醇类为分散剂,通过对SiO2微球表面进行疏水性处理改善其在油性介质中的分散性,采用改进的垂直沉积法在油性分散剂中制备SiO2胶体晶体。用扫描电子显微镜、红外光谱仪和紫外－可见光谱仪对SiO2胶体晶体薄膜的形貌、结构和光学性能进行了观察测试。结果表明;较大密度的分散剂能有效降低SiO2微球的沉降速度,组装成直径在700～2000nm范围的SiO2微球的胶体晶体。获得的SiO2光子晶体具有长程有序结构,并在近红外区具有显著的光子频率带隙。     

聚苯乙烯胶晶模板法制备三维有序大孔SiO2材料

以聚苯乙烯微球(polystyrene microsphere)自然沉积形成的胶体晶体作模板,将以正硅酸甲酯制备的SiO2溶胶填充到模板间隙中,原位形成凝胶,最后通过焙烧除去模板,得到三维有序大孔SiO2.通过SEM检测,观察到六方和四方2种有序的大孔排列方式.大孔孔径及孔径收缩率分别为240nm和19%.2种排列中,大孔之间由小窗口连通,构成三维有序大孔结构.XRD显示,制备的3DOM材料由无定形SiO2组成.     

单分散胶体颗粒的应用研究进展

综述了近年来重质油国家重点实验室在单分散SiO2胶体微球和单分散聚苯乙烯胶体微球方面的应用研究成果和进展.这些研究成果包括单分散胶体微球的组装、复合微球的制备和组装、二元胶体颗粒的组装、三维有序大孔材料的合成、重油大孔催化剂、有机/无机复合质子膜和纳米亚微米粒度标准物质等.     

以聚苯乙烯为模板制备有序大孔氧化铝

采用少皂乳液聚合法成功制备了单分散的聚苯乙烯微球,以微球自组装后的聚苯乙烯胶体晶体为大孔模板,铝溶胶为前驱体填充模板,干燥焙烧除去模板后制备了氧化铝载体。用激光粒度仪、扫描电镜、X射线衍射和氮气吸脱附对聚苯乙烯胶体晶体和氧化铝载体进行了表征。结果表明:少皂乳液聚合法制备的聚苯乙烯微球具有粒径较小(100~350 nm)、单分散性好(0.005)、收率高(约80%)等优点;自组装的胶体晶体呈规则有序排列,微球表面光滑洁净,并以此为模板成功制备了具有三维有序结构的、大孔孔径可调的氧化铝材料。     

高比表面积三维有序大孔炭材料的合成与表征

将粒径为540nm的SiO2胶体微球通过自然沉积组装为胶体晶体模板,以葡萄糖的水溶液为前体填充模板间隙,高温炭化后,以HF溶液溶去模板,得到三维有序大孔炭材料。根据SEM检测,大孔以六方有序的方式排列,其孔径及孔径收缩率分别为510nm和5.6%。大孔之间由小窗口连通,构成内部三维交联的大孔网络。低温N2吸附测试表明,大孔孔壁上存在2～10nm为主的中孔孔隙,同时由于前体的表面复制作用,使样品BET比表面积达到948m2/g。XRD表征显示,所制备的3DOM材料由无序石墨结构的炭质组成。     

单分散SiO2/Ag/SiO2核壳结构微球制备及自组装光子晶体

应用湿化学方法,在SiO2微球表面先后包覆5 nm银层、20 nm SiO2介质膜,制备了直径约300 nm的单分散SiO2/Ag/SiO2核壳结构微球.用提拉技术实现微球的自组装,获得了长程有序的面心立方结构排列的光子晶体,并研究了其光学性能.结果表明:在可见至近红外波段存在非完全光子带隙;SiO2/Ag/SiO2球体自组装成的光子晶体并非完全密堆排列.     

Surface characterization of nanoparticles carrying pH-responsive polymer hair

The surface of near-monodisperse colloidal polystyrene (PS) latex particles carrying pH-responsive poly[2-(diethylamino)ethyl methacrylate] (PDEA) polymer chains as a steric stabilizer has been extensively characterized in dry and wet states. X-ray photoelectron spectroscopy and contact angle measurement studies confirm that PDEA chains are located on the PS latex particle surface. Transmission electron microscopy (TEM) studies reveal that the sterically stabilized PS particles have a core-shell morphology and wet atomic force microscopy data confirm that the pH-responsive PDEA component covers the PS latex core and the thickness of the protonated steric polymer is estimated to be approximately 15 nm. The PS latex particles can be easily dispersed in acidic aqueous media (pH 3.0) whilst they flocculate in basic aqueous media (pH 10.0) due to the pH-responsive PDEA hair. This dispersion-flocculation cycle of the PS latex is fully reversible.     

Effect of the composition of structured rubber particles on the toughness of poly(methylmethacrylate)

Composite natural rubber (NR) and monodisperse poly(n-butylacrylate) (PBuA) based latex particles were tested as possible impact modifiers for a poly(methylmethacrylate) (PMMA) matrix. A continuous extrusion process was used for the incorporation of wet latexes directly into a twin-screw extruder. All latexes had been coated by a PMMA shell. Furthermore, polystyrene (PS) subinclusions were introduced into the NR core. The impact resistance of the prepared PMMA blends can be most effectively improved by NR particles containing a large weight fraction of compatibilising PMMA in the shell. The degree of crosslinking of the shell polymer has to be restricted. PBuA based latex particles of 180 nm in size are ineffective to toughen the PMMA matrix. The degree of grafting of the NR phase in core–shell particles containing PS subinclusions is not crucial. Scanning electron microscopy was used to analyse the failure processes in composite rubber particle toughened PMMA blends at fast (impact conditions) and slow (tensile testing) deformation speeds.     

Preparation of transparent polystyrene nano-latexes by an UV-induced routine emulsion polymerization

Transparent polystyrene (PS) latexes were prepared by photo-polymerization of a routine styrene (St) emulsion with a surfactant concentration of 0.4 wt% and a monomer concentration of 10 wt%, by using UV light as well as a hydrophilic photo-initiator. The entire polymerization could be performed within 1-2 h and display a conversion higher than 90%. The particle sizes could be tuned in the range of 20-40 nm. The formation mechanism for these of nano-sized latex particles was attributed to an in situ formation of PS chains with terminal hydroxyl groups. The presence of the hydroxyl-functionalized polymer chains seemed to promote a colloidal stability of the small latex particles and prevent coagulation even at low surfactant concentrations.     

Preparation of polystyrene–clay nanocomposites via dispersion polymerization using oligomeric styrene‐montmorillonite as stabilizer

This study describes the preparation of polystyrene–clay nanocomposite (PS‐nanocomposite) colloidal particles via free‐radical polymerization in dispersion. Montmorillonite clay (MMT) was pre‐modified using different concentrations of cationic styrene oligomeric (‘PS‐cationic’), and the subsequent modified PS‐MMT was used as stabilizer in the dispersion polymerization of styrene. The main objective of this study was to use the clay platelets as fillers to improve the thermal and mechanical properties of the final PS‐nanocomposites and as steric stabilizers in dispersion polymerization after modification with PS‐cationic. The correlation between the degree of clay modification and the morphology of the colloidal PS particles was investigated. The clay platelets were found to be encapsulated inside PS latex only when the clay surface was rendered highly hydrophobic, and stable polymer latex was obtained. The morphology of PS‐nanocomposite material (after film formation) was found to range from partially exfoliated to intercalated structure depending on the percentage of PS‐MMT loading. The impact of the modified clay loading on the monomer conversion, the polymer molecular weight, the thermal stability and the thermomechanical properties of the final PS‐nanocomposites was determined. Copyright © 2012 Society of Chemical Industry     

Monodisperse ellipsoidal polystyrene latex particles: Preparation and characterisation

An improved version of a novel method first employed by Nagy & Keller for the preparation of monodisperse ellipsoidal polystyrene latex particles is described. The method involves embedding monodisperse spherical polystyrene latex particles as starting material in a deformable polymer matrix such as poly(vinyl alcohol) and deforming these mechanically to various predetermined macroscopic draw ratios to give ellipsoids of various axial ratios. Ellipsoids with lengths ranging from about 350 to 12250nm were prepared. Stable aqueous dispersions of these were recovered and characterised with respect to particle size and axial ratio distributions and surface morphology using electron microscopy. Axial ratios ranging from 2.0 to 5.65 were obtained for the resulting ellipsoids. Various factors influencing the monodispersity of the resulting ellipsoids in the preparation method are discussed.     

Carboxylic acid-functionalized, core-shell polystyrene@polypyrrole microspheres as platforms for the attachment of CdS nanoparticles

Polypyrrole-coated polystyrene latex particles bearing N-carboxyl functional groups (PS@PPyCOOH) were prepared by the in-situ copolymerization of pyrrole (Py) and the active carboxyl-functionalized pyrrole (PyCOOH) in the presence of 390 nm diameter-sized polystyrene (PS) latex particles. Uncoated PS particles were prepared by emulsion polymerization of styrene. The initial comonomer fractions (in mol%) were 25/75, 50/50, 75/25 and 100/0 for pyrrole and PyCOOH, respectively. The PS@PPyCOOH_x particles, where x stands for the initial molar fraction of PyCOOH (x = 0, 25, 50 or 75%), were characterized in terms of particle size, surface morphology, chemical composition and electrochemical redox activity using transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), FTIR, TGA and cyclic voltammetry respectively. TEM showed an increase of the latex particle diameter after coating by the conducting polymer layer, from 390 nm for uncoated PS to 430 nm for PS@PPyCOOH₅₀ particles, allowing an estimation of the PPyCOOH shell thickness to 20 nm. FTIR and XPS detected PyCOOH 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@PPyCOOH_x particles was confirmed by etching the polystyrene core in THF, leading to the formation of hollow conducting polymer capsules. Positively charged CdS nanoparticles were electrostatically assembled onto the surface of PS@PPyCOOH₅₀ particles, as a function of pH. It was found that, contrarily to unfunctionalized PPy-coated latex particles, PS@PPyCOOH₅₀ particles could be evenly decorated with stabilized CdS nanoparticles, at pH 5.The films of the PS@PPyCOOH@CdS-coated ITO electrodes are shown to be electroactive and electrochemically stable.     

Composite polymeric particles with ZnS shells

We report on a preparation of hybrid particles with polymeric cores and ZnS shells. Two types of monodisperse sterically stabilized polystyrene particles with hydroxyl-terminated PEG chains (PS/PEGMA) or β-diketone groups (PS/AAEM) on the surface have been prepared and characterized. Formation of ZnS layer on the surface of submicron particles has been studied by SEM and EDX. Deposition of ZnS on the surface of PS/PEGMA particles is not uniform and leads to formation of ‘raspberry’ morphology with rough surface. It has been found that presence of β-diketone groups on the particle surface leads to formation of well-defined ZnS layers. It has been assumed that such effect is due to the complexation of Zn cations by β-diketone groups leading to nucleation and growth of ZnS crystals on the polymer particle surface. Polymeric particles were completely covered with ZnS if the loaded amount of inorganic material was higher then 40 wt%. The thickness of ZnS layer on the particle surface can be easily varied by changing the ZnS load (in present study maximal thickness of the ZnS shell was 70 nm). It has been found that increase of the ultrasound power leads to considerable increase of the ZnS deposition on the particle surface without strong changes of the particle morphology. Hybrid particles have been investigated with XRD technique and their optical properties were studied by UV-spectroscopy. The colloidal stability of obtained particles was studied by separation analyser. Sedimentation experiments indicate that colloidal stability of obtained composite particles depends strongly on loaded ZnS amount and pH value of the aqueous medium. It has been found that highest sedimentation velocities (or maximum of instability) were determined by ZnS loads, which provide complete coverage of the particle surface. Increase of the ZnS layer thickness led to better stability of hybrid particles in aqueous medium.     

Latex interpenetrating polymer networks based on high styrene resin

Latex interpenetrating polymer networks based on high styrene resin (“HSR300”) as seed latex and polystyrene as the second polymer have been synthesized in different compositional ratios. The morphology of resultant materials was determined by field emission electron microscopy, atomic force microscopy, transmission electron microscopy, and by dynamic mechanical analysis. A polystyrene (PS) rich shell is observed in the latex particles. At higher second polymer ratios, a PS‐rich shell can be resolved, but in general the majority of the polymer is incorporated as domains within each particle. The two crosslinked polymers are well intermeshed at the microscopic level, as reflected not only by morphology but also by single tan δ peaks in dynamic mechanical analysis (DMA) data. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 622–628, 1999     

STUDIES ON SYNTHESIS OF SILICA SOL-ORGANIC POLYMER COMPOSITE EMULSION

An emulsion of polystyrene/poly (butylacrylate-methyl methacrylate acrylic acid) core/shell latex particles (PS/P (BA-MMA-AA)) has been prepared by use of three synthetic methods. The effects of synthetic methods on the distribution of carboxyl groups in latex particles were studied. The results show that the seed emulsion polymerization in which the pre-emulsified monomers were added by dropping method to the second stage is the best technique for obtaining the optimum distribution of carboxyl groups on the surface of the latex particles. Furthermore, by using PS/P (BA-MMA-AA), a type of novel composite emulsion of silica sol-PS/P (BA-MMA-AA) was synthesized with the above method. By observation through transmission EM, the morphology of the latex particles obtained shows that a composite structure has been formed between silica sol particles and organic polymer particles.