A general synthesis for PEDOT-coated nonconductive materials and PEDOT hollow particles by aqueous chemical polymerization

A method for coating functionalized poly(3,4-ethylenedioxythiophene) (PEDOT) on nonconductive substrates in aqueous solution allows the deposition of PEDOT thin layers on various substrates, including silica and polystyrene (PS) nanoparticles, siliceous mesocellular foam, and chitosan-alginate fibers. The surface property is tuned by controlling the monomer composition in the aqueous solutions. Using appropriate organic solvents to remove the PS cores of PEDOT-coated PS nanoparticles, hollow PEDOT particles with single holes and PEDOT capsules can be formed.     

纳米TiO2改性及其掺杂聚苯乙烯性能的研究

为了增强无机化合物纳米TiO2的亲油性能,采用钛酸酯偶联剂LICA38对纳米TiO2表面进行预处理,并采用原位聚合工艺制备掺杂纳米Ti02的聚苯乙烯（PS）。采用DCA（dynamic contact angle）、XRD、FTIR、XPS、TEM等现代分析手段,对纳米TiO2预处理效果和掺杂材料的性能进行分析。结果表明,钛酸酯偶联剂在纳米TiO2的表面发生化学吸附,粒子的分散性提高,一定含量纳米TiO2的掺杂有助于提高PS的抗拉强度。     

羟基磷灰石/苯乙烯的原位(共)聚合

采用羟基磷灰石(HA)/苯乙烯(S t)原位聚合和HA/乙烯基三乙氧基硅烷(V S)/S t原位共聚合处理HA表面。研究结果表明,HA的存在对S t的聚合没有阻聚作用,PS在HA表面有明显的接枝效应,且原位共聚合较原位聚合更有利于PS的接枝。在原位(共)聚合过程中,聚合得到的PS的重均分子量均在30万以上。随着单体用量增加,PS的分子量呈增高的趋势、分子量分布趋于变窄,且原位共聚合所得PS的分子量比原位聚合所得PS的分子量高、分子量分布要窄。     

Grafting of polystyrene on nitrogen-doped multi-walled carbon nanotubes

Polymer grafting of polystyrene (PS) on nitrogen-doped multiwall carbon nanotubes (CNx) was successfully obtained by a "grafting from" technique. The production method involves the immobilization of initiators, using wet chemistry, onto the nanotube surface, followed by an in situ surface-initiated polymerization. The polymer-grafting carbon nanotubes synthesis includes the free radical functionalization of CNx and the "controlled/living" Nitroxide Mediated Radical Polymerization (NMRP). The obtained products were studied using several microscopic techniques as scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and electron energy loss spectroscopy (EELS). The characterization also includes thermogravimetric analysis (TGA), Raman spectroscopy, infrared spectroscopy, and electron spin resonance (ESR), among others. The analyzed samples were also compared with solutions fabricated by physical blending of the polymer and CNx nanotubes. These results indicate that the nanotube radical functionalization, the chemical grafting, and the polymerization reaction were obtained over CNx when NMRP method was successfully used, giving rise to a uniform PS layer of several nanometers grafted on the outer surface of the CNx nanotubes. Several properties of the PS-grafted CNx nanotubes were also studied. It is shown that the production method leads to a narrower distribution of the external diameters. Moreover, their solubilization in organic solvents is greatly improved. Finally, the dispersion of PS-grafted CNx into a PS matrix is studied to determine the differences in filler dispersion and interfacial adhesion strength, in comparison with nanocomposites elaborated with as-produced CNx.     

轻质高导电镀银复合粒子的制备研究

采用分散聚合工艺,以聚乙烯吡咯烷酮为分散剂,偶氟二异丁腈为引发剂,无水乙醇为分散介质,制备出粒径2.0μm、表面光滑、分散均匀的聚苯乙烯微球.将其进行表面磺化处理后运用化学镀工艺制备出了具有轻质高导电特性的聚苯乙烯/银复合粒子.对所制备的复合粒子进行了扫描电镜、红外光谱以及体积电阻率的测试.结果表明:所制备的复合粒子包覆均匀、导电性能良好;表面修饰提高了PS微球表面的电负性和亲水性并引入了磺酸基团,对PS微球表面镀银起到了重要作用;另外,随着PdCl2浓度和AgNO3/PS质量比的增加,复合粒子包覆完整性和导电性能都随之增加,最佳体积电阻率为1.61×10 -4Ω·cm.     

多孔高分子微球的制备研究

以苯乙烯、二乙烯苯为单体,引入混合溶剂作为致孔剂,采用悬浮聚合的方法制备了多孔交联聚苯乙烯微球,并通过有机萃取等方法带出致孔剂,形成永久性大孔.分析了搅拌速度、分散剂用量、致孔剂等因素对微球粒径分布和孔比表面积的影响,研究了不同工艺条件下的微球形态.结果表明,转速在180r/min左右,分散剂质量分数在0.15%左右时,可以制得粒径范围为0.2～0.8mm的聚苯乙烯微球,且微球具有良好的粒径分布.采用石蜡/甲苯、石蜡/乙酸乙酯为致孔剂时,可以形成纳米级小孔,且当石蜡/甲苯用量为86%时,孔比表面积可达到33.07m2/g,并随着交联剂用量的增加而增大.     

Improved mechanical properties of HIPS/hydroxyapatite composites by surface modification of hydroxyapatite via in-situ polymerization of styrene

High impact polystyrene (HIPS)/hydroxyapatite (HA) composites are potential biomaterials for bone replacements due to their good biocompatibility and adequate mechanical properties. At the present work, the surface of the micron-sized hydroxyapatite (HA) particles was modified by in situ polymerization of styrene (St), then compounded with HIPS. The effect of the modification of HA surface on morphology and mechanical properties of HIPS/HA composites were investigated. The results showed that the HA particles does not inhibit the polymerization of St. The PS segments coated on the HA surface by in situ polymerization of St enhances the compatibility between HA and HIPS, improves the dispersion of HA particles in HIPS matrix, and enhances the interfacial adhesion between HA and matrix. Thereby, the stiffness, tensile strength and notch impact strength of HIPS/HA composites are improved at the same time. And there is a critical coating thickness of PS on the HA surface for the optimum mechanical properties of HIPS/HA composites.     

Surface characteristics and photoactivity of silver-modified palygorskite clays coated with nanosized titanium dioxide particles

This paper presents the results of a study in which nanosized titanium dioxide (TiO₂) crystal particles were coated onto the surface of palygorskite fibrous clay which had been modified by silver ions using titanium tetrachloride as a precursor. Coated TiO₂ particles with the anatase structure were formed after calcining at 400 °C for 2 h in air. Various analytical techniques were used to characterize the surface properties of titanium dioxide particles on the palygorskite. Transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses showed that TiO₂ particles were supported on the surface of the palygorskite clays and their size was in the range of 3–6 nm. The titanium oxide coatings were found to be very active for the photocatalytic decomposition of methylene blue.     

Polyethylene/palygorskite nanocomposites with macromolecular comb structure via in situ polymerization

Polyethylene/palygorskite nanocomposites with “macromolecular comb” structure were prepared via in situ polymerization. The TiCl₄ catalyst was first loaded on the surface of the nanoscale whiskers of palygorskite. Subsequently the ethylene was introduced into the reaction system, and the polyethylene molecular chain was generated directly at the surface of the palygorskite whiskers. As a result, a polyethylene molecular chain with “macromolecular comb” structure was generated. The product thus obtained was blended with regular polyethylene to make a polymer blend, which was characterized by transmission electron microscope (TEM). Finely dispersed palygorskite whiskers in polyethylene matrix were found, which resulted in the improvement of mechanical strength of the polymer blends. Compared with regular polyethylene, the impact strength and tensile strength of the polymer blend were improved by 63.5% and 21.3% respectively at 25°C, when the palygorskite content of the nanocomposite was 20 wt%.     

Toughening of polystyrene by natural rubber-based composite particles: Part II Influence of the internal structure of PMMA and PS-grafted core-shell particles

This work was focused on the influence of the internal structure of natural rubber (NR)-based core-shell particles on the toughness of polystyrene (PS). Several emulsion polymerization processes were used to control the degree of grafting of the NR phase and the site of polymerization, which determines the final morphology of the prepared composite NR-based particles. PS subinclusions were introduced into the NR core in order to determine their influence on the deformation behaviour of PS. A continuous extrusion process was adapted for the direct feeding of the wet NR-based latexes into the molten PS matrix. Impact testing indicated that core-shell particles based on NR containing a large number of small crosslinked PS subinclusions toughened PS most effectively. A very effective toughening agent is obtained if a hard shell of 25 wt% crosslinked PMMA surrounds the composite rubber particle. Grafting of NR chains during the subinclusion synthesis has to be avoided since a high rubber particle modulus is detrimental for craze nucleation in PS. From the fracture surface morphology the craze nucleating and stabilizing efficiency of composite NR particles having different morphologies or grafting degrees could be deduced. This revised version was published online in November 2006 with corrections to the Cover Date.     

Preparation of multilayered organic-inorganic hybrid core-shell particles by stepwise surface formation

This paper introduces a stepwise formation method for micro-sized, multilayered core-shell particles comprising an inorganic core, organic inner shell, and inorganic outer shell. A silica core was coated with a polystyrene seed layer, followed by surface seed polymerization with styrene, to afford the inner shell. These particles were then coated with a silica outer shell by a surface sol-gel reaction with tetraethoxysilane. The versatility of this combined surface seed polymerization and sol-gel method is emphasized by the precise control achieved over particle diameter as well as shell thickness and count. Moreover, the organic inner shell can be readily eliminated to afford a single-core-containing micro-capsular structure.     

修饰纳米CdS/聚合物的界面相互作用与光学性能

采用微乳液法结合原位表面修饰合成了纳米尺度的硫化镉粒子,采用溶液共混和静态铺膜方法制备了纳米粒子/聚合物复合体系,以研究纳米粒子与聚合物间的界面作用.结果表明,经修饰的纳米CdS粒子比较均匀地分散于聚合物基体内,纳米粒子与聚合物基体间存在较强的相互作用.根据复合体系的紫外-可见吸收光谱和荧光光谱,分析了表面修饰(表面修饰剂种类、表面修饰剂用量等)对纳米粒子的分散以及复合体系界面特性的影响,证实了表面修饰剂具有促进纳米粒子分散和消除粒子表面缺陷的作用.     

Nanoparticles of latexes from commercial polystyrene

Nanoparticles of polystyrene (PS) (Mw = 1.0-3.0 x 10(6) g/mol) latexes have been successfully prepared from their respective dilute PS (commercial) solutions in cyclohexane, toluene/methanol, or cyclohexane/toluene at each theta temperature. The cationic surfactant cetyltrimethylammonium bromide (CTAB) was used to stabilize the formed PS latex particles. By varying different concentrations of CTAB and PS solution of various Mw, we have successfully produced, for the first time, stable bluish-transparent latex particles ranging from about 10 to 30 nm in diameter (Dw). The number of polymer chains per latex particle (np) is directly proportional to the volume occupied by each latex particle and hence associated to its Dw. The characteristics of these preformed PS latex particles are quite similar to those obtained from the microemulsion polymerization of styrene as reported in literature. These PS latex particles could be further grown by seeding polymerization of styrene to about 50 nm (Dw) with a monodisperse size distribution of Dw/Dn = 1.08.     

Advances in Ripplon Surface Laser-Light Scattering Measurement for Highly Viscous Polymer-Solvent System

The surface properties of a polymer organic-solvent system was measured using a ripplon surface laser-light scattering (SLLS) technique. The power spectrum (PS) of a ripplon can be obtained by fast Fourier transform (FFT) analysis of the beat signal of scattered light using ripplon SLLS. However, the PS peak shifts to lower frequencies due to the low surface tension of typical organic solvents. This shift means that the PS can be easily affected by external vibrational noise. In addition, higher viscosities broaden the shape of the spectra so that the peak becomes less clear. It is therefore difficult to find a definite peak frequency and to determine its width at half maximum for analyzing surface properties. To address these issues, a new system for SLLS was developed and was used to demonstrate that the available viscosity measurement range can be extended to the higher values needed for organic-solvent systems.     

超浓乳液界面引发制备核-壳粒子

利用超浓乳液界面引发制备疏水性核／亲水性壳的两性粒子,首先,通过超浓乳液聚合得到聚苯乙烯胶体粒子,作为疏水性的核,然后,通过界面引发使丙烯酰胺在核的表面聚合,形成亲水性的聚丙烯酰胺的壳层,界面引发体系由过氧化羟基导丙苯和硫酸亚铁组成,控制条件,可得到网孔（半包覆）,褶皱（全包覆）两种结构的壳层,核－壳间无化学键键连,无共聚物过渡层,另外,壳层孔的存在使得核层聚合物能与外界接触。     

PS／OMMT纳米复合材料作为润滑油添加剂的摩擦学性能

用乳液聚合法制备了聚苯乙烯/有机蒙脱土(PS/OMMT)纳米复合材料,并利用 XRD对其结构进行表征.利用四球机考察了纳米复合材料在AN 10油中的摩擦学性能,表明所合成的PS/OMMT纳米杂化材料能提高基础油的抗磨性能及承载能力,降低其摩擦系数;复合材料中OMMT含量对摩擦学性能影响很大.EDX能谱研究结果表明,在低负荷下PS/OMMT纳米复合材料在钢球表面铺展成膜,在高负荷下,聚合物分解,裸露出纳米结构的高度分散蒙脱土片层具有高活性,能在钢球的磨斑表面成膜,改善润滑油高负荷下的摩擦学性能.     

TiO2／PS复合粒子制备技术研究

本文首先通过优选表面活性剂和处理方式,实现了纳米TiO2粒子表面疏水处理,然后利用超声波的分散、粉碎、活化、引发等多重作用,在实现纳米TiO2粒子在反应介质中均匀分散的同时,引发苯乙烯（St）单体在纳米TiO2粒子表面进行分散聚合反应,最终制备出了TiO2／聚苯乙烯（TiO2／PS）复合粒子,并对其结构进行了表征。     

Robust fabrication of fluorine-free superhydrophobic steel mesh for efficient oil/water separation

A facile and environmentally friendly method was reported for the fabrication of superhydrophobic steel mesh by depositing with dual-scale Polystyrene@Silica (PS@SiO₂) particles coated with hexadecyltrimethoxysilane (HDTMS), which provided 3D multi-scale hierarchical rough surface structure with low surface energy to perform the superhydrophobic effect. PS particles of ~1 μm and ~200 nm were first synthesized via dispersion polymerization and emulsion polymerization, respectively. The obtained PS particles were then used as template for the silification using tetraethyl orthosilicate as the precursor. After treated with HDTMS, the PS@SiO₂ particles were deposited on steel mesh forming dual-sized hierarchical structures. The as-prepared film exhibited excellent water repellence with a water contact angle of 161.6° ± 1.1° and water contact angle hysteresis of 3.4°. It also showed efficient and rapid oil/water separation ability and could be repeatedly used for at least 5 times. This facile synthesis strategy for fabricating multifunctional steel mesh provides potential applications in large-scale oil–water separation.     

Toughening of polystyrene by natural rubber-based composite particles: Part I Impact reinforcement by PMMA and PS grafted core-shell particles

This work was focused on the influence of the morphology of composite natural rubber (NR)-based particles on the toughness of polystyrene (PS). Emulsion polymerization processes were used to adjust the microstructure of the latex particles. In order to be suitable for the reinforcement of PS, the NR-based particles were coated with a shell of crosslinked polymethyl methacrylate (PMMA) or PS. Furthermore, PS subinclusions were introduced into the natural core. A continuous extrusion process was adapted for the incorporation of these natural rubber based impact modifiers into thermoplastics. High deformation speeds (impact testing) were necessary in order to evaluate the mechanical properties of PS blends with a series of the prepared structured latexes. PS could only be toughened by core-shell particles. A PMMA shell proved to be advantageous because it is easier to produce by emulsion polymerization than a hydrophobic PS shell. Pre-vulcanized NR-based particles, which do not cavitate easily, were ineffective. Core-shell particles based on NR-containing PS subinclusions toughened PS more effectively. Solid NR particles caused premature craze and polymer fracture, as the rubber particles break down, debond from the matrix and form large voids at the craze/particle interface. Scanning electron microscopy (SEM) of Izod fracture surfaces showed clearly the cavities of debonded solid rubber particles and demonstrated that subinclusions within the rubber core permitted a larger volume of plastic deformation before failure. This revised version was published online in November 2006 with corrections to the Cover Date.     

Surface reaction of LiCoO2/Li system under high-voltage conditions by X-ray spectroscopy and two-dimensional correlation spectroscopy (2D-COS)

We studied the surface reactions of a LiCoO(2)/Li cell under high-voltage conditions using X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and two-dimensional correlation spectroscopy (2D-COS). 2D XPS correlation spectra show that Li(2)CO(3) is formed first by decomposition of the organic solvents, and then polycarbonate, which is formed by polymerization of the electrolytes, is produced on the cathode surface of the LiCoO(2)/Li system under high-voltage conditions. XAS measurements also confirm that the solid electrolyte interface (SEI) layer is formed on the LiCoO(2) electrode by decomposition of the organic solvents. The thickness of the SEI layer is less than 100 ?.