Electrochemical activity of sulfur networks synthesized through RAFT polymerization

Novel results concerning the inverse vulcanization of sulfur using reversible addition–fragmentation chain transfer (RAFT) polymerization are here reported. It is shown that RAFT polymerization can be used to carry out this crosslinking process, with the additional possibility to extend the reaction time from a few minutes as with classical free radical polymerization (FRP) to several hours. Higher control on viscosity and processability of the synthesized networks, as well as, the implementation of semibatch feed policies during crosslinking are important advantages of the RAFT process here explored comparatively to the FRP inverse vulcanization. Using cyclic voltammetry, it was assessed the electrochemical activity of the synthesized sulfur‐rich polymer networks. It is shown that the fundamental electrochemical activity of the elemental sulfur was preserved in the produced materials. Testing of electrochemical cells assembled with lithium in the anode and different sulfur based materials in the cathode, including the synthesized RAFT networks, is also shown. The results here presented highlight the new opportunities introduced by reversible‐deactivation radical polymerization mechanisms on the control of the synthesis process and in the design of such advanced materials and show also that many potential derivatizing possibilities can be achieved. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43993.     

纳米氧化锌在抗菌材料中的应用

对抗菌材料及纳米ZnO进行了概述,并探究了纳米ZnO的抗菌机理和影响纳米ZnO抗菌性能的主要因素。将无机抗菌材料进行掺杂或复合改良是一种新型趋势,以纳米ZnO为无机抗菌剂制成的抗菌材料对于未来的应用发展具有广阔空间。     

RAFT聚合制备PMPS-b-PNIPAM嵌段共聚物及温敏性纳米粒子

利用可逆加成-断裂链转移(RAFT)活性自由基聚合合成了一系列分子量可控、分子量分布窄的甲基丙烯酸-3-三甲氧基硅丙酯(MPS)和N-异丙基丙烯酰胺(NIPAM)的嵌段共聚物，在水溶液中分散制备温敏性的含硅纳米粒子。保持疏水链段PMPS的长度恒定，改变亲水链段PNIPAM的长度，在不同pH的水溶液中进行实验，研究亲水链段长度、pH对聚合物的临界聚集浓度、纳米粒子的尺寸和形貌以及温度变化过程中的相分离行为的影响，得到尺寸较小、溶液稳定的温度响应性含硅纳米粒子，同时具有有机物和无机物的优良特点，在生物医学、化学催化、纳米反应器、染料涂料等多领域具有广泛的应用前景。     

Effect of cations and anions on properties of zinc oxide particles synthesized in supercritical water

Hydrothermal synthesis of zinc oxide fine particles from zinc salt (Zn(CH₃COO)₂, ZnSO₄, Zn(NO₃)₂) and alkali metal hydroxide (LiOH, KOH) aqueous solution was carried out with a Ti alloy batch reactor in supercritical water. Particle size synthesized in LiOH solution was relatively smaller than that in KOH. Emission spectra of the particle produced from ZnSO₄ and LiOH aqueous solution shows the highest intensity among these systems. Hydrothermal synthesis of zinc oxide fine particles from Zn(NO₃)₂ and LiOH solution was also carried out with a flow-through apparatus for continuous production and rapid heating of the starting solution to supercritical states. Nanoparticles having an average particle diameter of 16 nm was produced at 659 K and 30 MPa.     

pH- and temperature-responsive amphiphilic diblock copolymers of 4-vinylpyridine and oligoethyleneglycol methacrylate synthesized by RAFT polymerization

Diblock copolymers of 4-vinylpyridine (4VP) and oligoethyleneglycol methyl ether methacrylate (OEGMA) were synthesized for the first time using RAFT polymerization technique as potential drug delivery systems. Effects of the number of ethylene glycol units in OEGMA, chain length of hydrophobic P4VP block, pH, concentration and temperature on the solution behavior of the copolymers were investigated comprehensively. Copolymer chains formed micelles at pH values higher than 5 whereas unimeric polymers were observed to exist below pH 5, owing to the repulsion between positively charged P4VP blocks. The size of the micelles was dependent on the relative length of blocks, P4VP and POEGMA. Thermo-responsive properties of copolymers were investigated depending on the pH and length of P4VP block. The increase in the length of P4VP block decreased the LCST substantially at pH 7. At pH 3, LCST of copolymers shifted to higher temperatures due to the increased interaction of copolymers with water through positively charged P4VP block.     

撞击流反应-沉淀法制备纳米氧化锌

在浸没循环撞击流反应器中,以纯碱与硝酸锌反应-沉淀制得前驱体,经煅烧后得到纳米氧化锌产品。通过正交设计实验研究了Zn(NO3)2浓度、反应温度、反应时间、Na2CO3与Zn(NO3)2摩尔比等因素对产品收率的影响。初步确定了制备纳米氧化锌的最优工艺条件:Zn(NO3)2浓度1.5 mol/L,反应温度60℃,反应时间1 h,Na2CO3与Zn(NO3)2摩尔比1.3∶1;该条件下锌收率可达94%。制得的氧化锌产品经XRD表征,其纯度较高;经TEM表征,其形貌为球形或接近球形;在最优工艺条件下制取的产品平均粒径为20 nm。建立了相关工艺条件与产品收率的数学关系式。     

分散聚合法包覆无机纳米粒子的研究进展

综述了国内外分散聚合方法包覆无机纳米粒子的研究进展,包括包覆工艺、包覆机理、关键技术及发展趋势。重点分析了聚合温度、引发剂、单体、稳定剂类型和用量、分散介质、无机纳米粒子、包覆时间等因素对包覆效果的影响,结果表明,提高无机纳米粒子和聚合物的亲和性以及无机纳米粒子的分散性是分散聚合包覆无机纳米粒子的关键。     

Diameter control of ultrathin zinc oxide nanofibers synthesized by electrospinning

Electrospinning is a versatile technique, which can be used to generate nanofibers from a rich variety of materials. We investigate the variation of a zinc oxide (ZnO)-polyvinylpyrrolidone (PVP) composite structure in morphology by electrospinning from a series of mixture solutions of ZnO sol–gel and PVP. Calcination conditions for the crystallization of ZnO nanofibers and removal of the PVP component from the ZnO-PVP composite nanofibers were also studied. The progression of the ZnO-PVP composite structure from grains to nanofibers was observed, and ZnO-PVP nanofibers as thin as 29.9 ± 0.8 nm on average were successfully fabricated. The size of the resultant ZnO-PVP composite nanofibers was considerably affected by two parameters: the concentrations of zinc acetate and PVP in the precursor solution. The concentration of zinc acetate particularly influenced the diameter distribution of the ZnO-PVP nanofibers. The ZnO-PVP nanofibers could be subsequently converted into ZnO nanofibers of a pure wurtzite phase via calcination in air at 500°C for 2 h.     

Photoluminescence of zinc oxide nanopowder synthesized by a combustion method

Zinc oxide (ZnO) nanopowder was synthesized by a simple and quick combustion method using zinc nitrate as a precursor and glycine as a fuel material. The starting materials were mixed at room temperature and spontaneous ignition of which resulted into the ZnO nanopowder. The synthesized nanopowder was characterized by X-ray diffraction (XRD), scanning electronic microscope (SEM), Infrared (IR) spectrophotometer and spectroflurometer in order to study the structural, morphological, compositional and photoluminescence (PL) properties. The ZnO powder shows polycrystalline nature with preferential peak (101) having crystallite size 25 nm. A significant band at 532 cm⁻¹ in the IR spectrum corroborates the presence of characteristic band of ZnO. Room temperature photoluminescence spectrum of the synthesized nanopowder exhibits a dominant, sharp and strong ultraviolet (UV) emission with a suppressed deep-level emission indicating good crystal quality and optical properties.     

Investigation of polymer blends of polyamide-6 and poly(methyl methacrylate) synthesized by RAFT polymerization

Morphological and thermal properties of immiscible and incompatible polymer blends of commercial polyamide-6 (PA-6) and poly(methyl methacrylate) (PMMA) synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization have been studied in the presence of a compatibilizer consisting of either a random copolymer of styrene-maleic anhydride (SMA) or a diblock copolymer poly(methyl methacrylate) and polystyrene (PMMA-PS) also synthesized via RAFT polymerization. Blends of PA-6/PMMA were obtained by extrusion mixing. During melt compounding in the extruder, the functional groups of the polymer components were reacted in the presence of a compatibilizer, which changed considerably the morphology of the blend. After compatibilization, particles of PMMA in the PA-6 were smaller and better dispersed. The morphology and thermal properties of the blends were characterized using scanning electron microscopy (SEM) and differential scanning calorimetry (DCS).     

Templated synthesis of urchin-like zinc oxide particles by micro-combustion

Micro-combustion initiated by dielectric barrier discharge plasma has been applied for the removal of carbon template to prepare urchin-like ZnO particles. The combustion is operated at atmospheric pressure and low gas temperature (less than 150 °C), and the template is fully decomposed and rapidly removed. The obtained urchin-like ZnO possesses two distinct morphologies: nanosheets and sub-micro rods. The unique morphologies form on ZnO hexagonal nuclei with the template effect of activated carbon.     

Field emission characteristics of zinc oxide nanowires synthesized by vapor-solid process

Vertically aligned ZnO nanowire (NW) arrays have been synthesized on silicon substrates by chemical vapor deposition. The growth of ZnO NWs may be dominated by vapor-solid nucleation mechanism. Morphological, structural, optical, and field emission characteristics can be modified by varying the growth time. For growth time that reaches 120 min, the length and diameter of ZnO NWs are 1.5 μm and 350 nm, respectively, and they also show preferential growth orientation along the c-axis. Room-temperature photoluminescence spectra exhibit a sharp UV emission and broad green emission, and the enhanced UV-to-green emission ratio with increasing growth time might originate from the reduced concentration of surface defects. Furthermore, strong alignment and uniform distribution of ZnO NWs can also effectively enhance the antireflection to reach the average reflectance of 5.7% in the visible region. The field emission measurement indicated that the growth time plays an important role in density- and morphology-controlled ZnO NWs, and thus, ZnO NWs are expected to be used in versatile optoelectronic devices.     

氨法制取纳米氧化锌的粒径控制研究

为有效控制氨法制取纳米氧化锌的粒径,在蒸氨前将浸出原液用一定量的纯净水稀释,可增加初期沉淀生成的晶核数,使沉淀粒径更加均匀和细化,同时发现蒸氨残液不可以作为浸出原液的稀释剂回用.蒸氨的加热方式对纳米氧化锌的粒径也有影响,选择蒸汽直接加热,当溶液含锌质量浓度小于0.3 g/L时,所制取的纳米氧化锌粒径满足GB/T 19589-2004纳米氧化锌的要求 .     

纳米氧化锌表面修饰及其应用研究进展

纳米氧化锌（ZnO）是一种广泛使用的多功能材料。本文介绍了ZnO的性质和应用,并阐述了表面修饰的重要性。表面修饰会引起ZnO粒径、缺陷和表面化学性质变化。在对表面修饰方法作简单分类后,结合应用综述了表面修饰对ZnO光学性质、抗菌性、生物毒性以及对ZnO/聚合物纳米复合材料性质的影响,并从不同角度分析其原因。适当的表面修饰可提高ZnO的稳定性和分散性,增强其抗紫外、光催化、光致发光和抗菌性质,降低其毒性,并能调控和协调其性质,而不当的表面修饰会导致ZnO性质劣化。然而,要全面和准确地预测并实现表面修饰的优势效果仍面临较大挑战。在表面修饰剂和表面修饰方法的选择、表面修饰剂体系的建立、表面修饰机理及性能优化等方面还需要更深入系统的研究。     

In situ polarity functionalization and properties of styrenic triblock copolymers synthesized via RAFT emulsion polymerization

The in situ polarity functionalization of the styrenic triblock copolymers was accomplished via the block introduction of polar monomer, n‐butyl acrylate, with the help of reversible addition‐fragmentation chain transfer (RAFT) emulsion polymerization. The polarity functionalization, microphase separation, static and dynamic mechanical properties, water resistance, transparency, and thermal stability of the synthesized polarity‐functionalized triblock copolymers, polystyrene‐block‐poly(n‐butyl acrylate)‐block‐polystyrene (SAS), were extensively studied. The poly(n‐butyl acrylate) (PBA) middle block higher than 10 wt % has the favorable toughening effect on polystyrene (PSt) two‐end block due to the microphase separation in SAS. The glass transition of the continuous plastic phase (mainly composed of PSt block) has a much greater influence on the storage modulus than that of the dispersed rubber phase (mainly composed of PBA block). The polarity‐functionalized SAS has good water resistance, high transparency, and robust thermal stability. The polarity‐functionalized SAS will have such a potential application broadening as polar adhesive. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44603.     

Preparation and characterization of zinc hydroxide carbonate and porous zinc oxide particles

A simple urea aqueous solution process at low temperature (85 °C) was employed for the preparation of zinc hydroxide carbonate from zinc nitrate. The influence of different additives on the final particle morphology was studied. Porous spherical particles in the shape of chrysanthemums with an average size of 4 μm and a surface area of 16 m²/g were obtained in the presence of poly-vinyl pyrrolidone (PVP-K30). After heat treatment ZnO particles were formed that preserved the size and shape of the hydrozincite precursor. The morphology and crystallinity of the solids obtained before and after the heat treatment were characterized by FE-SEM, XRD, FTIR, BET and TG methods.     

纳米SiO_2包覆硼酸锌及其原位聚合PET的阻燃性能

在乙醇/水体系中,采用溶胶-凝胶法在硼酸锌(ZB)表面包覆纳米SiO_2对其进行改性,利用扫描电镜(SEM)和透射电镜(TEM)研究了H_2O/TEOS的摩尔比对SiO_2粒子大小及包覆效果的影响。然后利用原位共聚法制备出阻燃聚酯,研究了包覆后的硼酸锌对聚酯缩聚过程及阻燃性能的影响。结果表明:当体系原料H_2O/NH_3/TEOS的摩尔比为7.1:3.3:1时,SiO_2可以在硼酸锌表面形成致密的保护层,成功抑制了Zn离子对聚酯缩聚过程的催化效应。将包覆后的硼酸锌与阻燃剂2-羧乙基苯基次膦酸的乙二醇酯化液(CEPPA-EG)一起加入到聚酯聚合中,能发挥很好的协同作用,聚酯的阻燃性能得到明显提高,极限氧指数(LOI)值由22提高到35,UL-94等级由V-2级提高到V-0级,炭层石墨化程度明显增高。     

二氧化硅对纳米氧化锌热稳定性的影响

为了抑制纳米氧化锌的光催化活性,通过硅酸钠水解生成二氧化硅对氧化锌进行表面包覆。对包覆二氧化硅的纳米氧化锌进行热处理,研究了二氧化硅对纳米氧化锌热稳定性的影响。利用X射线衍射仪(XRD)、氮吸附仪和高分辨透射电子显微镜(HRTEM)对所得样品进行表征,并对纳米氧化锌的光稳定性进行评价。结果表明,合适的热处理温度为600℃,适当的热处理有助于提高包覆层的均匀性和致密性,而且在热处理过程中纳米氧化锌的晶粒生长得到了有效抑制。     

油基纳米氧化锌分散浆的制备及其流变特性

选用硬脂酸钠对ZnO进行表面湿法改性，以环十五硅氧烷硅油为溶剂，PEG-10聚二甲基硅氧烷为分散剂，通过机械球磨法制备了纳米ZnO分散浆。利用水接触角、热重、TEM和FTIR对纳米ZnO粉体进行表征。结果表明，硬脂酸钠改性后，粉体具有疏水性，且硬脂酸钠最佳包覆量为6%（以ZnO的质量计，下同）。硬脂酸钠包覆量为6%的疏水性纳米ZnO粉体，包覆层厚度约为2 nm，此时水接触角最大为145.4°。模拟防晒乳液的防晒性能测试中，纳米氧化锌分散浆的紫外屏蔽性能显著优于粉体。流变特性测试表明，分散浆为假塑性流体，流动曲线符合Ostwald-de Wale幂律方程，具有剪切稀化特性；分散浆的黏度低，触变性小，储存稳定性高；温度升高，黏度降低，配方生产中对温度的敏感程度较小 。