Soluble network polymers based on trifluoropropyl-substituted open-cage silsesquioxane: Synthesis,properties, and application for surface modifiers

Fluorinated completely condensed polyhedral oligomeric silsesquioxanes (F-CC-POSSs) are widely utilized as surface modifiers for polymeric materials because of their polyhedral and fluorine-rich structures, which generate polymers with lower surface energies under molecular-level control. In contrast, their derivatives, fluorinated incompletely condensed or open-cage POSSs (F-IC-POSSs), have similarly intriguing structures, but their utilization for polymer synthesis remains undeveloped. Herein, fluorinated network polymers were prepared based on a 3,3,3-trifluoropropyl-substituted IC-POSSs via hydrosilylation polymerization with isobutyl- and phenyl-substituted IC-POSS under optimized conditions. In addition to their good thermal stability and tunable refractive indices, these polymers exhibited solution processability and their casting films showed excellent optical transparency, indicating their potential for constructing fluorinated polymers. Their utilization as surface modifiers was examined by addition to poly(methylmethacrylate) (PMMA) films. Intriguingly, modified PMMA films with 2.0 and 0.5 wt% addition showed similar hydrophobicity and surface energies to the films prepared with only fluorinated network polymers.     

Polypropylene plasticization and photodegradation with a TiO2/poly(ethylene oxide)/methyl linoleate paint photocatalyst system

The photodegradation of polypropylene (PP) film was performed by a TiO₂/polyethylene oxide (PEO)/plant oil paint photocatalyst system. The photodegradation underwent two stages of development as follows: Initially PP reacted with linoleic acid radical originated from the photoreaction of plant oil component. Second, the linoleic acid graft‐polymer was decomposed, and then PP chain scission was caused. The process was studied using methyl linoleate (ML) in detail. The melting point of the 24 h‐photodegraded PP slightly decreased, and those of the 48 h‐ and 96 h‐ones drastically did as compared with the pristine PP. The crystallinity (χ_c) decreased at the 48 h photodegradation time and drastically increased at the 96 h one. The 24 h‐photodegraded PP showed the 77% Young's modulus, 88% tensile strength, and 103% strain at break values to those of the pristine PP. The ML graft‐polymerization and decomposition brought about the PP plasticizing and chemi‐crystallization, causing the PP degradation. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39909.     

Bioaugmented membrane bioreactor (MBR) with a GAC-packed zone for high rate textile wastewater treatment

The long-term performance of a bioaugmented membrane bioreactor (MBR) containing a GAC-packed anaerobic zone for treatment of textile wastewater containing structurally different azo dyes was observed. A unique feeding strategy, consistent with the mode of evolution of separate waste streams in textile plants, was adopted to make the best use of the GAC-zone for dye removal. Dye was introduced through the GAC-zone while the rest of the colorless media was simultaneously fed through the aerobic zone. Preliminary experiments confirmed the importance of coupling the GAC-amended anaerobic zone to the aerobic MBR and also evidenced the efficacy of the adopted feeding strategy. Following this, the robustness of the process under gradually increasing dye-loading was tested. The respective average dye concentrations (mg/L) in the sample from GAC-zone and the membrane-permeate under dye-loadings of 0.1 and 1 g/L.d were as follows: GAC-zone (3, 105), permeate (0, 5). TOC concentration in membrane-permeate for the aforementioned loadings were 3 and 54 mg/L, respectively. Stable decoloration along with significant TOC removal during a period of over 7 months under extremely high dye-loadings demonstrated the superiority of the proposed hybrid process.     

Well‐Defined Functional Linear Aliphatic Diblock Copolyethers: A Versatile Linear Aliphatic Polyether Platform for Selective Functionalizations and Various Nanostructures

Low‐temperature anionic ring‐opening homopolymerizations and copolymerizations of two glycidol derivatives (allyl glycidyl ether (AGE) and ethoxyethyl glycidyl ether (EEGE)) are studied using a metal‐free catalyst system, 3‐phenyl‐1‐propanol (PPA) (an initiator) and 1‐tert‐butyl‐4,4,4‐tris(dimethylamino)‐2,2‐bis[tris‐(dimethylamino)phosphoranylidenamino]‐2Λ⁵,4Λ⁵‐catenadi(phosphazene) (t‐Bu‐P₄) (a promoter) in order to obtain well‐defined functional linear polyethers and diblock copolymers. With the aid of the catalyst system, AGE is found to successfully undergo anionic ring‐opening polymerization (ROP) even at room temperature (low reaction temperature) without any side reactions, producing well‐defined linear AGE‐homopolymer in a unimodal narrow molecular weight distribution. Under the same conditions, EEGE also undergoes polymerization, producing a linear EEGE‐homopolymer in a unimodal narrow molecular‐weight distribution. In this case, however, a side reaction (i.e., chain‐transfer reaction) is found to occur at low levels during the early stages of polymerization. The chemical properties of the monomers in the context of the homopolymerization reactions are considered in the design of a protocol used to synthesize well‐defined linear diblock copolyethers with a variety of compositions. The approach, anionic polymerization via the sequential step feed of AGE and EEGE as the first and second monomers, is found to be free from side reactions at room temperature. Each block of the obtained linear diblock copolymers undergoes selective deprotection to permit further chemical modification for selective functionalization. In addition, thermal properties and structures of the polymers and their post‐modification products are examined. Overall, this study demonstrates that a low‐temperature metal‐free anionic ROP using the PPA/t‐Bu‐P₄ catalyst system is suitable for the production of well‐defined linear AGE‐homopolymers and their diblock copolymers with the EEGE monomer, which are versatile and selectively functionalizable linear aliphatic polyether platforms for a variety of post‐modifications, nanostructures, and their applications.     

Characterization by Stm and Electrical Conductivity of Single-Walled Carbon Nanotubes

Abstract

Single-walled carbon nanotubes (SWCNT) prepared by a DC-Arc-Discharge and purified by a hydrothermal treatment followed by several steps of procedures including heating, burning, extracting and acid-washing are investigated by a conventional STM technique morphologically and spectroscopically. The electical resistivities of compacted pellets (mats) of SWCNT are measured as a function of temperature in the range from the room-temperature to 1.5K. The behaviors seems to be essentially originated in the metallic nature of individual SWCNT.     

苏州多层住宅建筑生命周期评价

依据美国开发的BEES软件,选择张家港当地某一栋具体的多层住宅建筑(6层,每层大约750 m2)进行了生命周期评价.把建筑的全生命周期范围确定为建材准备阶段(包括原材科开采、运输、原材料加工等)、建造阶段、运行阶段(运行70年)、拆毁阶段和建筑垃圾处理阶段.依据确定的范围进行了清单分析.根据建筑的结构形式,计算得到各种建材的需求量和建造、运行、拆毁、建筑垃圾处理时的各种输入输出,以统一的功能单位(一栋建筑)合并各种输入输出数据,得到总的数据清单.采用BEES分类表征方法进行影响评价.根据我国的具体情况确定环境影响因子和类别(酸雨、全球变暖、资源枯竭等),将不同的环境影响因子分配到一个或多个环境影响类别中,再根据具体情况确定各指标的权重系数进行加权,得到综合的评价结果.找出了建筑物全生命周期阶段中产生环境影响最大的阶段,即运行阶段.     

Electrochemical properties of N-doped hydrogenated amorphous carbon films fabricated by plasma-enhanced chemical vapor deposition methods

Nitrogen-doped hydrogenated amorphous carbon thin films (a-C:N:H, N-doped DLC) were synthesized with microwave-assisted plasma-enhanced chemical vapor deposition widely used for DLC coating such as the inner surface of PET bottles. The electrochemical properties of N-doped DLC surfaces that can be useful in the application as an electrochemical sensor were investigated. N-doped DLC was easily fabricated using the vapor of nitrogen contained hydrocarbon as carbon and nitrogen source. A N/C ratio of resulting N-doped DLC films was 0.08 and atomic ratio of sp³/sp²-bonded carbons was 25/75. The electrical resistivity and optical gap were 0.695 Ω cm and 0.38 eV, respectively. N-doped DLC thin film was found to be an ideal polarizable electrode material with physical stability and chemical inertness. The film has a wide working potential range over 3 V, low double-layer capacitance, and high resistance to electrochemically induced corrosion in strong acid media, which were the same level as those for boron-doped diamond (BDD). The charge transfer rates for the inorganic redox species, Fe^2+/3+ and Fe(CN)₆^4−/3− at N-doped DLC were sufficiently high. The redox reaction of Ce^2+/3+ with standard potential higher than H₂O/O₂ were observed due to the wider potential window. At N-doped DLC, the change of the kinetics of Fe(CN)₆^3−/4− by surface oxidation is different from that at BDD. The rate of Fe(CN)₆^3−/4− was not varied before and after oxidative treatment on N-doped DLC includes sp² carbons, which indicates high durability of the electrochemical activity against surface oxidation.     

In situ binary sol–gel reaction of various trifunctional alkoxysilane in the silane‐grafted polyolefin matrix and its effect upon the mechanical properties

The vinyltrimethoxysilane‐grafted ethylene‐propylene copolymer/trifunctional methoxysilane (EPR‐g‐VTMS/RTMS) composites were prepared via in situ silica sol–gel reactions. Five trifunctional methoxysilane compounds (n‐hexyltrimethoxysilane, n‐decyltrimethoxysilane, n‐tetradecyltrimethoxysilane, n‐octadecyltrimethoxysilane, and phenyltrimethoxysilane) have been selected for this study. The water‐cross‐linked EPR‐g‐VTMS/RTMS composites were characterized by attenuated total reflectance‐Fourier transform infrared spectroscopy, gel content, solid‐state ²⁹Si CP/MAS NMR, wide‐angle x‐ray scattering, tensile strength, and field emission scanning electron microscopy measurements. The type of RTMS additive has a substantial influence on the nature of siloxane band networks and eventually the mechanical tensile properties. This finding suggests that the interaction and/or entanglement between the EPR‐g‐VTMS matrix and the substituent of the RTMS additives are crucial for the modifying mechanical properties. Moreover, for the water‐cross‐linked EPR‐g‐VTMS/CnTMS (n = 6, 10, 14, and 18) composites, the joint evidence provided by attenuated total reflectance‐Fourier transform infrared spectroscopy, ²⁹Si CP/MAS NMR, and wide‐angle x‐ray scattering results suggested the formation of ladder‐type poly(n‐alkyl silsesquioxane)s and the presence of the highly ordered structure with a thickness equal to the length of two n‐alkyl groups in all‐trans conformation. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers.     

Facile one-step route to polyaniline–silver nanocomposite particles and their application as a colored particulate emulsifier

Polyaniline–silver nanocomposites were synthesized in the form of colloidal particles by the facile one-step aqueous chemical oxidative dispersion polymerization of aniline using silver nitrate as an oxidant and poly(vinyl alcohol) as a colloidal stabilizer. Aniline monomer was oxidized by silver ions, yielding polyaniline and elemental Ag simultaneously. The synthesized nanocomposite particles were colloidally stable over 2 years and transmission electron microscopy studies indicated the production of spherical, plate and rod-shaped polyaniline–silver nanocomposite particles with a silver core–polyaniline shell morphology. The conductivity of a pressed pellet of the nanocomposite particles using the conventional four-point probe technique was 1.4 × 10^?2 S/cm at 25 °C. The nanocomposite particles behaved as a ‘colored’ particulate emulsifier for the stabilization of transparent oil-in-water emulsions.