Ultrahigh Molecular mass Polyethylene/ Carbon Nanotube CompositesCrystallization and melting properties

Ultrahigh molecular mass polyethylene (UHMMPE) is filled with carbon nano-tubes (CNTs) by solution in the presence of maleic anhydride grafted styrene-(ethylene-co-butylene)-styrene copolymer (MA-SEBS) as a compatibilizer. The UHMMPE/CNT composites crystallized from melt were prepared at a cooling rate of 20°C min^-1. The melting and crystallization behaviors of UHMMPE/ CNT composites were investigated by differential scanning calorimetry. The results showed that onset melting temperature (T _m) and degree of crystallinity (X _c) of UHMMPE/CNT composites crystallized from solution are higher than those from melt due to the larger crystalline lamellar thickness. The onset crystallization temperature (T _c) of UHMMPE/CNT composites tends to shift to higher temperature region with increasing CNT content in the composites. Tm and Tc of UHMMPE phase in UHMMPE/CNT composites decrease with the addition of MA-SEBS. Moreover, the crystallization rate of UHMMPE phase in UHMMPE/CNT composite is increased due to the introduction of CNTs. MA-SEBS acts as compatilizer, enhances the dispersion of CNTs in the UHMMPE matrix. Thereby, the crystallization rate of UHMMPE phase in UHMMPE/CNT composite is further increased with the addition of MA-SEBS. This revised version was published online in August 2006 with corrections to the Cover Date.     

Preparation and characterization of polyaniline-containing Na-AlMCM-41 as composite material with semiconductor behavior

Composite material formed from a mesoporous aluminosilicate, Na-AlMCM-41, with conducting polyaniline (PANI) has been synthesized by an in situ polymerization technique. Studies of aniline adsorption over mesoporous Na-AlMCM-41 synthesized in our laboratory allowed us to find the modes in which aniline interacts with the active sites of Na-AlMCM-41. In order to obtain the best reaction conditions to polymerize aniline onto Na-AlMCM-41, aniline was first polymerized to produce pure PANI. Hence, the oxidative in situ polymerization was carried out by two procedures, differing in the polymerization time and in static or stirring conditions. Studies of infrared spectroscopy and UV-vis spectroscopy indicated that higher polymerization time and static conditions allowed us to obtain mainly polyaniline in emeraldine form on the host. The N(2) isotherm of the polyaniline/Na-AlMCM-41 composite (PANI/MCM) indicated that the shape was similar to that of MCM, but the shift to saturation transition to lower partial pressure shows that the channels are occupied by PANI and they are now narrowed. The thermal properties of PANI, Na-AlMCM-41, and composite were investigated by TGA analyses and we found that the polymer shows higher thermal stability when it is forming the composite. Scanning electron microscopy indicated that PANI is not on the outer surface of the host. Conductivity studies show that PANI/Na-AlMCM-41 exhibits semiconductor behavior at room temperature and its conductivity was 7.0 x 10(-5) S/cm, smaller than that of pure polyaniline. PANI/Na-AlMCM-41 conductivity shows an increase as temperature increases. Magnetic measurements at room temperature confirmed that the composite has paramagnetic behavior; at lower temperatures the composite became diamagnetic.     

Morphology and thermal properties of conductive polyaniline/polyamide composite films

Polyaniline (PANI) in an emeraldine‐base form, synthesized by chemical oxidation polymerization, was doped with camphor sulfonic acid (CSA). The conducting complex (PANI–CSA) and a matrix, polyamide‐66, polyamide‐11, or polyamide‐1010, were dissolved in a mixed solvent, and the blend solution was dropped onto glass and dried for the preparation of PANI/polyamide composite films. The conductivity of the films ranged from 10^?7 to 10⁰ S/cm when the weight fraction of PANI–CSA in the matrices changed from 0.01 to 0.09, and the percolation threshold was about 2 wt %. The morphology of the composite films before and after etching was studied with scanning electron microscopy, and the thermal properties of the composite films were monitored with differential scanning calorimetry. The results indicated that the morphology of the blend systems was in a globular form. The addition of PANI–CSA to the films resulted in a decrease in the melting temperature of the composite films and also affected the crystallinity of the blend systems. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2531–2538, 2002     

静电纺丝制备Tb-PEG+Eu-PEG/PANI/PAN荧光导电相变三功能复合纤维

以聚丙烯腈(PAN)为载体基质、 以铕-聚乙二醇(Eu-PEG)和铽-聚乙二醇(Tb-PEG)为相变荧光材料, 加入掺杂的导电聚苯胺(PANI), 采用静电纺丝技术制得Tb-PEG+Eu-PEG/PANI/PAN复合纤维. 采用扫描电子显微镜(SEM)、 荧光光谱(FL) 仪、 差示扫描量热(DSC)仪及宽频介电松驰谱(BDS)仪等方法对相变荧光导电复合纤维的性能进行分析. 研究结果表明, 复合纤维具备良好的荧光、 相变及导电性能. 在294 nm紫外光激发下, 通过调节Tb-PEG和Eu-PEG的质量比可调节复合纤维的发光强度和颜色, 同时复合纤维的相变温度在5467 ℃之间. 复合纤维的电导率达到10^-6 S/cm, 随着PANI含量的增加, 电导率和介电常数增加. 通过调节Tb-PEG, Eu-PEG和PANI的比例及PEG的分子量, 可以实现复合纤维荧光、 导电及相变性能的可控调整.     

聚苯胺/凹凸棒石纳米纤维复合材料对溶液中痕量Cr(VI)的吸附性能

采用原位聚合法合成了盐酸掺杂聚苯胺/凹凸棒石黏土(PANI/ATP)纳米纤维复合材料。 研究了它对含痕量Cr(Ⅵ)废水的吸附,考察了物料配比、投料质量、吸附时间、吸附温度和pH值对其吸附性能的影响。 结果表明,复合材料中的物料配比为m(An)∶m(ATP)=2∶1,用量为0.4 g,50 min时对Cr(Ⅵ)的吸附量达到99.8%,符合Langmuir等温吸附方程。 该复合材料充分发挥了有机和无机吸附材料的协同作用,具有成本低、再生性能良好的特点。     

原位溶液聚合聚苯胺与聚苯乙烯溶液共混复合材料的制备及表征

以DNSA掺杂剂,在醇(或酮)-水介质中采用原位溶液聚合法制备出了聚苯胺,以溶液共混法制备出了聚苯胺/聚苯乙烯复合材料,采用红外光谱、热失重、元素分析、扫描电镜对产物进行了表征。结果显示：掺杂的聚苯胺电导率最高为0.65 S/cm,优于常用的DBSA,具有一定实用价值和理论意义。该复合材料表面电阻率最低为101Ω/□数量级,并在一定范围内可调,可用于电磁屏蔽,适合于聚合物表面使用。     

Conductive composite of polyaniline and tungsten carbide

Conductive polyaniline/tungsten carbide (PANI/TC) composite was synthesized via polymerization of the aniline monomer by (NH₄)₂S₂O₈/H₂SO₄ oxidant system in the presence of an aqueous suspension of TC. The structure, thermal stability and conductivity of PANI/TC composite were studied and the results were also compared with the pure PANI. The results showed that there was a strong interaction between the TC particles and PANI molecular chains. The crystalline structure of TC remained undisturbed upon with interaction with PANI chains. The thermal stability of PANI/TC composite was better than that of pure PANI. The direct current conductivity values of PANI/TC composite decreased slowly as the temperature increased from 25 to 165°C and PANI/TC composite exhibited significantly higher conductivity than the pure PANI.     

TiO_2聚苯胺复合膜的光电化学

利用电化学方法制备了TiO2 聚苯胺 (PANI)复合膜 .该膜具有比TiO2 或PANI膜更宽的吸收谱区 ,并且不同于利用聚苯胺光敏化的TiO2 膜 ,表现为两者复合材料膜的性质 .扫描电镜图表明 ,TiO2 微粒不完全覆盖着PANI膜 .根据TiO2 微粒光电流谱带的阈值能可得复盖在部分氧化态聚苯胺膜上的TiO2 微粒的禁带宽度为 3.0eV .部分氧化态聚苯胺膜的光电流谱遵循Fowler定律 ( 1/2 ～hυ成线性 ) .通过Fowler图得出部分氧化态聚苯胺的绝缘母体禁带宽度为 3.33eV ,并证实该绝缘母体为还原态聚苯胺 .从Mott Schottky图得到在 0 .0 5mol/LK3Fe(CN) 6 /K4 Fe(CN) 6 溶液中 (pH =8.52 )部分氧化态聚苯胺的平带电位为 0 .13V ,掺杂浓度为 5.3× 10 18cm- 3;TiO2 PANI复合膜的平带电位为 - 0 .6 5V ,掺杂浓度为 9.1× 10 19cm- 3.解释了TiO2 PANI复合膜的光电化学过程并描绘出其能带图 .利用TiO2 PANI复合膜能够有效地光降解苯酚溶液 .     

Structure of Composite Films Containing Polyaniline Studied by DSC

A structural study of conductive composite films consisting of ethylene-co-vinylacetate (EVA) copolymer, polyaniline (PANI) and dodecylbenzenesulfonic acid (DBSA), a part of which being complexed with PANI, was performed by using differential scanning calorimetry (DSC) and presented for the first time. An additional crystalline phase is formed during the film formation by thickening EVA chain-folded lamellae with participation of‘free’ DBSA molecules at lower net PANI content (up to 5 mass%) and of both ‘free’ and complexed DBSA molecules (up to 7.5 mass%). At higher PANI content PANI-DBSA complex starts to form its own crystals and at 17.5 mass% of PANI mixed crystals of EVA with ‘free’ DBSA alkyl chains are preferably formed. It is also found that the Fox' equation correlating the glass transition temperature of a miscible blend system with its composition can be actually used in estimating the miscibility of EVA/PANI blends no matter the presence of DBSA. This revised version was published online in August 2006 with corrections to the Cover Date.     

Multiple melting peak analysis with gel-spun ultra-high molar mass polyethylene

The multiple melting peaks observed on differential scanning calorimetry (DSC) of ultrahigh molar-mass polyethylene fibers (UHMMPE) are analyzed as a function of sample mass. Using modern DSC capable of recognizing single fibers of microgram size, it is shown that the multiple peaks are in part or completely due to sample packing. Loosely packed fibers fill the entire volume of the pan with rather large thermal resistance to heat flow. On melting, the fibers contract and flow to collect ultimately at the bottom of the pan. This process seems to be able to cause an artifact of multistage melting dependent on the properties of the fibers. A method is proposed to greatly reduce, or even eliminate, errors of this type. The crucial elements of the analysis of melting behavior and melting temperature are decreasing the sample size and packing the individual fibers in a proper geometry, or to introduce inert media to enhance heat transport.This work was supported by the Division of Materials Research, National Science Foundation, Polymers Program, Grant # DMR 90-00520 and the Division of Materials Sciences, Office of Basic Energy Sciences, US Department of Energy at Oak Ridge National Laboratory, managed by Lockheed Martin Energy Research Corp. for the US Department of Energy, under contract number DE-ACOS-96OR22464. Support for instrumentation came from TA Instruments, Inc. and Mettler-Toledo, research support was also given by ICI Paints.     

制备条件对PANI/PATP/Au和TiO_2-PANI/PATP/Au膜光电化学性能的影响

应用电化学方法在不同条件下制备聚苯胺 (PANI)膜和TiO2 -PANI复合膜 ,并对其光电化学性能进行研究 .实验表明 ,制备条件是影响膜光电化学性能的重要因素 .对氨基硫酚 (PATP)的组装有利于改善PANI膜的附着力 ;部分氧化态PANI膜的光电化学响应明显优于还原态和氧化态PANI膜的光电化学响应 ;部分氧化态PANI膜的厚度对其光电化学性能有一最佳值 ;热处理虽然有利于改善TiO2 的光电化学性能 ,但温度太高 ,将破坏PANI膜的表面结构 ,对于TiO2 -PANI复合膜有一最佳的热处理温度 .优化制备条件大可改善TiO2 -PANI复合膜和PANI膜的光电化学性能     

聚苯胺/二氧化钛复合薄膜的制备及其气敏性能

室温条件下, 运用静电力自组装和原位化学氧化聚合相结合的方法制备了聚苯胺/纳米二氧化钛(PANI/TiO2)复合薄膜和聚苯胺(PANI)薄膜, 并通过XPS和SEM对薄膜进行了分析表征. 采用平面叉指电极式器件制备了PANI/TiO2复合薄膜和PANI薄膜气体传感器, 研究了其在常温下对有毒气体NH3和CO 的敏感性能. 结果表明, PANI/TiO2复合薄膜较PANI薄膜具有更优的灵敏度和响应恢复特性.     

Electrically conductive,melt‐processed ternary blends of polyaniline/dodecylbenzene sulfonic acid,ethylene/vinyl acetate,and low‐density polyethylene

Although polyaniline (PANI) has high conductivity and relatively good environmental and thermal stability and is easily synthesized, the intractability of this intrinsically conducting polymer with a melting procedure prevents extensive applications. This work was designed to process PANI with a melting blend method with current thermoplastic polymers. PANI in an emeraldine base form was plasticized and doped with dodecylbenzene sulfonic acid (DBSA) to prepare a conductive complex (PANI–DBSA). PANI–DBSA, low‐density polyethylene (LDPE), and an ethylene/vinyl acetate copolymer (EVA) were blended in a twin‐rotor mixer. The blending procedure was monitored, including the changes in the temperature, torque moment, and work. As expected, the conductivity of ternary PANI–DBSA/LDPE/EVA was higher by one order of magnitude than that of binary PANI–DBSA/LDPE, and this was attributed to the PANI–DBSA phase being preferentially located in the EVA phase. An investigation of the morphology of the polymer blends with high‐resolution optical microscopy indicated that PANI–DBSA formed a conducting network at a high concentration of PANI–DBSA. The thermal and crystalline properties of the polymer blends were measured with differential scanning calorimetry. The mechanical properties were also measured. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3750–3758, 2004     

Preparation and characterization of PVC/PANI conductive composite with extremely low percolation threshold

Aniline was polymerized in the presence of poly(vinyl chloride) (PVC) powders in hydrochloric acid to in situ prepare poly(vinyl chloride)/polyaniline (PVC/PANI) composite particles. UV‐vis spectra and FT‐IR spectra indicate PANI in PVC/PANI composite particles possessed a higher oxidation state with decreased aniline content in reactants. Both conductivity and impact strength of the dodecylbenzenesulfonic acid (DBSA) doped PANI composites (PVC/PANI‐DBSA), which were compression molded from the in situ prepared PVC/PANI particles, increase with the pressing temperature and decrease with the increase of DBSA doped PANI (PANI‐DBSA) loading. An excellent electric conductivity of 5.06 × 10^?2 S/cm and impact strength of 0.518 KJ/m² could be achieved for the in situ synthesized and subsequently compression molded composite. Copyright © 2004 John Wiley & Sons, Ltd.     

Sulfonated poly(ether ether ketone)/polyaniline composite proton-exchange membrane

Sulfonated poly(ether ether ketone) (PEEK) was prepared by sulfonation of commercial Victrex^@ PEEK and degree of sulfonation was found to be about 44.5% by ¹H NMR. Sulfonated PEEK/polyaniline composite membranes, in order to prevent methanol crossover, were prepared by chemical polymerization of a thin layer of polyaniline (PANI) in the presence of a high oxidant concentration on a single face modification. FTIR and PANI coating density studies confirmed the loading of PANI in sulfonated PEEK membrane matrix. PANI composite membranes with different polymerization time were prepared and subjected to thermogravimetric analysis as well as electrochemical and methanol permeability study to compare with sulfonated PEEK and Nafion 117 membrane. Ion-exchange capacity, water uptake, proton transport numbers and proton conductivities for different PANI composite sulfonated PEEK (SPEEK) membranes were found to be dependent on the coating density of the PANI in the membrane matrix and were slightly lower than that of Nafion 117 membrane. Methanol permeability of these membranes (especially SPEEK/PANI-1.5) was about four times lower than Nafion 117 membrane. Among the all SPEEK membranes synthesized in this study, SPEEK-1.5 appears to be more suitable for direct methanol fuel cell (DMFC) application considering optimum physicochemical and electrochemical properties, thermal stability as well as very low methanol permeability. Above all, the cost-effective and simple fabrication technique involved in the synthesis of such composite membranes makes their applicability quite attractive.     

Polyaniline/1-tetradecanol composites

Polyaniline (PANI)/1-tetradecanol (TD) composite materials, a kind of novel composite that can conduct electricity and store thermal energy at the same time, thus possess the ability to endure certain heat shock, were prepared for the first time. FTIR and XRD results showed that there were some interactions existed between PANI and TD. The thermal stability of the composites exhibited both the characteristics of PANI and TD. The DSC experiments showed that the highest phase change enthalpy of the composites could be as 73% as that of TD, indicating it was a good form-stable phase change material. The thermal conductivity of the composites was also improved. The AC (Alternating Current) conductivity of the composites was enhanced to close to that of PANI when the mass fraction of PANI in the composite was increased to 46%. Heat shock experiments showed that the heat shock resistibility of the composite was greatly improved comparing to that of pure PANI.     

Preparation and photoelectrochemical characterization of nano-particulate TiO2 and polyaniline composite films on Au

TiO₂ and polyaniline(PANI) composite film was obtained by electrochemical methods^[1] and investigated for solar energy conversion application. A strong rectifying effect was found in the cyclic voltammogram of the film in dark when the scan speed was slow enough (5 mV/s) and a quasi-reversible voltammogram of the film was observed when the scan speed was fast (100 mV/s). The results of both the cyclic voltammograms and the SEM images of the composite film show that the PANI film is almost completely covered with nano-particulate TiO₂. Two anodic photocurrent bands and a cathodic band was observed in the spectra of the photocurrent of the TiO₂/PANI/PATP(p-aminothiophenol)/Au film in 0.05 mol/L Fe(CN)₆^3-/Fe(CN)₆^4- solution. The band at 300~400 nm (3.1~4.1 eV) can be ascribed to the photocurrent band of TiO₂ particles and the bands at 450~730 nm (1.7~2.8 eV) can be ascribed to those of the PANI. The partially-oxidized PANI has internal photoemission function and the insulating matrix of PANI is verified to be reduced PANI with a 3.33 eV bandgap energy. The flat-band potentials of partially-oxidized PANI and TiO₂/PANI composite film in 1.0 mol/LHClO₄ solution are determined as 0.87 V and 0.09(SHE) from Mott-Schottky plots, respectively.     

Thermal stability and glass transition behavior of PANI/γ-Al2O3 composites

Polyaniline/γ-Al₂O₃ (PANI/γ-Al₂O₃) composites were synthesized by in-situ polymerization at the presence of HCl as dopant by adding γ-Al₂O₃ nanoparticles into aniline solution. The composites were characterized by FTIR and XRD. The thermogravimetry (TG) and modulated differential scanning calorimetry (MDSC) were used to study the thermal stability and glass transition temperature (T _g) of the composites, respectively. The results of FTIR showed that γ-Al₂O₃ nanoparticles connected with the PANI chains and affected the absorption characteristics of the composite through the interaction between PANI and nano-sized γ-Al₂O₃. And the results of XRD indicated that the peaks intensity of the PANI/γ-Al₂O₃ composite were weaker than that of the pure PANI. From TG and derivative thermogravimetry (DTG) curves, it was found that the pure PANI and the PANI/γ-Al₂O₃ composites were all one step degradation. And the PANI/γ-Al₂O₃ composites were more thermal stable than the pure PANI. The MDSC curves showed that the nano-sized γ-Al₂O₃ heightened the glass transition temperature (T _g) of PANI.     

Preparation and electrochemical characterization of cation- and anion-exchange/polyaniline composite membranes

Composite membranes were prepared by chemical polymerization of a thin layer of polyaniline (PANI) in the presence of a high oxidant concentration on a single face of a sulfonated cation-exchange membrane (CEM) and quaternary aminated anion-exchange membrane (AEM). IR and SEM studies for both types of membranes confirmed PANI loading on the ion-exchange membranes. PANI composite ion-exchange membranes were characterized as a function of the polymerization time by ion-exchange capacity, coating density, and membrane conductance measurements. Membrane potential measurements were performed in various electrolyte solutions in order to observe the selectivity of these membranes for different types of counterions. Membrane potential data in conjunction with membrane conductance data was interpreted on the basis of frictional considerations between membrane matrix and solute. Electrodialysis experiments, using PANI composite ion-exchange membranes with 4 h polymerization time, were performed in single and mixed electrolyte solutions for observing electromigration of solute across PANI composite ion-exchange membranes. Relative dialytic rates of Na(2)SO(4), CaCl(2), and CuCl(2) were estimated with reference to NaCl on the basis of electrodialysis experiments and it was concluded that it is possible to separate different electrolytes using PANI composite ion-exchange membranes.     

聚苯胺纳米线/SnO2复合光催化材料的光化学制备与性能

将具有确定形态的聚苯胺(PANI)纳米线作为复合单元, 直接分散在SnSO₄和H₂SO₄的混合溶液中, 通 过紫外光照射获得PANI纳米线/SnO₂纳米颗粒复合材料. 对复合材料的形态和成分进行了分析, 发现二者 相互交织在一起且部分颗粒直接生长在纳米线上. 以罗丹明B溶液为目标降解污染物研究了复合材料在低 功率紫外灯下的光催化活性. 结果表明, PANI纳米线可以明显增强SnO₂的光催化活性, 且增强效果与光照 复合时间呈规律性变化, 在最优复合时间下复合材料的光催化活性是纯SnO₂的近3倍. 通过对能级结构与光催化反应过程的测试分析, 认为Z型异质结的形成促进了光生电子-空穴的分离, 进而增强了材料的光催化活性.