磺化聚苯乙炔/多壁碳纳米管复合材料导电特性和机理的研究

将磺化聚苯乙炔(SPPA)与多壁碳纳米管(MWCNTs)超声共混制备得到SPPA/MWCNTs复合材料. 用X光电子能谱仪、固体紫外-可见分光光度计、X射线衍射仪、四探针、场发射扫描电镜等对复合材料导电特性及机理进行研究. 结果表明: SPPA/MWCNTs 复合材料中SPPA与MWCNTs发生电荷转移而被掺杂, 并且由于SPPA与MWCNTs间的电荷转移, 彼此间存在一定的相互作用力; 复合材料电阻呈负温度系数效应; SPPA/MWCNTs复合材料电导率发生两次突跃. 可能的导电机理为, 复合材料中SPPA不仅被MWCNTs物理填充, 同时还被MWCNTs掺杂, 复合材料中存在两种导电通路, 一是SPPA与MWCNTs的碳原子发生电荷转移而被掺杂, 彼此之间存在一定的相互作用力, 导致SPPA包裹MWCNTs形成独立导体单元, 这种独立单元相互接触形成导电通路; 二是MWCNTs彼此之间相互接触形成导电通路, 并建立了该导电机理的理论模型.     

石墨烯/聚吡咯的添加对磷酸钙骨水泥结构与性能的影响

自然骨具有压电效应,结合电刺激可以促进骨组织生长与修复,因此制备具有导电性人工骨材料尤为重要.本文通过在骨水泥(CPC)固相中添加不同含量的高导电率的还原氧化石墨烯(RGO)/聚吡咯(PPy)复合材料,研究不同含量RGO/PPy的添加对CPC结构与性能的影响.结果表明,添加RGO/PPy复合材料的CPC,其初凝时间和终凝时间都有所减小,但凝固时间均能满足临床使用要求.RGO/PPy的添加对CPC的物相组成没有影响,但对其抗压力学性能、微观形貌、导电性能的影响较大.其中,CPC的抗压力学性能随着RGO/PPy添加量的增加而减小,导电性随着RGO/PPy的添加量的增加而增大.     

聚氨酯微粉在环氧复合材料中的应用

将聚氨酯(PU)微粉MP750与环氧树脂(Epon 828)混合、固化,制备得到不同PU添加量的环氧树脂/PU复合材料。研究表明,随着PU微粉的加入,显著提升了环氧树脂复合材料的冲击强度、韧性、剥离强度及粘合力。当PU添加量为15%时,环氧树脂复合材料的剥离强度由原来的1.09N/mm提高到1.8N/mm,层间粘合力从原来的0.71N/mm提高到1.38N/mm,提升率均达60%以上。     

MWCNTs/PVA-co-PE纳米纤维膜导电性能的研究

通过原位自组装法制备MWCNTs/PVA-co-PE复合材料,将此复合材料与纤维素酯共混后,利用热塑性聚合物熔融共混相分离法制备了MWCNTs/PVA-co-PE复合纳米纤维。通过SEM和TEM分析表征了MWCNTs/PVA-co-PE复合纳米纤维的形态、结构以及多壁碳纳米管在纳米纤维中的分布状态;研究了多壁碳纳米管添加量对MWCNTs/PVA-co-PE复合纳米纤维导电性能的影响。结果表明,当多壁碳纳米管的添加量大于6%时,MWCNTs/PVA-co-PE复合材料的表面电阻会显著下降;提高MWCNTs的添加量会使MWCNTs/PVA-co-PE复合纳米纤维的表面电阻稍微下降,但是效果不大,这可能是由于MWCNTs在纳米纤维内部不能形成良好的导电通道。     

多壁碳纳米管对聚甲醛性能的影响

将多壁碳纳米管(MWCNTs)和聚甲醛(POM)在转矩流变仪中熔融混合得到POM/MWCNT复合材料.研究了复合材料的形态,导热性能,导电性能,流变性能和结晶性能.结果表明,MWCNTs在没有经过处理的情况下能够均匀地分散在POM基体中;当向POM中添加1.0 wt%含量MWCNTs时,复合材料的导热系数上升到0.5289 W/(K m),比纯POM的导热系数0.198 W/(K m)提高1.5倍,通过有效介质方法(EMA)验证了体系导热系数提高幅度不大的原因是MWCNTs与POM之间形成了很高的界面热阻;当MWCNTs的含量为1.0 wt%时,体系产生了导电逾渗效应,逾渗值在0.5 wt%~1.0 wt%之间;MWCNTs对POM有显著的成核作用,当向POM中添加0.5 wt%含量的MWCNTs时,POM的结晶温度提高6℃左右,但当MWCNTs的添加量进一步增加时,结晶温度几乎不再变化,成核效果呈现"饱和"状态.另外,材料的复数黏度,储能模量和损耗模量随MWCNTs含量的增加而增加.     

碳纳米管改性环氧树脂的导热和阻燃性能

以双酚A二缩水甘油醚(DGEBA)环氧树脂(Epoxy Resin,EP)为基体、甲基六氢苯酐(MHHPA)为固化剂、以多壁碳纳米管(MWCNTs)为添加剂制备了环氧树脂/碳纳米管纳米复合材料。通过对微观结构、玻璃化转变温度(Tg)、热失重、热导率和锥形量热测试结果分析,研究了质量分数少于1.5%的MWCNTs对环氧树脂的导热和阻燃性能影响,结果表明,MWCNTs质量分数为1.5%时,复合材料发生团聚;纳米复合材料随着MWCNTs质量分数的增加Tg值先增加后降低;失重5%时,对应的温度先增加后降低,残炭量增加;样品的热导率呈现先升高后降低的趋势,当MWCNTs质量分数为1%时,复合材料的热导率最大;MWCNTs加入后环氧树脂的总释热量减少,释烟量增加,阻燃性得到一定程度的提高。     

掺杂羧基化碳纳米管的纳米碳纤维前驱体的制备及表征

为获得结构完整、 性能优良的纳米碳纤维前驱体, 采用静电纺丝法制备了掺杂羧基化多壁碳纳米管(MWCNTs)的聚丙烯腈(PAN)纳米纤维. 用扫描电子显微镜、 偏振红外光谱、 透射电子显微镜、 拉曼光谱及拉伸性能测试等对杂化纳米纤维的微观结构和力学性能进行了研究, 分析了MWCNTs含量的影响. 实验结果表明, 5%(质量分数)的MWCNTs掺杂量为杂化纳米纤维直径的突变点, 且MWCNTs的加入有利于PAN分子链的取向, MWCNTs在PAN纤维中大体上沿纤维轴向取向分布. 3%MWCNTs/PAN杂化纳米纤维的拉伸强度和拉伸模量分别达到88.6 MPa和3.21 GPa.     

乙烯-乙烯醇共聚物/碳纳米管复合发泡材料的电磁屏蔽性能研究

选用高机械强度和耐气候性乙烯-乙烯醇共聚物(EVOH)作为基体,添加高效导电填料多壁碳纳米管(MWCNTs),同时为了进一步提高材料性能,添加了聚醚多元醇(EOPO)与4,4’-二苯基甲烷二异氰酸(MDI)的共聚物.采用绿色环保的超临界二氧化碳发泡法制备EVOH/MDI-g-EOPO/MWCNTs纳米复合发泡材料,结果表明在EVOH/MDI-g-EOPO/MWCNTs复合材料中引入多孔结构,利用多层界面反射-吸收电磁波,比电磁屏蔽性能提升270%.通过调控MWCNTs体积含量与泡孔结构,当MWCNTs体积含量达到2.7 wt%时,EVOH/MDI-g-EOPO/MWCNTs复合发泡材料在X波段(9～12 GHz)表现出优异的比电磁屏蔽效能(41.76 dB·cm³/g).     

聚ε-己内酯/聚吡咯电纺膜的制备与性能

以吡咯(Py)和聚ε-己内酯(PCL)为原料、氯仿为溶剂,并掺杂一定量的十二烷基硫酸钠制备电纺膜,利用三氯化铁的氧化作用原位生成聚吡咯(PPy).对所得到的PCL/PPy电纺膜用红外光谱进行表征,在扫描电镜和透射电镜下观察纤维形貌,并测定力学性能和体积电阻率.结果表明,所生成的PPy以纳米粒子形式附着在电纺纤维表面,随着Py相对于PCL的质量百分含量由0增加到20%,PCL/PPy电纺膜的纤维直径从(730±341)nm逐渐下降至(325±84)nm;膜的拉伸模量和拉伸强度由不含Py的(25.7±0.8)MPa和(2.48±0.14)MPa分别增加至含有20%Py的(48.4±7.6)MPa和(5.05±0.59)MPa,断裂伸长率由(129±27)%下降至(86.2±9.1)%;体积电阻率降低了2～3个数量级.该PCL/PPy电纺纤维膜以期可作为电活性材料用于功能或生物医用领域.     

MnO2/PPy/PANI三元纳米管复合材料的合成及其电化学电容性能

在聚苯胺（PANI）和二氧化锰（MnO2）存在的条件下,以FeCl3/甲基橙为模板,通过化学氧化法聚合吡咯(Py)单体,制备MnO2/PPy/PANI纳米管复合材料。 利用X射线衍射、透射电子显微镜、红外光谱和电化学测试等多种测试技术对复合材料进行物性表征和电化学电容性能测试,并讨论了不同含量的PANI对复合物材料的结构和性能的影响。 结果表明,由于PANI、MnO2与PPy三者的相互协同作用,以及材料管状结构的大比表面积,使三元复合材料具有比二元复合材料要大的电化学活性。 所合成的三元复合材料最大比容量达到458.4 F/g。     

吡咯在一些聚合物基质中聚合生成导电高分子复合物的研究

用电化学氧化聚合方法将吡咯在聚氨酯(PU)、聚已内酰胺(Nylon 6)、聚芳砜酰胺(PSu)及聚对苯二甲酰对苯二胺(PPTA)等绝缘聚合物中聚合生成聚吡咯(PP_y)的高分子复合物PU/PP_y、Nylon 6/PP_y、PS_u/PP_y、PPTA/PP_y等。它们具有良好的电导率及力学性能、报导了他们的制备方法及电导率、力学性能、电化学活性、扫描电镜、X-射线衍射的表征。     

Synthesis of electromagnetic functionalized nickel/polypyrrole core/shell composites

Microstructured Ni/PPy (PPy: polypyrrole) core/shell composites were prepared from an in situ chemical oxidative polymerization of pyrrole (Py) monomer in the presence of Ni powder, with ammonium persulfate (APS) as oxidant and citric acid (C6H8O7) as dopant. X-ray diffraction and Fourier transform infrared analyses indicate that there is no chemical interaction between Ni powder and protonated PPy. The mass percentages of PPy, calculated from the remanent weight percentages of Ni/PPy composites after thermogravimetric analysis, are in consistent with those as designed. The prepared Ni/PPy composites are soft and ferromagnetic materials, where a linear increase of saturation magnetization (MS) and remanent magnetization (MR) as a function of Ni powder content is proposed. The permeability of Ni/PPy composites presents a natural magnetic resonance at 6.0 GHz, and Cole-Cole semicircle was applied to explain the permittivity. Electromagnetic absorption less than -10 dB is found for Ni/Py=4:1 (11-15.4 GHz) and Ni/Py=2:1 (12-17.5 GHz). The ternary Debye relaxations for enhanced dielectric loss induced by PPy coatings and proper electromagnetic impedance matching due to the synergetic consequence of the Ni cores and PPy shells contribute to the improvement of the electromagnetic absorption of the Ni/PPy core/shell composites. It is important to notice that dielectric loss and electrical conductivity should be considered simultaneously in designing dielectric-type electromagnetic absorbing materials.     

The processing and properties of conductive polypropylene/polypyrrole composites

Polypropylene (PP) particles were chemically coated with polypyrrole (PPy). The content of polypyrrole varied from 0.8 to 7.6 wt.-%. Electrical conductivity of compression moulded samples depends on the concentration of polypyrrole and reached values from 4×10⁻¹⁰ to 5×10⁻³ S/cm, which is about 7 orders of magnitude higher than the conductivity in the blends prepared by mechanical mixing of PP and PPy in the same PPy concentration range. Highly conductive composites were also obtained from a mixture of coated and non-coated PP particles. The PP/PPy composites were characterized by elemental analysis, SEM and mechanical testing. The antistatic properties of PP/PPy composites were demonstrated. The electrical and mechanical properties depend on processing of composites.     

Synthesis and characterization of a novel polyurethane/polypyrrole‐p‐toluenesulfonate (PU/PPy‐pTS) electroactive nanofibrous bending actuator

Electroactive actuators based on conductive polymers currently have attracted a great deal of attention. In this study, a nanofibrous structure of polypyrrole (PPy) was used to fabricate an electroactive bending actuator. For this purpose, polyurethane/PPy (PU/PPy) nanofibrous bending actuator was fabricated through the combined use of electrospinning and in‐situ chemical polymerization. The response surface methodology (RSM) was considered to find the optimal electrospinning conditions for producing PU nanofibers with the minimum diameter. The in‐situ chemical polymerization method was then used to prepare a conductive layer of PPy on the surface of optimum electrospun nanofibers with p‐toluenesulfonate (pTS) as the dopant. The coated nanofibers were used in the fabrication of PU/PPy‐pTS nanofibrous bending actuator. The morphology and electrical, thermal, electrochemical, and electrochemomechanical properties of the fabricated actuator were investigated. By using optimum conditions of electrospinning, PU nanofibers were obtained with a diameter of 221 nm. The results showed that the produced PU/PPy‐pTS nanofibers enjoy good thermal stability and have an electrical conductivity of about 276.34 S/cm. The obtained cyclic voltammetric and dynamo‐voltammetric responses showed that the dominant mechanism of actuation in the fabricated PU/PPy‐pTS nanofibrous actuator is the exchange of perchlorate anions with a partial exchange of lithium cations in 1M lithium perchlorate electrolyte solution. The fabricated actuator was capable of undergoing 141° reversible angular displacement during a potential cycle. The results demonstrated that, given high porosity, large specific surface area, flexibility, and desirable electrical properties, PU/PPy nanofibrous electroactive actuator provides a lot of potential for developing artificial muscle applications.     

Composites of polypyrrole with conducting and ferromagnetic behaviors

Composites of polypyrrole (PPy) with electrical and ferromagnetic behaviors were synthesized by a chemical method in the presence of p‐dodecylbenzene sulfonic acid sodium salt (NaDS) as a surfactant and dopant. The magnetic properties of the resulting composites showed ferromagnetic behavior, such as high saturated magnetization (M_s = 3.06–43.7 emu/g), and coercive force (H_c = 9–57 Oe). The saturated magnetization linearly increased with increases in the Fe content. No influence of the counterion on this relationship was observed. The conductivity of the composites at room temperature depended on the counterion and doping degree. The highest conductivity of 10⁰ S/cm was achieved under the optimal synthetic conditions. A structural characterization by elemental analysis, Fourier transform infrared, and X‐ray diffraction proved that nanometer‐sized (16–20‐nm) iron oxide (Fe₃O₄) in the composites was responsible for the ferromagnetic behavior of the composites, whereas the high conductivity of the composites contributed to the difficult deprotonation of the doping PPy with DS⁻ counterion in a basic reaction medium. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2734–2739, 2000     

Morphology,microhardness, and electrical properties of composites based on polypropylene,montmorillonite, and polypyrrole

The morphology, microhardness, and electrical properties of composites consisting of conductive polypyrrole (PPy) dispersed into a nonconductive polypropylene matrix (PP) as pure component or in form of a sodium montmorillonite/PPy (MMT/PPy) composite have been studied. For comparison, also PP/MMT composites were studied. All types of composites were processed by compression molding or by melt mixing followed by compression molding into plates, which were used for characterization. Scanning electron microscopy and transmission electron microscopy was used to examine the morphology of the prepared materials. The investigation of electrical and dielectric properties was done by dielectric relaxation spectroscopy in a wide frequency range and was related to the composite composition and processing method. The analysis of the conductivity as a function of temperature indicated that the charge transfer mechanism could be described by the variable range hopping model in three dimensions. The microhardness of PP/MMT/PPy composites with different content of MMT or PPy was determined and the creep rate has been estimated. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 407–423, 2009     

Synthesis and characterization of carbon nanotube/polypyrrole core–shell nanocomposites via in situ inverse microemulsion

We demonstrate here a feasible approach to the preparation of multiwalled carbon nanotube (MWNT)/polypyrrole (PPy) core–shell nanowires by in situ inverse microemulsion. Transmission electron microscopy and scanning electron microscopy showed that the carbon nanotubes were uniformly coated with a PPy layer with a thickness of several to several tens of nanometers, depending on the MWNT content. Fourier transform infrared spectra suggested that there was strong interaction between the π‐bonded surface of the carbon nanotubes and the conjugated structure of the PPy shell layer. The thermal stability and electrical conductivity of the MWNT/PPy composites were examined with thermogravimetric analysis and a conventional four‐probe method. In comparison with pure PPy, the decomposition temperature of the MWNT/PPy (1 wt % MWNT) composites increased from 305 to 335 °C, and the electrical conductivity of the MWNT/PPy (1 wt % MWNT) composites increased by 1 order of magnitude. The current–voltage curves of the MWNT/PPy nanocomposites followed Ohm's law, reflecting the metallic character of the MWNT/PPy nanocomposites. The cyclic voltammetry measurements revealed that PPy/MWNT composites showed an enhancement in the specific charge capacity with respect to that of pure PPy. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6105–6115, 2005     

聚吡咯/Ba_(0.9)Nd_(0.1)Fe_(11.5)Cr_(0.5)O_(19)复合物的可控合成及电磁性能

用溶胶凝胶法制备了一系列Nd掺杂Ba-铁氧体粉末(Ba1-xNdxFe11.5Cr0.5O19,x=0.00,0.05,0.10,0.15,0.20),选取磁性能相对较好的Ba0.9Nd0.1Fe11.5Cr0.5O19作为磁核,通过原位聚合法制备了不同铁氧体含量的聚吡咯/Ba0.9Nd0.1Fe11.5Cr0.5O19(PPy/BNFCO)复合物.用X射线衍射(XRD)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、红外光谱(FTIR)、振动样品磁强计(VSM)、四探针测试仪和矢量网络分析仪等表征了铁氧体粉末和复合物微粒的结构、形貌以及电磁性能.结果表明,Nd的掺杂明显改变了Ba-铁氧体的饱和磁化强度和矫顽力;PPy/BNFCO复合物具有比较明显的核壳结构;复合物的饱和磁化强度随BNFCO含量的增加而增大;电导率则与PPy含量成正比,mpy/mBNFCO=5/1为复合体系渗流阈值;复合物对电磁波的反射损耗和有效带宽是PPy和ZCGFO协同作用的结果,当mpy/mBNFCO为5/1时,PPy/ZCGFO复合物中组分间的协同作用达到最大,其反射峰值和有效带宽分别达到-27.68dB和9.04GHz.PPy/ZCGFO复合物由于良好的微波吸收性能,有望成为电磁波吸收与屏蔽领域的候选材料.     

Polypyrrole (PPy) chemical synthesis with xylan in aqueous medium and production of highly conducting PPy/nanofibrillated cellulose films and coatings

Polypyrrole was chemically synthesised by using, for the first time, Birchwood xylan as additive, and ammonium peroxydisulfate (APS) as oxidant. The impact of additive concentration, polymerisation time and reagents concentration on PPy conductivity was studied. It was shown that, once fixed the pyrrole (Py)/APS and Py/xylan optimal ratios, the best conductivities (26 S/cm) were obtained for short polymerisation times (30 min) and increased reactants concentration. Morphological analysis of PPy particles, Py depletion kinetics and oxido-reduction potential measurements of the solutions provided interpretation elements on the impact of the polymerisation time on PPy pellet conductivity. Furthermore, optimised PPy particles obtained with xylan (PPy_x) were mixed with nanofibrillated cellulose (NFC) in order to obtain freestanding films. Their electrical and handling performances were evaluated at increasing PPy weight fraction in the samples. The conductivity mechanism of the most conductive sample (in comparison with a low performing sample) was investigated by measuring the conductivity as a function of temperature (4–350 K) and two transport regimes were identified. Selected formulations were finally used to produce conducting PPy/NFC coatings on non-absorbent (glass) and absorbent (copy paper) substrates. The impact of NFC in the percolation of PPy particles, then in the coating conductivity, was investigated.     

Preparation of conductive PTFE nanocomposite containing multiwalled carbon nanotube via latex heterocoagulation approach

Conductive poly(tetrafluoroethylene) (PTFE) composites containing surface-modified multiwalled carbon nanotubes (MWCNTs) were prepared by a simple heterocoagulation process in water. Two different types of MWCNT were used and compared: carboxylated MWCNT and cetyltrimethyl ammonium bromide (CTAB)-stabilized MWCNT. Aqueous PTFE dispersion was mixed with the well-dispersed MWCNT dispersions and they were heterocoagulated with the aid of a flocculant, polyaluminum chloride at an elevated temperature. After particle growth and successive stabilization step, particulated PTFE/MWCNT composites were prepared in the size range of 10–100 μm. The MWCNT-containing PTFE composites have improved thermal stability and electrical conductivity. Importantly, the percolation threshold for the electrical conductivity was achieved at a low concentration of MWCNT using this heterocoagulation process.