Carbon nanotube/polyaniline nanocomposites and their electrorheological characteristics under an applied electric field

A conducting polyaniline (PANI) was synthesized via an oxidative dispersion polymerization technique, using poly(vinyl alcohol) (PVA) as a polymeric stabilizer, in the presence of multi-walled carbon nanotubes (MWNT) purified in acidic solution, and dispersion stability of the MWNT in an aqueous solution of PVA was studied for different PVA concentrations. Their morphology was confirmed by a scanning electron microscope. Its electrorheological (ER) characteristics were also investigated by dispersing the PANI/MWNT composite particles in an insulating silicone oil. Its ER properties were examined using a rotational rheometer under varying applied DC electric field strengths, in which the ER fluid is generally composed of a suspension of conducting particles dispersed in an insulating fluid, which shows a rapid and reversible change in shear viscosity with an applied electric field. Synthesized PANI/MWNT composite particles are observed to enhance interparticular interactions, since the degree of polarization of PANI/MWNT composite particle increases with applied electric field strengths. The shear stresses of the PANI/MWNT nanocomposite based ER fluid increase with the electric field strength for a broad range of shear rates.     

Synthesis and Properties of Polyacrylamide-Based Conducting Gels with Enhanced Mechanical Strength

A nanocomposite conducting hydrogel, polyacrylamide/MWNT/clay (abbreviated as PAM/MWNT/clay), prepared through in situ free radical aqueous polymerization and crosslinked by both clay, as a functional physical crosslinker, and N,N′-methylenebisacrylamide (MBA) as a chemical crosslinker, is reported. The morphology of the gels was characterized by scanning electron microscopy (SEM). The mechanical properties and electrical conductivity were also studied. The results show that the prepared hydrogels had the expected chemical components, with a highly porous structure, and the gels also showed high mechanical strength. The mechanical strength and electrical conductivity value increased with increasing content of multi-walled nanotube (MWNT), and decreased with increasing content of water.     

Synthesis and characterization of polycaprolactone-grafted carbon nanotubes via click reaction

Polycaprolactone (PCL) was covalently grafted on the surface of carbon nanotubes by a simple click reaction of propargyl-terminated PCL (propargyl-PCL) and carbon nanotubes (CNTs) containing azide groups (MWNT-N₃). Propargyl-PCL was synthesized by the ring-opening polymerization of ε-caprolactone using propargyl alcohol and stannous octoate. MWNT-N₃ was prepared from MWNT having 2-bromoisobutyryl groups (MWNT-Br) with sodium azide by azidation. The melting temperature of propargyl-PCL was shifted to the high temperature in PCL-grafted MWNT. The thermal stability of PCL-grafted MWNT was enhanced as compared to that of propargyl-PCL. PCL was coated on the surface of MWNT with a high density of PCL chains, which showed good solubility of PCL-grafted MWNT in organic solvents. PCL-grafted MWNT was characterized with FT-IR, ¹H NMR, Raman, differential scanning calorimetry, thermogravimetric analysis, and scanning electron microscopy.     

Oxygen Diffusion into Multiwalled Carbon Nanotube Doped Polystrene Latex Films Using Fluorescence Technique

This study examines the oxygen diffusion into polystyrene (PS) latex/multiwalled carbon nanotube (MWNT) nanocomposite films (PS/MWNT) consisting of various amounts of MWNT via steady state fluorescence technique (SSF). PS/MWNT films were prepared from the mixture of MWNT and pyrene (P)-labeled PS latexes at various compositions at room temperature. These films were then annealed at 170 °C above glass transition (T_g) temperature of PS. Fluorescence quenching measurements were performed for each film separately to evaluate the effect of MWNT content on oxygen diffusion. The Stern-Volmer equation for fluorescence quenching is combined with Fick’s law for diffusion to derive the mathematical expressions. Diffusion coefficients (D) were produced and found to be increased from 1.1?×?10^?12 to 41?×?10^?12 cm²s^?1 with increasing MWNT content. This increase was explained via the existence of large amounts of pores in composite films which facilitate oxygen penetration into the structure.     

Rheological and Mechanical Characterization of Multi-Walled Carbon Nanotubes/Polypropylene Nanocomposites

The rheology and morphology of multi-walled carbon nanotube (MWNT)/polypropylene (PP) nanocomposites prepared via melt blending was investigated. The minor phase content of MWNT varied between 0.25 and 8 wt%. From morphological studies using a scanning electron microscopy technique a good dispersion of carbon nanotubes in the PP matrix was observed. The rheological studies were performed by a capillary rheometer, and mechanical properties of the nanocomposites were studied using a tensile and flexural tester. Both PP and its nanocomposites showed non-Newtonian behavior. At low shear rates the addition of MWNT content causes an increase in viscosity; however, viscosity is less sensitive to addition of MWNT content at higher shear rates. Flow activation energy for the nanocomposites was calculated using an Arrhenius type equation. From this calculation it was concluded that the temperature sensitivity of nanocomposites was increased by increasing of nanotube content. An increase in tensile and flexural moduli and Izod impact strength was also observed by increasing the MWNT content. From rheological and mechanical tests it was concluded that the mechanical and rheological percolation threshold is at 1.5 wt%.     

Functional multi-walled carbon nanotube/polyaniline composite films as supports of platinum for formic acid electrooxidation

Embedding of carbon nanotubes in conducting polymeric matrices for various nanocomposites material is now a popular area. In this article, a concise chemical method has been described for the preparation of homogeneous nanocomposite of multi-walled carbon nanotube (MWNT)/polyaniline (PANI) by electrochemical codeposition. For this we functionalized the MWNTs via the diazotization reaction. This helped to disperse the nanotubes in aniline. The composite films were dispersed Pt by electrodeposition technique. The presence of MWNTs and platinum in the composite films was confirmed by XRD analysis and transmission electron microscopy (TEM). Four-point probe investigations revealed that the MWNT/PANI composite films exhibited a good conductivity. Cyclic voltammograms (CV) showed that Pt-modified MWNT/PANI composite films perform higher electrocatalytic activity and better long-term stability than Pt-modified pure PANI film toward formic acid oxidation. The results imply that the MWNT/PANI composite films as a promising support material improves the electrocatalytic activity for formic acid oxidation greatly.     

Covalent attachment of polystyrene on multi-walled carbon nanotubes via nitroxide mediated polymerization

A new method to attach polymers on carbon nanotubes has been studied. We used nitroxide mediated polymerization (NMP) to graft polystyrene from multi-walled carbon nanotubes (MWNTs). Carboxyl groups on MWNTs were activated with thionyl chloride (SOCl₂) to give acyl chloride derivative (MWNT-COCl). NMP initiator was introduced to MWNT by esterification of 1-hydroxy-2-phenyl-2-(2′,2′, 6′, 6′-tetramethyl-1′-piperidinyloxy)ethane (HO-PE-TEMPO) with acyl chloride groups of MWNTs. The obtained MWNT-PE-TEMPO was used for initiation of bulk polymerization of styrene, yielding polystyrene-grafted MWNTs (MWNT-g-pSt). The resulting composites of MWNT-g-pSt were analyzed by TEM, SEM, FT-IR and TGA.     

Polystyrene/multi-wall carbon nanotube composites prepared by suspension polymerization and their electrorheological behavior

Polystyrene and polystyrene/multi-wall carbon nanotube composites, PS/MWNT, with MWNT content up to 1 wt.% were prepared in the form of microspheres through in situ suspension polymerization. The morphology of the fraction of 32–64 μm was examined by SEM and TEM microscopy. On the surface of the spheres the presence of MWNT was not observed. The microspheres intersections showed the structure of aggregates of sintered beads a few micrometers in size with heterogeneous interface. No MWNT material was observed inside the beads; it seemed to be situated in the heterogeneous phase of microspheres. Suspensions of PS/MWNT in silicone oil show electrorheological effect, whose intensity strongly depends on MWNT content in composite microspheres.     

Polyurethane‐Carbon Nanotube Nanocomposites Prepared by In‐Situ Polymerization with Electroactive Shape Memory

In‐situ polymerization was employed to achieve well‐dispersed carbon nanotube‐reinforced polyurethane composites. In‐situ polymerization showed predominant as primarily dispersal of carbon nanotubes in the matrix polymer according to scanning electron microscopy (SEM) observation and atomic force microscopy (AFM) images. Differential scanning calorimetry (DSC) results suggested that the addition of multi walled nanotubes (MWNTs) into polyurethane increased the rate of crystallization, this effect being more significant in polyurethane (PU)‐MWNT composite, which was prepared by an in‐situ polymerization process. The composites obtained by in‐situ polymerization showed enhanced mechanical properties as well as good electroactive shape memory. The original shape of the sample was almost recovered with bending mode when an electric field of 50 V was applied.     

Preparation and Characterization of Linear Low Density Polyethylene/Carbon Nanotube Nanocomposites

Linear low‐density polyethylene (LLDPE)/multiwalled carbon nanotube (MWNT) nanocomposites were prepared via melt blending. The morphology and degree of dispersion of nanotubes in the polyethylene matrix were investigated using scanning electron microscopy (SEM). Both individual and agglomerates of MWNTs were evident. The rheological behavior and mechanical and electrical properties of the nanocomposites were studied using a capillary rheometer, tensile tester, and Tera ohm‐meter, respectively. Both polyethylene and its nanocomposites showed non‐Newtonian behavior in almost the whole range of shear rate. Addition of carbon nanotubes increased shear stress and shear viscosity. It was also found that the materials experience a fluid‐solid transition below 1 wt% MWNT. Flow activation energy for the nanocomposites was calculated using an Arrhenius type equation. With increasing nanotube content, the activation energy of flow increases. A decrease of about 7 orders of magnitude was obtained in surface and volume resistivity upon addition of 5 wt% MWNT. In addition, a difference between electrical and rheological percolation thresholds was observed. The results confirm the expected nucleant effect of nanotubes on the crystallization process of polyethylene. A slight increase in Young's modulus was also observed with increasing MWNT content.     

Chemical vapor deposition of multi-walled carbon nanotubes from nickel/yttria-stabilized zirconia catalysts

Multi-walled carbon nanotubes (MWNT) were produced by chemical vapor deposition using yttria-stabilized zirconia/nickel (YSZ/Ni) catalysts. The catalysts were obtained by a liquid mixture technique that resulted in fine dispersed nanoparticles of NiO supported in the YSZ matrix. High quality MWNT having smooth walls, few defects, and low amounts of by-products such as amorphous carbon were obtained, even from catalysts with large Ni concentrations (>50 wt. %). By adjusting the experimental parameters, such as flux of the carbon precursor (ethylene) and Ni concentration, both the MWNT morphology and the process yield could be controlled. The resulting YSZ/Ni/MWNT composites can be interesting due to their mixed ionic-electronic transport properties, which could be useful in electrochemical applications. PACS 61.46.Fg; 81.15.Gh; 82.45.Jn     

Broadband optical limiting performance of polymer-wrapped carbon nanotubes in the orange-NIR region

Soluble multi-walled carbon nanotubes (MWNTs) have been obtained by noncovalent modification with poly [2-methoxy,5-(2′-ethyl-hexyloxy)-p-phenylene vinylene] (MEH-PPV). For the composite MWNT/MEH-PPV, there is π-π interaction between the MEH-PPV and MWNTs in addition to the wrapping of the polymer. The nonlinear optical transmittance was measured using a nanosecond optical parametric oscillator pumped with a Nd:YAG system. Excellent optical limiting performance of the composite MWNT/MEH-PPV was observed both in the visible region of 590-680 nm and at the wavelength of 1064 nm. By means of time-correlated single-photon counting fluorescence measurement, an explanation based on the nonlinear absorption of MWNT dominated by the intermolecular energy transfer was proposed.     

A fluorescence study for the critical behavior of polymethylmethacrylate doped by multiwalled carbon nanotube (PMMA–MWNT) composite bulk gel systems

Polymethylmethacrylate (PMMA) doped by multiwalled carbon nanotube (MWNT) bulk gels were prepared with different amounts of MWNTs varying in the range between 1 and 20 wt%. Free-radical cross-linking copolymerization of PMMA–MWNT composite bulk gels was characterized by the steady-state fluorescence technique. Ethylene glycol dimethacrylate (EGDM) and pyrene (P _y ) were introduced as cross linker and fluorescence probe, respectively. Changes in the viscosity of the pregel solutions due to glass formation dramatically increased the P _y fluorescent intensities, which were used to study the glass transition of PMMA–MWNT composite gels for various MWNT contents. The fluorescence intensity of P _y is proportional to the average size of the glassy regions below and to the strength of the infinite network above the glass transition point. Observations around the glass transition point show that there are three regimes for MWNT concentration in which the gel fraction exponent, β, and the weight average degree of polymerization exponent, γ, differ drastically from percolation results, given in three dimensions as β=0.41 and γ=1.80.     

Nitroxide-controlled free radical copolymerization of styrene and acrylonitrile monitored by electron spin resonance and fourier transform infrared technique in situ

Nitroxide-mediated homopolymerization of styrene (St) and copolymerization of styrene and acrylonitrile (An) were monitored respectively by electron spin resonance and Fourier transform infrared technique in situ, and the polymerization kinetics was investigated in detail. Homopolymerization of St was well controlled in the presence of 4-hydroxyl-2,2,6,6-tetramethyl-l-piperidinyloxy (HTEMPO, N*) at high temperature. The initiation reactions and polymerization rates were changed by varying initiators, such as benzoyl peroxide (BPO), 2,2-azobis-isobutylonitrile (AIBN) and dicyclohexyl dicarbonate peroxide (DCPO) because of the different half-period values of the initiators. For the St system containing the DCPO with longer half-period value, the reaction rate was enhanced and the final conversion was increased because the larger amount of the DCPO residual released continuously the excess radicals to increase growing radical concentration. But the polydispersity of the resulting polymer became somewhat larger. The copolymerization of St and An with AIBN as initiator in the presence of HTEMPO was also tamed in the living fashion of stable free radical polymerization in the range of the total monomer conversion below 40%. The hydrogen-abstracting effect on the penultimate unit of the primary radicals or growing radical was observed through a copolymerization process. The larger amount of St was combined into the copolymers, leading to an increase of the An contents especially in the latter period of copolymerization, due to the inhibited addition of An on the growing radicals with end An unit. The normal random copolymerization was interrupted, resulting in the different virtual reactivity ratio. The dissociation and combination equilibrium between N* and the different end St and An units on propagating radicals affected the consuming rates of St and An. A possible copolymerization mechanism containing hydrogen-abstracting reaction was suggested.     

Critical Exponents of Gelation and Conductivity in Polyacrylamide Gels Doped by Multiwalled Carbon Nanotubes

Polyacrylamide (PAM) doped by multiwalled carbon nanotube (MWNT) gels were prepared with different amounts of MWNTs varying in the range between 0.1 and 15 wt%. The PAM–MWNT composite gels were characterized by the steady state fluorescence technique (SSF). The alternative electrical conductivity (AC) of PAM–MWNT composite gels was measured by the dielectric spectroscopy technique. Observations around the gel point, t _gel for PAM–MWNTs composite gels showed that the gel fraction exponent β obeyed the percolation result. The critical exponent r of AC electrical conductivity for the composite PAM–MWNT gel was also measured and found to be about 2.0, which agrees with a random resistor network.     

纳米铝粉/聚苯乙烯包覆粒子的制备及表征

利用超声波的分散和粉碎作用,对纳米Al粒子进行了表面疏水处理。然后,以无水乙醇为反应介质,苯乙烯为单体,偶氮二异丁腈为引发剂,聚乙烯吡咯烷酮为分散剂,在氮气保护环境下,利用超声波的活化和引发作用,引发苯乙烯单体在纳米Al粒子表面进行分散聚合反应,制备出了纳米铝粉/聚苯乙烯包覆粒子。最后,运用多种测试手段对纳米Al/PS包覆粒子形貌、粒径大小及分布、表面特性、化学组成及结构等进行了表征。测试结果表明,所制备的纳米Al/PS包覆粒子已经形成了完整的球型核壳包覆结构,表面完整无缺陷,粒径大小约为2.0 m。     

聚苯胺-碳纳米管复合体的制备及其光响应

纳米尺寸导电材料对功能分子材料及分子器件的作用越来越显得重要.采用原位乳液聚合法制备聚苯胺 碳纳米管复合体，SEM和TEM照片显示复合管的直径为60—70nm，聚苯胺的包裹层厚度约25—30nm.x射线衍射及热分析表明纳米复合管的结晶性能增强，热稳定性得到提高.光电响应试验表明复合管的光吸收增强，光电流增大，说明聚苯胺 碳纳米复合管薄膜受光照射后发生了光诱导电荷分离现象. 关键词： 聚苯胺 碳纳米管 复合纳米管 光电流     

用分散聚合反应制备SiO2/PS包覆粒子（英）

采用分散聚合反应制备了纳米SiO2/PS包覆粒子,并对其结构进行了表征。首先在超声波场中用表面活性剂对纳米SiO2粒子进行亲油化处理,然后在氮气保护下利用超声波的分散、粉碎、活化、引发等多重作用,在实现纳米SiO2粒子在反应介质中纳米分散的同时,引发苯乙烯单体在纳米SiO2粒子表面发生分散聚合反应,制备出纳米SiO2/PS包覆粒子。最后,采用SEM,TEM,FTIR,XPS等测试手段对纳米SiO2/PS包覆粒子进行了表征,测试结果表明,PS实现了对纳米SiO2的包覆,形成了核壳包覆结构。     

Melt mixing of polycarbonate/multi-wall carbon nanotube composites

—Composites of polycarbonate (PC) with multi-wall carbon nanotubes (MWNT) of different concentrations are prepared by diluting a PC based masterbatch containing 15 wt% MWNT using melt mixing in a DACA-Micro Compounder (4 g scale). Electrical resistivity measurements indicate that the percolation of MWNT is reached between 1 and 1.5 wt%. In addition, melt rheology was applied as another sensitive method to detect the percolation of the nanotubes. Atomic Force Microscopy and visual observations of the composite dispersions in a PC-solvent were used to characterise the state of MWNT dispersion. Differential Scanning Calorimetry and Dynamic Mechanical Analysis were applied to detect changes in the glass transition temperature of PC as a result of processing and of MWNT interactions with the PC matrix including the state of dispersion. In addition, DMA confirmed the reinforcement effect of the nanotubes. The results show that the nanotube incorporation also influences the processing behaviour. Due to the enhancement in melt viscosity by adding nanotubes and the enhanced shear forces, the molecular weight of the PC in the composites is reduced as compared to PC extruded under the same conditions. This effect leads to changes in the glass transition temperature and modulus which counteracts the effects originating from the nanotube-polymer interaction.     

Control of one-dimensional transport in multi-wall carbon nanotubes by wall destruction

We have investigated the damage in multi-wall carbon nanotubes (MWNTs) destroyed by electrical breakdown and focused ion beam bombardment (FIBB). The transport properties of a MWNT destroyed by electrical breakdown have been compared with those of a MWNT destroyed by FIBB. Also the Tomonaga–Luttinger transport (TLT) model has been applied to each type of destroyed MWNT. The MWNT destroyed by FIBB showed TLT behavior because of the weak destruction of the remaining walls. However, in the case of MWNTs destroyed by electrical breakdown, three-dimensional variable-range hopping (VRH) was observed in the low temperature transport. This suggests that the local damage has been caused by strong breakdown. There exists a clear difference between the effects of electrical breakdown and FIBB. Wall destruction by FIBB could be applied to control the one-dimensional transport of MWNTs.