Polypyrrole/carbon nanotube composites: Molecular modeling and experimental investigation as anti-corrosive coating

In this work we present a computational method based on molecular mechanics (MM) and dynamics (MD), to predict mechanical properties of polypyrrole (PPy)/polyaminobenzene sulfonic acid-functionalized single-walled carbon nanotubes (CNT-PABS) and PPy/carboxylic acid-functionalized single-walled carbon nanotubes (CNT-CA) composites. Furthermore, experiments were carried out to assess the anticorrosive features of the PPy film and CNT-PABS and CNT-CA PPy reinforced composite coatings. Computational bulk models of PPy/CNT-PABS and PPy/CNT-CA were implemented at atomistic scale and composite coatings were grown in situ onto carbon steel (OL 48-50) electrodes. PPy, PPy/CNT-PABS and PPy/CNT-CA computational models and films were investigated concerning mechanical properties by using computational tools. The obtained films were assessed experimentally as anticorrosive materials using potentiodynamic measurements, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results clearly confirmed that the CNT-PABS and CNT-CA are properly dispersed in the composite coatings and have beneficial effect on mechanical integrity. Moreover, the anticorrosion protecting ability of the composite coatings is significantly higher than the one characteristic to pure PPy. The Young's moduli generally increased with increasing of CNT content and values ranged from 2.67 GPa in the case of pure PPy to 4.15–4.61 GPa in the case of PPy/CNT-PABS composite system.In agreement with earlier results from the literature for conducting polymer organic coatings, the higher conductivity of material leads to a more efficient anticorrosion protection capability, our results exhibited an enhance of conducting features even for very low mass of CNT-PABS or CNT-CA loaded in composites coatings therefore, an improvement of anticorrosion protecting ability.     

Single-walled carbon nanotube/Nafion composites as methanol sensors

Single-walled carbon nanotube (SWCNT)/Nafion composite films were fabricated on an interdigitated electrode by using a simple casting method. Nafion acts as a polymer backbone to give stable and homogeneous cast thin films. The potential use of the composites as sensors of methanol concentration in water was investigated. The composites are operative even at ambient temperatures, and respond quickly to concentration changes. The resistance increases significantly with increasing concentration between 0.5 M and 4 M. The composites may be useful as a material to measure the concentration of methanol for direct fuel cells.     

Molecular mechanics modeling of carbon nanotube fracture

The fracture of carbon nanotubes (CNTs) is studied in this paper. Molecular mechanics models that incorporate the modified Morse potential and reactive empirical bond-order potential are developed to envisage the fracture behavior of perfect CNTs. The tensile strength, fracture strain, and fracture angle under tension are discussed, and special attention is paid to the effects of tube chirality. Explicit expressions for the fracture solutions for achiral carbon nanotubes are presented, but only numerical results are available for chiral carbon nanotubes. The predicted results of the present model are in good agreement with existing data and those of molecular mechanics simulations via the Materials Studio software package, which indicates the effectiveness of the developed models.     

Effects of nanotube size and roof-layer coating on viscoelastic properties of hybrid diamond-like carbon and carbon nanotube composites

Hybrid carbon nanobuffers are developed by exploiting the ultra-hardness and wear-resistant properties of diamond-like carbon (DLC) coatings and the inherent viscoelasticity properties of vertically aligned carbon nanotubes (VACNTs). The viscoelastic properties of carbon nanobuffers incorporating thin-walled and thick-walled CNTs, respectively, are characterized by means of nanoindentation dynamic mechanical analysis tests. It is shown that the thin-walled nanobuffer has a better damping performance than the thick-walled nanobuffer due to its buckling-driven friction and post-buckling behaviors; particularly under large displacements. In addition, it is shown that under large indenter displacements, the VACNT arrays with DLC coatings display the improved stress distributions and enhanced strain energy dissipation performances due to the load transfer on the top of VACNTs. Molecular dynamics (MD) simulations are performed to investigate the roof-layer effect on damping behavior and structural deformation of the coated and uncoated VACNTs under nanoindentation. The results confirm that the VACNT with a DLC coating exhibits the significantly damping characterizations than the non-coated VACNT. Overall, the results presented in this study reveal the potential for tuning the damping performance of CNT-based nanobuffers through a careful control of the CNT size.     

Single-walled carbon nanotube buckypaper and mesophase pitch carbon/carbon composites

Carbon/carbon composites consisting of single-walled carbon nanotube (SWCNT) buckypaper (BP) and mesophase pitch resin have been produced through impregnation of BP with pitch using toluene as a solvent. Drying, stabilization and carbonization processes were performed sequentially, and repeated to increase the pitch content. Voids in the carbon/carbon composite samples decreased with increasing impregnation process cycles. Electrical conductivity and density of the composites increased with carbonization by two to three times that of pristine BP. These results indicate that discontinuity and intertube contact barriers of SWCNTs in the BP are partially overcome by the carbonization process of pitch. The temperature dependence of the Raman shift shows that mechanical strain is increased since carbonized pitch matrix surrounds the nanotubes.     

碳纳米管／橡胶复合材料研究进展

介绍了碳纳米管(CNT)/橡胶复合材料的制备方法,综述了CNT对橡胶复合材料硫化行为、物理机械性能及电性能的影响.指出CNT在橡胶中分散不均、与橡胶界面结合不佳是CNT/橡胶复合材料拉伸强度提高不显著的主要原因.今后该领域的研究方向应是通过采用新的制备方法或改进现有方法促使CNT在橡胶基质中均匀分散,以提高橡胶复合材料的拉伸强度.     

Preparation and properties of multi-walled carbon nanotube/carbon/polystyrene composites

Multi-walled carbon nanotube (MWCNT)/C/polystyrene (PS) composite materials were prepared by in situ polymerization of monomer in preformed MWCNT/C foams. MWCNT/C foams were preformed using polyurethane foam as template. The preformed MWCNT/C foams had a more continuous conductive structure than the carbon nanotube networks formed by free assembly in composites. The structure of the MWCNT/C foam network was characterized with scanning electron microscopy. The MWCNT/C/PS composites have an electric conductivity higher than 0.01 S/cm for a filler loading of 1 wt.%. Enhancement of thermal conductivity and mechanical properties by the preformed MWCNT/C foam were also observed.     

Polyaniline / carbon nanotube composites: starting with phenylamino functionalized carbon nanotubes

Summary Composites of carbon a nanotube with polymers are a developing and interesting area of research. The dispersion of the nanotube in polymer matrices is an important factor while making its nanocomposites. Even though in-situ polymerization approach offers a better approach for synthesizing homogeneous polymer nanotube composites, the dispersion of the nanotubes in the monomer solution is a problem. In this article we report a new chemical method for dispersing nanotubes in monomer and the preparation of uniform tubular composite of polyaniline (PANI) and multiwalled carbon nanotube (MWNT). For this the oxidized multiwalled nanotube (o-MWNT) was functionalized with p-phenylenediamine, which gave phenylamine functional groups on the surface. This functionalization helped to disperse the nanotubes in acidic solution. The in-situ polymerization of aniline in the presence of these well dispersed nanotubes gave a new tubular composite of carbon nanotube having an ordered uniform encapsulation of doped polyaniline. The phenylamine functional groups on the surface were grown into polyaniline chain so that the composite contains polyaniline functionalized CNT and they were no more an impurity in the final nanocomposite. The microscopic and structural properties of this composite were compared with that of a composite prepared under identical condition using o-MWNT.     

Electrical conductivity modeling of carbon black/polycarbonate,carbon nanotube/polycarbonate,and exfoliated graphite nanoplatelet/polycarbonate composites

Adding conductive carbon fillers to electrically insulating thermoplastic polymers increases the resulting composite's electrical conductivity, which would enable them to be used in electrostatic dissipative and semiconductive applications. In this study, varying amounts of carbon black (CB: 2 to 10 wt %), multiwalled carbon nanotubes (CNT: 0.5 to 8 wt %), or exfoliated graphite nanoplatelets (GNP: 2 to 15 wt %) were added to polycarbonate (PC) and the resulting composites were tested for electrical conductivity (EC = 1/electrical resistivity). The percolation threshold was ～ 1.2 vol % CNT, ～ 2.4 vol % CB, and ～ 4.6 vol % GNP. In addition, three EC models (Mamunya, additive, and general effective media) were developed for the CB/PC, CNT/PC, and GNP/PC composites. The general effective media (GEM) model showed the best agreement with the experimental results over the entire range of filler concentrations (above and below the percolation threshold) for all three composite systems. In addition, the GEM model can be easily adapted for composites containing combinations of different conductive fillers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Tensile modulus modeling of carbon black/polycarbonate,carbon nanotube/polycarbonate,and exfoliated graphite nanoplatelet/polycarbonate composites

Conductive fillers are often added to thermoplastic polymers to increase the resulting composite's electrical conductivity (EC) which would enable them to be used in electrostatic dissipative and semiconductive applications. The resulting composite also exhibits increased tensile modulus. The filler aspect ratio plays an important role in modeling composite EC, and tensile modulus. It is difficult to measure the filler aspect ratio after the manufacturing process (often extrusion followed by injection molding) in the composite, especially when nanomaterials are used. The EC percolation threshold is a function of the filler aspect ratio; hence, knowledge of this percolation threshold provides a means to extract the filler aspect ratio. In this study, the percolation threshold of the composite was determined from EC measurements and modeling, which in turn was used to determine the filler aspect ratio for tensile modulus modeling. Per the authors' knowledge, this approach has not been previously reported in the open literature. The fillers; carbon black (CB: 2–10 wt %), multiwalled carbon nanotubes (CNT: 0.5–8 wt %), or exfoliated graphite nanoplatelets (GNP: 2–12 wt %); were added to polycarbonate (PC) and the resulting composites were tested for EC and tensile modulus. With the filler aspect ratio determined from EC values for CNT/PC and GNP/PC composites, the three‐dimensional randomly oriented fiber Halpin‐Tsai model accurately estimates the tensile modulus for the CNT/PC composites and the Nielsen model predicts the tensile modulus well for the CB/PC and GNP/PC composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Biocompatible hyperbranched polyurethane/multi-walled carbon nanotube composites as shape memory materials

Multi-walled carbon nanotube (MWCNT)-based composites have been prepared by in situ technique using Mesua ferrea L. seed oil-based hyperbranched polyurethane (HBPU) as the matrix. The scanning electron microscope, transmission electron microscope and Fourier transform infrared spectroscopy analyses revealed good dispersion as well as interaction of MWCNT with the matrix. Remarkable recovery of shape to the extent of 98% was obtained after composite formation. More than 300% improvement in tensile strength was observed as compared to the pristine HBPU. Significant enhancement of thermal stability up to 275 °C was found even at low MWCNT loading (1 wt.%). Bacterial degradation of the composite films was tested using two strains of Pseudomonas aeruginosa, MTCC 7814 and MTCC 7815. The composites exhibited enhanced biodegradability as compared to the pristine polymer. The cytocompatibility test based on hemolysis of red blood cells showed that the material lacks cytotoxicity. The investigation indicates that the material has high potential as shape memory biomaterial.     

Doped polyaniline/multiwalled carbon nanotube composites: Preparation and characterization

Polyaniline (PANI)/multiwalled carbon nanotube (MWNT) composites with a uniform tubular structure were prepared from in situ polymerization by dissolving amino‐functionalized MWNT (a‐MWNT) in aniline monomer. For this the oxidized multiwalled nanotube was functionalized with ethylenediamine, which provided ethylenediamine functional group on the MWNT surface confirmed by Fourier‐transform infrared spectra (FT‐IR). The a‐MWNT was dissolved in aniline monomer, and the in situ polymerization of aniline in the presence of these well dispersed nanotubes yielded a novel tubular composite of carbon nanotube having an ordered uniform encapsulation of doped polyaniline. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) showed that the nanotubes were coated with a PANI layer. The thermal stability and electrical conductivity of the PANI /MWNTs composites were characterized by thermogravimetric analysis (TGA) and conventional four‐probe method respectively. Compared with pure PANI, the electrical conductivity and the decomposition temperature of the MWNTs/PANI composites increased with the enhancement of MWNT content in PANI matrix. POLYM. COMPOS., 34:1119–1125, 2013. © 2013 Society of Plastics Engineers     

Crystallization and biodegradation of polylactide/carbon nanotube composites

The crystallization behavior of polylactide/carbon nanotube composites was studied using differential scanning calorimeter and polarized optical microscope. The nucleation mechanisms and the crystallization kinetics were explored. The results show that the presence of nanotubes has nucleating effect on both the melt crystallization and the cold crystallization of PLA. However, the nanotubes also play the role of physical barrier, impeding the crystal growth dynamically. In the experimental range of temperatures, the presence of nanotubes accelerates the melt crystallization, while retards the overall kinetics of the cold crystallization. The biodegradability of the samples with various crystallization histories was then further examined. The results show that the presence of nanotubes reduces the biodegradation rate of PLA, and the amorphous sample shows the highest degradation levels. Moreover, a lower degradation level is observed both on the surface and inside the sample with melt crystallization history in contrast to the one with cold crystallization history. POLYM. ENG. SCI., 50:1721–1733, 2010. © 2010 Society of Plastics Engineers     

Development and characterization of PEEK/carbon nanotube composites

New poly(ether ether ketone) (PEEK) based composites have been fabricated by the incorporation of single-walled carbon nanotubes (SWCNTs) using melt processing. Their structure, morphology, thermal and mechanical properties have been investigated. Scanning electron microscopy observations demonstrated a more uniform distribution of the CNTs for samples prepared following a processing route based on polymer ball milling and CNT dispersion in ethanol media. Thermogravimetric analysis indicated a remarkable improvement in the thermal stability of the matrix by the incorporation of SWCNTs. Differential scanning calorimetry showed a decrease in the crystallization temperature with increasing SWCNT content, whilst no significant changes were observed in the melting of the composites. The crystallite size determined by X-ray diffraction decreased at high SWCNT loading, which is attributed to the spatial limitations on crystal growth by confinement within the CNT network. Dynamic mechanical analysis revealed an increase in the storage moduli, hence in the rigidity of the systems, with increasing SWCNT content. Their addition shifts the glass transition peak to higher temperatures due to the restriction in chain mobility imposed by the CNTs. Higher thermal stability and mechanical strength were found for composites with improved dispersion of the SWCNTs.     

Synthesis and characterization of polyaniline/carbon nanotube composites

The synthesis of polyaniline (PANI) containing different carbon nanotubes (CNTs) by in situ polymerization is reported in this study. The samples were characterized by X‐ray diffraction and scanning electron microscopy. Fourier transform infrared and ultraviolet–visible spectroscopy were used to determine the change in structure of the polymer/CNT composites. Thermogravimetric analysis showed that the composites had better thermal stability than the pure PANI. Photoluminescence spectra showed a blueshift in the PANI–single‐walled nanotube (SWNT) composite. Low‐temperature (77–300 K) electrical transport properties were measured in the absence and presence of a magnetic field up to 1 T. Direct‐current conductivity exhibited a nonohmic, three‐dimensional variable range hopping mechanism. The room‐temperature magnetoconductivity of all of the investigated samples except the PANI–SWNT composite were negative; however, it was positive for the PANI–SWNT composite, and its magnitude decreased with increasing temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thionine-interlinked multi-walled carbon nanotube/gold nanoparticle composites

Multi-walled carbon nanotube (MWCNT)/thionine/gold nanoparticle composites were prepared by binding gold nanoparticles to the surfaces of thionine-coated carbon nanotubes. TEM images show gold nanoparticles distributed uniformly on nanotube walls and ends. UV-Vis, Raman, FT-IR, and zeta potential measurements were used to examine the properties of the resulting products. The composites demonstrate significant electrocatalytic activity for oxygen reduction. Although only gold nanoparticles were investigated here, the method could be easily extended to attach other metallic nanoparticles to the sidewalls of carbon nanotubes.     

碳纳米管/聚合物复合吸波材料的研究进展

简要介绍了吸波材料研究的重要性,综述了碳纳米管/聚合物吸波材料的研究现状,主要包括碳纳米管/环氧树脂(ER)复合材料、碳纳米管/聚苯胺(PANI)复合材料以及碳纳米管/聚氯乙烯(PVC)复合材料的制备方法和吸波性能;并展望了碳纳米管/聚合物复合材料在航天工业领域的发展方向.     

碳纳米管/聚合物复合材料研究进展

介绍了碳纳米管(CNTs)的物理改性方法和化学改性方法,特别综述了CNTs/聚合物复合材料的制备方法(静电纺丝法和层层自组装法),并简单介绍了其独特的力学性能、电学性能和光学性能。最后对CNTs/聚合物复合材料研究归纳了一些现存的问题,并对其应用前景进行了展望。