Synthesis and properties of the amino‐functionalized multiple‐walled carbon nanotubes/polyimide nanocomposites

The 1,6‐hexanediamine‐functionalized multi‐walled carbon nanotubes(a‐MWNTs)/polyimide(PI) nanocomposite films were prepared through in‐situ polymerization followed by mixture casting, evaporation, and thermal imidization. To increase the compatibility of carbon nanotubes with the matrix polyimide, a‐MWNTs was used as the filler. According to the results, a‐MWNTs were homogeneously dispersed in the nanocomposite films. With the incorporation of a‐MWNTs, the mechanical properties of the resultant films were improved due to the strong chemical bonding and interfacial interaction between a‐MWNTs and 4,4′‐oxydiphthalic anhydride(ODPA)/4,4′‐Oxydianiline(ODA) polyimide matrix. The thermal stability of the a‐MWNTs/polyimide nanocomposite was also improved by the addition of a‐MWNTs. The electrical tests showed a percolation threshold at about 0.85 vol% and the electrical properties were increased sharply. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Thermal properties of hyperbranched polyborate functionalized multiwall carbon nanotube/polybenzoxazine composites

Using a noncovalent functionalization strategy, hyperbranched polyborate (HBb) acts as a solubilizer for carbon nanotubes (CNTs), and a stable HBb‐CNT dispersion in N‐methyl‐pyrrolidone was produced. The thermal properties of the resulting HBb‐CNT/polybenzoxazine (B‐BOZ) composites and their carbonized structures were investigated. Scanning electron microscopy demonstrated that the fracture surface of HBb‐CNT/B‐BOZ composites was rather rough and plenty of plastic deformation was exhibited. Thermogravimetric analysis indicates an improvement in the thermal stability of the composite with CNTs, especially that of 2.0 wt% CNT modified composite. The increase in the thermal stability is due to the good nanotube dispersion and the effective polymer‐CNT interaction. Graphite‐like boron carbonitride ceramic compounds were found after the composites were carbonized at 1,100°C for 2 h, and there was more B‐C, B‐N, and C‐N bonds in the carbonized HBb‐CNT/B‐BOZ composite than that of HBb/B‐BOZ composite. The result implied that CNTs can promote the ceramic process of HBb/B‐BOZ composite, and the strategy of introducing ceramic precursor into polymer composites may be useful to improve their ablation properties. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

In situ preparation of polyimide/titanium carbide composites with enhanced dielectric constant

A series of polyimide/titanium carbide (PI/TiC) composites with different TiC contents were prepared using the ultrasonic dispersion and in situ polymerization method. Atomic force microscopy (AFM), X‐ray diffraction (XRD), scanning electron microscope (SEM), mechanical, and electrometer were used to characterize the structure and properties of the obtained composites. The morphological study of composites by AFM and SEM showed that TiC particles had a homogeneous dispersion in polyimide matrix with nanoscale at low filler dosage (≤10% volume content). X‐ray diffractions (XRDs) indicated that the doping of TiC slightly reduced the packing density of polyimide and destructed the aggregation structure of polyimide molecules. Experimental results showed that the obtained PI/TiC composites exhibited appropriate mechanical properties and moderate electric breakdown strength. Dielectric investigation evidenced that the dielectric constant and the dielectric loss of these composites increased with the increase of the volume fraction of TiC particles. The composite with 20 vol% TiC particles showed a highest dielectric constant of 37 while retaining an appropriate dielectric loss of 0.026, as compared with the dielectric constant (3–4) of neat polyimide resin. In addition, the dielectric properties of the composites displayed good stability within a wide range of frequency. The results of this work demonstrate the potential use of a PI/TiC composite film in an embedded capacitor. POLYM. COMPOS., 125–130, 2016. © 2014 Society of Plastics Engineers     

In situ fabrication of HfC-decorated carbon nanotube yarns and their field-emission properties

HfC-decorated carbon nanotube (CNT) yarns have been fabricated by pre-coating pure CNT yarns with Hf and in situ current heating in vacuum. HfC nanocrystals were formed at about 1600 K through reaction of the CNTs with Hf. The fabricated HfC-CNT yarns had a work function of 3.9 eV, lower than that of pure CNT yarns. For field-emission applications, HfC-CNT sharp tips made up of HfC nanorods were obtained by Joule-heating-induced electrical breakdown above 2100 K. Their emission current could reach 320 μA with a calculated density of 800 A/cm² at an extraction voltage of 400 V. The emitters could operate under a rough vacuum of 10⁻² Pa without obvious degradation. These excellent field-emission properties are attributed to the HfC nanorods, which have a low work function and are resistant to ion bombardment.     

Preparation and properties of multiwalled carbon nanotube/epoxy‐amine composites

Different amounts of multiwalled carbon tubes (MWCNTs) were incorporated into an epoxy resin based on diglycidyl ether of bisphenol A and both epoxy precursor and composite were cured with 4,4′‐diamino diphenyl sulfone. Transmission and scanning electron microscopy demonstrated that the carbon nanotubes are dispersed well in the epoxy matrix. Differential scanning calorimetry measurements confirmed the decrease in overall cure by the addition of MWCNTs. A decrease in volume shrinkage of the epoxy matrix caused by the addition of MWCNTs was observed by pressure–volume–temperature measurements. Thermomechanical and dynamic mechanical analysis were performed for the MWCNT/epoxy composites, showing that the T_g was slightly affected, whereas the dimensional stability and stiffness are improved by the addition of MWCNTs. Electrical conductivity measurements of the composite samples showed that an insulator to conductor transition takes place between 0.019 and 0.037 wt % MWCNTs. The addition of MWCNTs induces an increase in both impact strength (18%) and fracture toughness (38%) of the epoxy matrix with very low filler content. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effects of crosslinking agents on the physical properties of polyimide/amino‐functionalized graphene oxide hybrid films

The effects of crosslinking agents (crosslinkers) on polyimide (PI)/graphene oxide (GO) hybrid films were extensively investigated. The surface of GO was modified with amino groups using 4‐aminobenzylamine to improve compatibility with pyromellitic dianhydride/4,4′‐oxydianiline PI, and two kinds of crosslinkers were used: tris(4‐aminophenyl)amine and 1,3,5‐triazine‐2,4,6‐triamine (melamine). The mechanical, thermal and optical properties of the PI hybrid films were investigated. In particular, the transparency and physical properties of the PI hybrid films containing amino‐functionalized GO with homogeneous dispersion were improved. As the content of the crosslinker increased, a crosslinking network was formed between the PI chains, and the stiffness of the hybrid films was increased. The glass transition temperature, heat resistance and mechanical properties were also enhanced. The PI hybrids prepared with a rigid crosslinker exhibited higher optical transparency due to the reduction of the intermolecular charge transfer interactions with increasing interchain spacing between the PI chains. © 2018 Society of Chemical Industry     

Network behavior of thermosetting polyimide/multiwalled carbon nanotube composites

In previous published research, network formation has been used to understand morphology and properties in polymer nanocomposites containing carbon nanotubes (CNTs) through measurements of rheological and electrical percolation thresholds, largely in thermoplastic matrices. In this research, these tools are explored as a means to understand network transport mechanisms and changes in CNT dispersion during curing in a thermosetting matrix. Specifically, rheological and electrical measurements were performed on the uncured nanocomposites, and electrical measurements were performed on the cured nanocomposites. The resulting data were applied to a percolation model. The results showed that the uncured resin played a limited role in mediating rheological transport and that little CNT aggregation occurred during curing. The results of this initial work suggest that such a combination of techniques is applicable to understanding dispersion changes resulting from curing and provides complementary insight to that provided by electron microscopy imaging of the same phenomenon.     

Ultradrawing properties of ultrahigh‐molecular weight polyethylene/functionalized carbon nanotube fibers and transmittance properties of their gel solutions

The influences of the dispersion level of carbon nanotubes (CNTs) and functionalized CNTs on the transmittance properties of ultrahigh‐molecular weight polyethylene (UHMWPE) gel solutions and on ultradrawing properties of their as‐prepared fibers are reported. The transmittance properties suggest that the dispersion level of functionalized CNTs in UHMWPE/functionalized CNTs gel solution is significantly better than plain CNTs in UHMWPE/CNTs gel solutions. The orientation factors, achievable draw ratios, tensile strength (σ_f), and modulus (E) values of UHMWPE/CNTs (F_xC_y) and UHMWPE/functionalized CNTs (F_xC_f‐y) as‐prepared fiber specimens reached a maximum value as their CNT and functionalized CNT contents approached optimum contents at 0.00015 and 0.0001 wt%, respectively. The σ_f and E values of both F_xC_0.0012 and F_xC_f‐0.001 series fiber specimens prepared at their optimum CNT and functionalized CNT contents reached another maximum as their UHMWPE approached optimum UHMWPE concentration of 1.7 wt%. Possible reasons accounting for these interesting properties are proposed. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

A comparative study on the properties of the different amino‐functionalized multiwall carbon nanotubes reinforced epoxy resin composites

Multiwall carbon nanotubes (MWCNTs) were amino‐functionalized by 1,2‐ethylenediamine (EDA)' triethylenetetramine (TETA), and dodecylamine (DDA), and investigated by fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and thermogravimetric analysis (TGA). The dispersion of the DDA functionalized MWCNT in DMF is better than that of the MWCNT functionalized by the EDA and the TETA. Carbon nanotubes reinforced epoxy resin composites were prepared, and the effect of the amino‐functionalization on the properties of the composites was investigated by differential scanning calorimetry (DSC), dynamical mechanical analysis (DMA), and TGA. The composites reinforced by the MWCNTs demonstrate improvement in various mechanical properties. The increase of T_g of the composites with the addition of amino‐functionalized MWCNT compared to the T_g of the composites with the addition of unfunctionalized MWCNT was due to the chemical combination and the physical entanglements between amino group from modified MWNTs and epoxy group from the epoxy resin. The interfacial bonding between the epoxy and the amino group of the EDA and the TETA‐modified MWCNT is more important than the well dispersion of DDA‐modified MWCNT in the composites for the improvement of the mechanical properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and properties of nadic‐end‐capped cyclotriphosphazene‐containing polyimide/carbon fiber composites

New novel fire‐resistant and heat‐resistant cyclotriphosphazene‐containing polyimide resins were prepared in situ by the polymerization of (p‐aminophenoxy)(phenoxy)cyclotriphosphazenes with 3,3′,4,4′‐benzophenonetetracarboxylic acid or 3,3′,4,4′‐diphenylsulfonetetracarboxylic acid and a crosslink agent, 5‐norbornene‐2,3‐dicarboxylic acid and were used as polymer matrix compositing with a woven carbon fiber to prepare nadic‐end‐capped cyclotriphosphazene‐containing polyimide/carbon fiber composites. The thermal stability, flame retardance, morphology of the surface fracture, and some physical properties of the composites were investigated by thermogravimetric analysis, scanning electron microscopy, and a material testing system, respectively. The composites had good thermal stability, flame retardance, and mechanical properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 810–818, 2003     

Ultradrawing properties of ultra‐high molecular weight polyethylene/functionalized carbon nanotube fibers

Systemic investigation of the influence of the plain and functionalized carbon nanotube (CNT) contents on the ultradrawing properties of ultrahigh molecular weight polyethylene/carbon nanotubes (UHMWPE/CNTs, FC_y) and UHMWPE/functionalized CNTs (FC_fx‐y) as‐prepared fibers are reported. In a way similar to those found for the orientation factor values, the achievable draw ratios (D_ra) of the FC_y and FC_fx‐y as‐prepared fibers approached a maximum value as their CNT and/or functionalized CNT contents reached their corresponding optimum values. The maximum D_ra values obtained for FC_fx‐0.001 as‐prepared fiber specimens prepared at varying maleic anhydride grafted polyethylene (PE_‐g‐MAH)/modified CNTs weight ratios were significantly higher that of the FC_0.0015 as‐prepared fiber specimen prepared at the optimum plain CNT content. Tensile property analysis further suggested that excellent orientation and tensile properties of the drawn FC_y and FC_fx‐y fibers can be obtained by ultradrawing the fibers prepared at their optimum plain CNT and/or functionalized CNT contents. To understand the interesting orientation, ultradrawing and tensile properties of FC_y and FC_fx‐y fiber specimens, FTIR, specific surface area, and SEM morphology analysis of the plain and functionalized CNTs were performed in this study. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

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.     

Synthesis and characterization of polyimide/multi‐walled carbon nanotube nanocomposites

Polyimide/multi‐walled carbon nanotube (PI‐MWNT) nanocomposites were fabricated by an in situ polymerization process. Chemical compatibility between the PI matrix and MWNTs is achieved by pretreatment of the carbon nanotubes in a mixture of sulfuric acid and nitric acid. The dispersion of MWNTs in the PI matrix was found to be enhanced significantly after acid modification. The glass transition (T_g) and decomposition (T_d) temperature of PI‐MWNT nanocomposites were improved as the MWNT content increased from 0.5 to 15 wt%. The storage modulus of the PI/MWNT nanocomposites is nine times higher than that of pristine PI at room temperature. The tensile strength of PI doubles when 7 wt% MWNTs is added. The dielectric constant of the PI‐MWNT nanocomposites increased from 3.5 to 80 (1 kHz) as the MWNT content increased to 15 wt%. The present study demonstrates that enhanced mechanical properties can be obtained through a simple in‐situ polymerization process. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Characterization and preparation of new multiwall carbon nanotube/conducting polymer composites by in situ polymerization

Composites based on poly(diphenyl amine) (PDPA) and multiwall carbon nanotubes (MWNTs) were prepared by chemical oxidative polymerization through two different approaches: in situ polymerization and intimate mixing. In in situ polymerization, DPA was polymerized in the presence of dispersed MWNTs in sulfuric acid medium for different molar composition ratios of MWNT and DPA. Intimate mixing of synthesized PDPA with MWNT was also used for the preparation of PDPA/MWNT composites. Transmission electron microscopy revealed that the diameter of the tubular structure for the composite was 10–20 nm higher than the diameter of pure MWNT. Scanning electron microscopy provided evidence for the differences in the morphology between the MWNTs and the composites. Raman and Fourier transform IR (FTIR) spectroscopy, thermogravimetric analysis, X‐ray diffraction, and UV–visible spectroscopy were used to characterize the composites and reveal the differences in the molecular level interactions between the components in the composites. The Raman and FTIR spectral results revealed doping‐type molecular interactions and coordinate covalent‐type interactions between MWNT and PDPA in the composite prepared by in situ polymerization and intimate mixing, respectively. The backbone structure of PDPA in the composite decomposed at a higher temperature (>340°C) than the pristine PDPA (～300°C). This behavior also favored the molecular level interactions between MWNT and PDPA in the composite. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3721–3729, 2006     

Amino‐functionalized multiple‐walled carbon nanotubes‐polyimide nanocomposite films fabricated by in situ polymerization

For the preparation of high‐quality polymeric carbon nanocomposites, it is required that carbon nanotubes are fully compatible with matrix polymers. For this purpose, amino‐functionalized multiple‐walled carbon nanotubes (a‐MWNTs) were synthesized. The a‐MWNTs/polyimide nanocomposite films were prepared through in situ polymerization. According to the spectroscopic characterizations, the a‐MWNTs were homogeneously dispersed in the nanocomposite films as the acid‐functionalized MWNTs. The mechanical properties of the polyimide composite were also studied. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The synthesis of covalent bonded single‐walled carbon nanotube/polyvinylimidazole composites by in situ polymerization and their physical characterization

Single‐walled carbon nanotube (SWCNT) polyvinylimidazole (PVI) composites have been prepared by in situ emulsion polymerization. Dispersion of raw SWCNTs in the PVI matrix was improved by surface modification of the SWCNTs using nitric acid treatment and air oxidation. The carbonyl‐terminated SWCNTs were covalently bonded to PVI by in situ polymerization and the SWCNT/PVI composite was thus obtained. The morphological and structural characterizations of the surface‐functionalized SWCNTs and SWCNT/PVI composites were carried out by Fourier transform infrared spectroscopy, X‐ray diffraction, conductivity measurements, scanning, and transmission electron microscopy. Thermograms of the materials were determined by the differential scanning calorimetry technique. The characterization results indicate that PVI was covalently bonded to SWCNTs and a new material was then obtained. The functionalized SWCNTs showed homogenous dispersion in the composites, whereas purified SWCNT resulted in poor dispersion and nanotube agglomeration. SWCNT/PVI composites exhibited chemical stability enhancement in many common solvents. I–V curves of the samples exhibit an ohmic character. Conductivity values for pure SWCNTs, pure PVI and SWCNT/PVI composite were measured to be 3.47, 2.11 × 10⁻⁹, and 2.3 × 10⁻³ S/m, respectively. Because of resonance, a large dielectric constant is obtained for SWCNT/PVI composite, which is not observed for ordinary materials. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

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.     

Spectroscopic study of double-walled carbon nanotube functionalization for preparation of carbon nanotube / epoxy composites

A spectroscopic study of the amino functionalization of double-walled carbon nanotubes (DWCNT) is performed. Original experimental investigations by near edge X-ray absorption fine structure spectroscopy at the C and O K-edges allow one to follow the efficiency of the chemistry during the different steps of covalent functionalization. Combined with Raman spectroscopy, the characterization gives direct evidence of the grafting of amino-terminated molecules on the structural defects of the DWCNT external wall, whereas the internal wall does not undergo any change. Structural and mechanical investigations of the amino functionalized DWCNT/epoxy composites show coupling between epoxy molecules and the DWCNTs. Functionalization improves the interface between amino-functionalized DWCNT and the epoxy molecules. Electrical transport measurements indicate a percolating network formed only by the inner metallic tubes of the DWCNTs. The activation energy of the barrier between connected metallic tubes is determined to be around 20 meV.     

The preparation of double-walled carbon nanotube/Cu composites by spark plasma sintering, and their hardness and friction properties

Double-walled carbon nanotube (DWCNT)/copper composite powders were prepared by a rapid route involving freeze-drying without oxidative acidic treatment or ball-milling. The DWCNTs are not damaged and are homogeneously dispersed in the matrix. Dense specimens were prepared by spark plasma sintering. The Vickers microhardness is doubled, the wear against a steel or an alumina ball seems very low and the average friction coefficient is decreased by a factor of about 4 compared to pure copper. The best results are obtained for a carbon loading (5 vol%) significantly lower than those reported when using multi-walled carbon nanotubes (10–20 vol%). Maximum Hertzian contact pressure data could indicate that the surface DWCNTs and bundles of them are deformed and broken, possibly resulting in the formation of a graphitized lubricating tribofilm in the contact.