Influence of nanoparticle-polymer interactions on the apparent migration behaviour of carbon nanotubes in an immiscible polymer blend

We investigate the influence of nanoparticle-polymer interactions on the apparent migration behavior of multiwall carbon nanotubes (CNTs) in an immiscible polymer blend of ethylene-acrylate copolymer (EA) and polyamide 12 (PA). The polymer-CNTs interaction is tuned by using different surface modification strategies, comprising grafting and coating. Poly(methyl methacrylate) (PMMA) and polystyrene (PS) are chosen as surface modifiers. The nanocomposite materials are prepared by melt-blending polymer-modified-CNTs in EA and PA. Polymer-grafted-CNTs tend to concentrate at the PA/EA interface, even if predispersed in PA, as opposed to pristine CNTs, which stay inside PA under the same circumstances. This new behavior is consistent with the morphology of PA/EA/(PMMA or PS) ternary blends and suggest a dominance of interfacial thermodynamics on CNTs localization. If we use polymer-coated-CNTs instead, the behavior depends on molar mass of the coating polymer. For low molar mass, it is similar to that of pristine CNTs and indicates desorption of the coating, owing to the weak interaction with the CNTs surface. Interestingly, we observe that long PS chains do not desorb and can drive the CNTs to the interface of the PA/EA blend. Moreover, the influence of kinetics is clearly observed through the dependence of CNTs interfacial confinement on dispersed droplet size.     

Localization of carbon nanotubes in polyamide 6 blends with non-reactive and reactive rubber

Blending of two immiscible polymer matrices can be an effective way to combine favourable properties of both blend partners. The additional incorporation of multiwalled carbon nanotubes (MWCNTs) in such thermoplastic blends may further enhance the blend properties and especially generate electrical conductivity.     

Polymer transcrystallinity induced by carbon nanotubes

In this work, we provide the evidence of polymer transcrystallinity in the presence of carbon nanotubes (CNTs). The interfacial morphology of carbon nanotube fiber-polypropylene matrix is investigated by means of polarized optical microscopy (POM), wide-angle X-ray diffraction (WAXD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The supramolecular microstructures of polypropylene transcrystals induced by the nanotube fiber are observed in the range of isothermal crystallization temperatures from 118 °C to 132 °C. The dynamic process of transcrystallization is analyzed by using the theory of heterogeneous nucleation. Microstructure analysis shows that the nanotubes can nucleate the growth of both α- and γ-transcrystal, and α-transcrystals dominate the overall interfacial morphology. Close to the nanotube fiber surface, a cross-hatched lamellar microstructure composed of mother lamellae and daughter lamellae is observed.     

Polymer blend emulsion stabilization using carbon nanotubes interfacial confinement

The present study demonstrates the effect of unfunctionalized MultiWalled Carbon Nanotubes (MWNTs) interfacial confinement on coalescence suppression in an immiscible polymer blend exhibiting a sea-island morphology. The effect of carbon nanotubes on morphological stabilization in polyamide (PA)/ethylene-methyl acrylate random copolymer (EA) blends is studied using electronic microscopy techniques. Owing to their interfacial localization, MWNTs are shown to enhance both phase dispersion and stability of the dispersed phase for long mixing time (at least 60 min) and very low filler content (0.5 wt.-% MWNTs) compared to what was previously observed in literature. MWNTs also produce a more uniform distribution of droplets size. The main stabilization mechanism proposed is the formation of a deformable barrier network providing a mechanical barrier against coalescence. Blends stabilized by solid anisotropic nanoparticles, like MWNTs, could therefore offer an interesting alternative to blends compatibilized by block-copolymers.     

The cutting of multi-walled carbon nanotubes and their strong interfacial interaction with polyamide 6 in the solid state

The cutting of multi-walled carbon nanotubes (MWCNTs) using solid state shear milling (S³M) method and their strong interfacial interaction with polyamide 6 (PA6) in the solid state were studied. Transmission electron microscopy showed that after milling, the CNTs were greatly reduced in length, and disentangled, being straighter with open ends. Fourier transform infrared spectra and differential scanning calorimeter analysis indicated the existence of strong interfacial interactions between MWCNTs and PA6 of the pan-milled PA6/CNTs powder. It was further quantified by thermogravimetric analysis that about 30 wt.% of PA6 formed a strong combining force with CNTs after pan-milling. The mechanism of cutting CNTs and the reason for their strong interfacial interactions with PA6 in the solid state were discussed. A fine and homogeneous dispersion of CNTs throughout PA6 matrix was observed by scanning electron microscopy. The tensile properties of the composites prepared by the S³M method were significantly improved compared to those of pure PA6 and composites prepared by conventional melt mixing. Upon incorporation of only 1.5 wt.% MWCNTs, the tensile modulus of PA6 was enhanced from 2448 MPa to 4439 MPa, by about 80%, and the tensile strength was increased by about 23%.     

The effect of carbon nanotubes on the rheology and electrical resistivity of polyamide 12/high density polyethylene blends

Different melt mixing sequences were applied to incorporate multiwalled carbon nanotubes (CNTs) into blends prepared from high density polyethylene (PE) and polyamide 12 (PA). Electron microscopy, rheology and electrical resistivity were used to characterize the morphology and microstructure. At a composition of 75PA/25PE, presence of CNT at the interface promoted by premixing the CNTs in the PE phase, resulted in finer phase morphology and a decrease in the resistivity of up to five decades relative to other mixing procedures used. At a composition of 25PA/75PE, premixing the CNT in the PA phase resulted in their segregation inside and around the PA domains and a four decade lower resistivity. Interestingly, compounds that yielded the lowest resistivity were also characterized by increased low frequency melt storage modulus (G′) which indicates the existence of a correlation between the two properties.     

Dispersability of multiwalled carbon nanotubes in polycarbonate-chloroform solutions

The dispersion of commercial multiwalled carbon nanotubes (MWCNTs, Nanocyl™ NC7000) in chloroform and in polycarbonate (PC)-chloroform solutions was investigated by variation of the polymer concentration, MWCNT amount and sonication time and compared with PC/MWCNT composites, which were processed by melt mixing, subsequently dissolved in chloroform and dispersed via sonication under the same conditions. The sedimentation behaviour was characterised under centrifugal forces using a LUMiSizer^® separation analyser. The space and time resolved extinction profiles as a measure of the stability of the dispersion and the particle size distribution were evaluated. Sonication up to 5 min gradually increases the amount of dispersed particles in the solutions. A significant improvement of the MWCNT dispersion in chloroform was achieved by the addition of PC indicating the mechanism of polymer chain wrapping around the MWCNTs. In dispersions of melt mixed PC/MWCNT composites the dispersion of MWCNTs is significantly enhanced already at a low sonication time of only 0.5 min due to very efficient polymer wrapping during the melt mixing process. However, the best dispersion quality does not lead to the highest electrical conductivity of thin composite films made of these PC/MWCNT dispersions.     

A change of phase morphology in poly(p-phenylene sulfide)/polyamide 66 blends induced by adding multi-walled carbon nanotubes

By adding a small amount of acid treated multi-walled carbon nanotubes (MWCNTs) into poly(p-phenylene sulfide)/polyamide 66 (60/40 w/w) blends, the morphology was found to change from sea-island to co-continuous structure. As the MWCNT content was increased, the morphology came back to sea-island but with increased domain size. It was very interesting to note that the MWCNTs were found to be selectively located in the PA66 phase, and their assembling determines the final morphology of PPS/PA66 blends. A dendritic contacted MWCNTs network was formed at low load, which leads to the formation of a co-continuous structure, and isolated MWCNT aggregates were observed at high load, which leads to the formation of sea-island morphology. Since the properties of multiphase polymeric materials are not only determined by the properties of the component polymers, but also by the morphology formed, our work indicates that the behavior of phase-separating polymer blends containing MWCNTs can be exploited to create a rich diversity of new structures and useful nanocomposites.     

Synthesis and characterization of multi-walled carbon nanotubes reinforced polyamide 6 via in situ polymerization

Polyamide 6 (PA6)/carbon nanotubes (PA6/CNTs) composites have been prepared by in situ polymerization of ε-caprolactam in the presence of pristine and carboxylated multi-walled carbon nanotubes (MWNT and MWNTCOOH). Viscosity measurements show that adding 0.5 wt% of carbon nanotubes (CNTs) does not affect the molecular weight of PA6. Compared with pure PA6, the yield strength of PA6/CNTs composites loaded with 0.5 wt% CNTs is almost unchanged, and the tensile strength is increased slightly. Dynamic mechanical analysis (DMA) demonstrates that both the storage modulus (E′) and glass transition temperature (T_g) of the PA6/CNTs composites increase, particularly for PA6/MWNTCOOH, indicating there is some chemical bonding between PA6 and MWNTCOOH. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and ultra small-angle X-ray scattering (USAXS) show that MWNT and MWNTCOOH are well dispersed in PA6 matrix. Comparison of the USAXS data with a stiff-rod model and wormlike rod model reveals that the CNTs are quite flexible, regardless the degree of chemical modification. Due to the flexibility of CNTs, mechanical properties of the PA6/CNTs composites are marginally enhanced.     

Enhanced interactions between multi-walled carbon nanotubes and polystyrene induced by melt mixing

The effect of melt mixing on the interaction between multi-walled carbon nanotubes (MWNTs) and polystyrene (PS) matrix has been investigated. The interaction between pristine MWNTs and PS in solution was found to exist but not strong enough to allow MWNTs to be soluble in solvent. In contrast, this interaction between MWNTs and PS was significantly enhanced by melt mixing, which led to increased amount of PS-functionalized MWNT exhibiting good solubility in some solvents. The mechanism of melt mixing on this enhanced interaction was attributed to both chemical bonding and physical interaction during the melt mixing.     

Surface functionalities of multi-wall carbon nanotubes after UV/Ozone and TETA treatments

A carbon nanotube (CNT) surface was successfully modified using the UV/Ozone treatment and a triethylenetetramine (TETA) solution for use as the reinforcement for polymer matrix composites. These treatments along with ultra-sonication are aimed to disperse the CNTs uniformly in the resin matrix, as well as to provide the CNT surface with chemical functionalities for adhesion with epoxy resin. Fourier transform infra-red spectroscopy and X-ray photoelectron spectroscopy are performed to evaluate the changes in chemical structure and surface functional groups arising from the UV/O₃ and TETA treatments, confirming the efficiency of the processes. The practical implications of the surface functional groups for improving the interfacial adhesion in CNT-epoxy composites are discussed.     

Influence of composition on the linear viscoelastic behavior and morphology of PP/HDPE blends

In this paper the influence of temperature and composition on the dynamic behavior and morphology of polypropylene (PP)/high-density polyethylene (HDPE) blends were studied. The blend composition ranged from 5 to 30 wt% of dispersed phase (HDPE) and the temperatures ranged from 180 to 220 °C. The interfacial tension between PP and HDPE at temperatures of 180, 200 and 220 °C was obtained from fitting Palierne's emulsion model [1] to the experimental data of PP/HDPE blends with different compositions and from the weighted relaxation spectra of PP/HDPE blends with different compositions, following Gramespacher and Meissner [2] analysis. The interfacial tension between PP and HDPE as inferred from the rheological measurements was shown to depend on PP/HDPE blend composition. However, the results indicated that there is a range of PP/HDPE blend composition for which interfacial tension between PP and HDPE is constant. Considering these values, it was shown that interfacial tension between PP and HDPE decreases linearly with increasing temperature.     

Modified and unmodified multiwalled carbon nanotubes in high performance solution-styrene-butadiene and butadiene rubber blends

The outstanding properties of carbon nanotubes have generated scientific and technical interests in the development of nanotube-reinforced polymer composites. Therefore, we investigated a novel mixing approach for achieving a good dispersion of multiwalled carbon nanotubes (CNTs) in a rubber blend. In this approach the CNTs were incorporated into a 50:50 blend of solution-styrene-butadiene rubber and butadiene rubber. First, the CNTs were predispersed in ethanol and then this CNT-alcohol suspension was mixed with the rubber blend at elevated temperature. The rubber nanocomposites prepared by such method exhibit significantly enhanced physical properties already at very low nanotube concentrations. Additionally, we have analysed the dielectric and thermal properties of the compound. The high aspect ratio of the carbon nanotubes enabled the formation of a conductive percolating network in these composites at concentrations below 2 wt.%. In contrast to the electrical conduction behaviour, the thermal conductivity of the composites has not been influenced significantly by the presence of carbon nanotubes. Dynamic mechanical analysis indicates that the incorporation of CNTs affects the glass transition behaviour by reducing the height of the tan δ peak considerably. Above the glass transition temperature the storage modulus has been increased after incorporation of a small amount of CNTs. Finally, the ‘Payne effect’, an indication of filler-filler interactions, was observed at very low concentrations of CNT in the rubber matrix.     

Structure, composition, and chemical reactivity of carbon nanotubes by selective nitrogen doping

Carbon nanotubes (CNTs) doped with a range of nitrogen contents (0-10 at.%) were prepared via a floating catalyst CVD method using ferrocene, NH₃, and xylene or pyridine. XPS and Raman microscopy were used to assess quantitatively the compositional and structural properties of the nitrogen-doped carbon nanotubes (N-CNTs). XPS analysis indicates a shift in and broadening of the C 1s spectra track with increasing disorder induced by selective nitrogen doping. N 1s XPS spectra show three principle types of nitrogen coordination (pyridinic, pyrolic, and quaternary), with the pyridinic-like fraction selectively increased from 0.0 to 4.5 at.%. First-order Raman spectra were fit with five peaks that vary in intensity and width with nitrogen content. The ratio of the D and G bands’ integrated intensities scaled linearly with nitrogen content. Iodimetric titrations were used to gauge the number of reducing sites on as-prepared N-CNTs, representing the first report of nitrogen doping as a means to deterministically effect the chemical reactivities of carbon nanotubes. The reported methodology for the regulated growth and selective nitrogen doping of CNTs presents new ways to study systematically the influence of nanocarbon composition and structure on chemical and electrochemical reactivity for a host of applications.     

Physical interactions at carbon nanotube-polymer interface

Mechanical properties of carbon nanotube (CNT) reinforced polystyrene rod and CNT reinforced epoxy thin film were studied and the CNT-polymer interface in these composites was examined. Transmission and scanning electron microscopy examinations of CNT/polystyrene (PS) and CNT/epoxy composite showed that these polymers adhered well to CNT at the nanometer scale. Molecular mechanics simulations and elasticity calculations were used to quantify some of the important interfacial characteristics that critically control the performance of a composite material. In the absence of chemical bonding between CNT and the matrix, it is found that the non-bond interactions, consist of electrostatic and van der Waals forces, result in CNT-polymer interfacial shear stress (at 0 K) of about 138 and 186 MPa, respectively, for CNT/epoxy and CNT/PS. The high interfacial shear stress calculated, about an order of magnitude higher than micro fiber reinforced composites, is believed attributed to intimate contact between the two solid phases at the molecular scale. Simulations and calculations also showed that local non-uniformity of CNT and mismatch of the coefficients of thermal expansions between CNT and polymer matrix also promote the stress transfer ability between the two.     

Effect of composition on the linear viscoelastic behavior and morphology of PMMA/PS and PMMA/PP blends

Here, the effect of concentration on the morphology and dynamic behavior of polymethylmethacrylate/polystyrene (PMMA/PS), for PS with two different molecular weight, and polymethylmethacrylate/polypropylene (PMMA/PP) blends was studied. The blends concentrations ranged from 5% to 30% of the dispersed phase (PS or PP). The dynamic data were analyzed to study the possibility of inferring the interfacial tension between the components of the blend from their rheological behavior using Palierne [Palierne JF. Rheol Acta 1990;29:204-14] [1] and Bousmina [Bousmina M. Acta 1999;38:73-83] [2] emulsion models. The relaxation spectrum of the blends was also studied. The dynamic behavior of 85/15 PS/PMMA blend were studied as a function of temperature. It was possible to fit both Palierne and Bousmina's emulsion models to the dynamic data of PMMA/PS blends, to obtain the interfacial tension of the blend. This was not the case for PMMA/PP. The relaxation spectrum of both blends was used to obtain the interfacial tension between the components of the blends. The values of interfacial tension calculated were shown to decrease when the concentration of the blends increased. It was shown using morphological analysis that this phenomenon can be attributed to the coalescence of the dispersed phase during dynamic measurements that occurs for large dispersed phase concentration. When the ‘coalesced’ morphology is taken into account in the calculations the interfacial tension inferred from rheological measurement did not depend on the concentration of the blend used. The values of interfacial tension found analyzing the dynamic behavior of one of the PMMA/PS blend were shown to decrease with temperature.     

Electrooxidation of DNA at glassy carbon electrodes modified with multiwall carbon nanotubes dispersed in polyethylenimine

This work reports the electrochemical response of the complex between dsDNA and PEI formed in solution and at the surface of glassy carbon electrodes (GCE) modified with a dispersion of multi-walled carbon nanotubes in polyethylenimine (CNT-PEI). Scanning Electron Microscopy and Scanning Electrochemical Microscopy demonstrate that the dispersion covers the whole surface of the electrode although there are areas with higher density of CNT and, consequently, with higher electrochemical reactivity. The adsorption of DNA at GCE/CNT-PEI is fast and it is mainly driven by electrostatic forces. A clear oxidation signal is obtained either for dsDNA or a heterooligonucleotide of 21 bases (oligoY) at potentials smaller than those for the oxidation at bare GCE. The comparison of the behavior of DNA before and after thermal treatment demonstrated that the electrochemical response highly depends on the 3D structure of the nucleic acid.     

Diblock copolymer stabilization of multi-wall carbon nanotubes in organic solvents and their use in composites

A versatile method for the preparation of dispersed nanotubes using polystyrene-b-polyisoprene diblock copolymers in different selective organic solvents is presented. Stable dispersions have been obtained in polar (DMF) and apolar (heptane) media depending on the selectivity of the diblock copolymers. They have been characterized by means of optical microscopy, TEM imaging and dynamic light scattering, showing the first demonstration of multiwall carbon nanotubes (MWCNTs) solutions with in situ characterization of diblock copolymer stabilization. The most effectively stabilized dispersions have been used to make nanotube/polystyrene composites. We find that the coating of the nanotubes by the diblock polymer does not prevent electrical transport, so that the system can exhibit a relatively high surface conductivity above the percolation threshold. The low percolation threshold experimentally determined is presumably due to weak attractive interactions between the nanotubes as the composites are dried.     

Barrier properties of polypropylene/polyamide blends produced by microlayer coextrusion

The gas barrier properties of injection molded structures prepared from polymer microlayers were investigated. Polypropylene and polyamide-66 were combined as microlayers with tens to thousands of layers. A thin tie layer of compatibilizer coextruded between the layers provided adhesion. Injection molding the microlayered materials at a temperature intermediate between the melting points of the constituents resulted in a high volume fraction of high aspect ratio polyamide-66 microplatelets dispersed in a polypropylene matrix. The resulting material had significantly reduced permeability to oxygen and carbon dioxide compared to the conventional melt blend. Structural models for permeability indicated that enhanced barrier arose primarily from increased tortuosity of the diffusion pathway provided by the oriented, flat platelets of high aspect ratio in the skin region of the complex injected molded structure.     

Easy synthesis of carbon nanotubes with polypyrrole nanotubes as the carbon precursor

An easy synthesis route for carbon nanotubes with polypyrrole nanotubes as a carbon precursor has been developed. Polypyrrole nanotubes were fabricated via a reactive self-degraded template method. Carbon nanotubes were further obtained by pyrolysis of the polypyrrole nanotube at 900 °C under a nitrogen atmosphere. The resultant carbon nanotube structure was found to be amorphous carbon on the basis of XRD, Raman spectra and high-resolution transmission electron microscopy (HRTEM) studies.