EB treatment of carbon nanotube-reinforced polymer composites

A small amount — less than 0.5% — carbon nanotube reinforcement may improve the mechanical properties of epoxy based composite materials significantly. The basic technical problem on one side is the dispersion of the nanotubes into the viscous matrix resin, namely, the fine powder-like — less than 100 nanometer diameter — nanotubes are prone to form aggregates. On the other side, the good connection between the nanofiber and matrix, which is determining the success of the reinforcement, requires some efficient adhesion promoting treatment. The goal of our research was to give one such treatment capable of industrial size application.A two step curing epoxy/vinylester resin process technology has been developed where the epoxy component has been cured conventionally, while the vinylester has been cured by electron treatment afterwards. The sufficient irradiation dose has been selected according to Raman spectroscopy characterization. Using the developed hybrid resin system hybrid composites containing carbon fibers and multiwalled carbon nanotubes have been prepared.The effect of the electron beam induced curing of the vinylester resin on the mechanical properties of the composites has been characterized by three point bending and interlaminar shear tests, which showed clearly the superiority of the developed resin system. The results of the mechanical tests have been supported by AFM studies of the samples, which showed that the difference in the viscoelastic properties of the matrix constituents decreased significantly by the electron beam treatment.     

A comprehensive assessment on degradation of multi-walled carbon nanotube-reinforced EMA nanocomposites

Thermal degradation kinetics of MWNT-reinforced EMA-based nanocomposites having different methyl acrylate (MA) contents (by % mass) ranging from 9 to 30% have been monitored. Kissinger and Flynn?CWall?COzawa methods for evaluating non-isothermal degradation of polymers have been examined. Overall, the thermal stabilities of the nanocomposites are the function of amount of MWNTs loading and their state of dispersion that depends on the MA content of respective EMAs. Composite samples exhibit higher activation energy (E _a) than the neat EMAs but the E _as of the composites diminish with increased MA contents of the matrices. TG-Mass spectrometry has been used to identify the volatile products resulting from thermal degradation of composites, and a promising mechanism has been proposed over different range of temperatures of degradation. It is proposed that the side-group scission of methoxycarbonyl group initiates thermal decomposition following combination of chain end and random chain scission reactions, ensuing pseudo second-order kinetics.     

Metallic single-walled carbon nanotubes for conductive nanocomposites

This article reports an unambiguous demonstration that bulk-separated metallic single-walled carbon nanotubes offer superior performance (consistently and substantially better than the as-produced nanotube sample) in conductive composites with poly(3-hexylthiophene) and also in transparent conductive coatings based on PEDOT:PSS. The results serve as a validation on the widely held view that the carbon nanotubes are competitive in various technologies currently dominated by conductive inorganic materials (such as indium tin oxide).     

Straightforward synthesis of conductive graphene/polymer nanocomposites from graphite oxide

The reduction of graphite oxide (GO) in the presence of reactive poly(methyl methacrylate) (PMMA), under mild biphasic conditions, directly affords graphene grafted with PMMA. The resulting nanocomposite shows excellent electrical conductivities resulting from the optimal dispersion and exfoliation of graphene in the polymer matrix.     

Effect of nanoplatelet dispersion on mechanical behavior of polymer nanocomposites

By manipulating processing conditions, three levels of exfoliation of synthetic α-zirconium phosphate (α-ZrP) nanoplatelets in epoxy matrices have been achieved. Transmission electron microscopy and wide angle X-ray diffraction were utilized to confirm the three different levels of exfoliation of nanoplatelets in epoxy/α-ZrP nanocomposites. As expected, it was found that modulus and strength of the nanocomposite are affected by how well the nanoplatelets disperse. It was also found that the operative fracture mechanisms depend strongly on the state of the nanoplatelets dispersion. The crack deflection mechanism, which leads to a tortuous path crack growth, was only observed for poorly dispersed nanocomposites. Delamination of intercalated nanoplatelets and crack deflection were observed in a moderately dispersed system. In the case of fully exfoliated system, the crack only propagated in a straight fashion, which indicates that the fully exfoliated individual nanoplatelet can not affect the propagation of crack at all. The implication of the present findings for structural applications of polymer nanocomposites is discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1459–1469, 2007     

Percolation of carbon nanomaterials for high-k polymer nanocomposites

This review summarized the recent progress towards high-k polymer composites bases on the near-percolated networks of carbon nanomaterials by focusing on the effects of distinct network morphologies on the dielectric properties. It is expected to give guidance on designing new near-percolated networks in polymer matrices towards next-generation polymer dielectrics.     

Novel conductive nanocomposites from perfluoropolyether waterborne polyurethanes and carbon nanotubes

The exceptional electrical conductivity of carbon nanotubes (CNTs) has been exploited for the preparation of conductive nanocomposites based on a large variety of insulating polymers. Among these, perfluoropolyether‐polyurethanes (PFPE‐PUs) represent a class of highly performing fluorinated materials with excellent water/oil repellency, chemical resistance, and substrate adhesion. The incorporation of highly conductive fillers to this class of highly performing materials allows them to be exploited in new technological and industrial fields where their unique properties need to be combined with the electrical conductivity or the electrostatic dissipation properties of carbon nanotubes. However, no studies have been presented so far on nanocomposites based on PFPE‐PUs and CNTs. In this work, polymer nanocomposites based on waterborne PFPE‐PUs and increasing amounts of carboxylated multiwall CNTs (COOH‐CNTs) were prepared and characterized for the first time. The effect of increasing concentration of COOH‐CNTs on the physical, mechanical, and surface properties of the nanocomposites was investigated by means of rheological measurements, dynamic mechanical analysis, thermal characterization, optical contact angle measurements, and scanning electron microscopy. In addition, electrical measurements showed that the highly insulating undoped PFPE‐PU system undergoes substantial modifications upon addition of COOH‐CNTs, leading to the formation of conductive nanocomposites with electrical conductivities as high as 1 S/cm. The results of this study demonstrate that the addition of COOH‐CNTs to PFPE‐PU systems represents a promising strategy to expand their possible use to technological applications where chemical stability, water/oil repellence and electrical conductivity are simultaneously required. Copyright © 2014 John Wiley & Sons, Ltd.     

Biodegradable polymer nanocomposites: An overview

Biodegradable polymer nanocomposites, due to their biodegradability and other improved properties possess tremendous scope in the industrial sector. This current article reviews the recent studies carried out over biodegradable polymer nanocomposites that includes preparation, characterization, properties, and applications of nanocomposites based on biodegradable polymers. An orderly introduction of nanocomposites prepared by using various biodegradable aliphatic polyesters and polymers obtained from biomass products has been brought about. A wide range of organic and inorganic nanoparticles was used as additives or fillers to prepare nanocomposites with improved desired properties. Considering vast research on layered silicates/polymer nanocomposites, a special emphasis has been summarized at the end of the review.     

An experimental investigation of the effect of strain on the electrical conductivity of a shape memory polymer

A thermally triggered shape memory polymer (SMP) was prepared by blending electrically conductive carbon black (CB) into the resin prior to curing. The CB filled composite can then be activated through resistive heating. With the aim of using such SMPs in reconfigurable structures and/or actuators, the effect of strain on the conductive nature of the SMP composite was investigated. The study has specifically focused on changes to conductivity in, i) the transverse direction during tensile elongation to assess the impact of the Poisson effect, and ii) in samples deformed in compression. The dynamic response characteristics of the electrically activated SMP were also tested to assess the feasibility of using the composite in tunable vibration damping applications. Findings have shown that the pattern of changes in the transverse conductivity, which is marked by an increase-decrease-increase sequence, resembles that seen in the axial direction. SEM imaging of the samples was performed along the axial and transverse axes of deformation and shows no anisotropy in the CB filler distribution. To demonstrate potential uses of a conductive SMP in the sub-T_g temperature range, a discussion of a vibration damping application has been included.     

An overview of boron nitride based polymer nanocomposites

Recently, boron nitride (BN) based materials have received significant attention in both academic and industrial sectors due to its interesting properties like large energy band gap, good resistance to oxidation, excellent thermal conductivity, thermal stability, chemical inertness, significant mechanical property and widespread applications. This review article deals with the preparation and properties of boron nitride and its nanocomposites with various polymers. Diverse polymers have been explored for the preparation of boron nitride filled polymer nanocomposites by adopting different mixing methods. Properties of the resulting polymer nanocomposites mainly depend up on filler size and dispersion, mixing conditions and type of interaction between polymer matrix and the filler. Herein, the structure, preparation and properties of various boron nitride based polymer nanocomposites are reviewed in detail along with a brief overview of different classes of BN nanomaterials.     

Modeling the solid-like behavior of entangled polymer nanocomposites at low frequency regimes

A theory for the linear viscoelastic behavior of entangled polymeric liquids reinforced with non-aggregated colloidal nanoparticles is presented. Composites with low filler concentration and strong polymer-particle interaction are considered. A fraction of entangled chains is assumed to be reversibly adsorbed on the surface of fillers, due to the affinity between the polymer molecules in the matrix and dispersed filler particles. The relaxation of the system is analyzed by the combination of stress relaxation functions for free and adsorbed polymer chains. It is demonstrated that the emergence of solid-like behavior at low frequency regimes, is due to the significant slow down in relaxation of adsorbed chains. Fitting the model predictions with relevant experimental data indicates that while the effect of constraint release should be considered to obtain a reasonable estimation of neat polymer behavior, the linear combination of stress relaxation functions of free and adsorbed chains (i.e., no thermal constraint release) leads to a better agreement with experimental data of filled systems.     

Eco‐friendly conductive polymer nanocomposites (CPC) for solar absorbers design

To reduce both the cost and the environmental impact of copper‐based thermal solar absorbers, we have investigated their possible substitution by bio‐based conductive polymer nanocomposite (CPC) elements. Our results show that carbon nanotubes (CNT) have no significant influence on polymers’ calorimetric properties such as T_m and T_g but lead to a strong increase in crystallinity of poly(lactic acid) (PLA) and to a lesser extent of poly(amide 12) poly(amide 12) (PA12) for 2 and 3 CNT wt % respectively. Percolation thresholds as low as 0.5 and 0.58 were obtained for PA12 and PLA, respectively, and visco‐elastic properties such as η*, G’ and G” were found to increase exponentially with CNT content confirming the formation of a CNT network within the matrix. All CPC are absorbing more energy in the visible and infrared than in the ultraviolet wavelength ranges. Finally, the thermal conductivity k of PLA–CNT and PA12–CNT were increased, respectively, of 85% and 24%, to reach 0.28 W.m^?1.K^?1 and 0.26 W.m^?1.K^?1, for only 5 wt% CNT. The figure of merit suggests that PA12 is the polymer which satisfies at best all criteria, particularly combining a lower viscosity at almost equivalent thermal conductivity and absorptivity. Copyright © 2013 John Wiley & Sons, Ltd.     

Thermal behavior of multiwall carbon nanotube/zeolite nanocomposites

Summary In this study we report the synthesis and thermal characterization of multiwall carbon nanotubes containing zeolite based nanocomposites. Three different zeolites (LTA, FAU and MFI) were used in this study and it was observed that the morphologies of the synthesized nanocomposites were significantly different. For FAU zeolite nanocrystals with a few nm in diameter were nucleated on the nanotubes covering their surface, however, for LTA and MFI zeolites bulky crystals with nanotubes crossing them were observed by transmission electron microscopy. One of the most important results of our study was the generation of secondary mesoporosity in the zeolites after removing the carbon nanotubes.     

Multiwalled carbon nanotube/polymer nanocomposites: Processing and properties

Nanocomposite materials were prepared with an amorphous poly(styrene‐co‐butyl acrylate) latex as a matrix with multiwalled carbon nanotubes (MWNTs) as fillers. The microstructure of the related films was observed by transmission electron microscopy, which showed that a good dispersion of MWNTs within the matrix was obtained. The linear and nonlinear mechanical behavior and the electrical properties were analyzed. Mechanical characterization showed a mechanical reinforcement effect of the MWNTs with a relatively small decrease of the elongation at break. The composite materials exhibited an elastic behavior with increasing temperature, although the matrix alone became viscous under the same conditions. The electrical conductivity of the composite filled with 3 vol % MWNTs was studied during a tensile test, which highlighted the late damage of the material. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1186–1197, 2005     

Effect of small amounts of metal/carbon nanocomposites on the properties of polymer materials

Metal/carbon nanocomposites have been studied by electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS). EPR study has revealed the existence of delocalized electrons on the carbon shells and the presence of reduced paramagnetic states of nickel in the nickel/carbon nanocomposite. XPS has detected the change in the atomic magnetic moment of the metal. For polycarbonate as an example, conditions for modification of the polymer composition with small amounts of metal/carbon nanoparticles (0.01–0.0001%) have been determined. On the basis of the data obtained, a mechanism of the effect of metal/carbon nanoparticles on the structure and properties of polymer materials has been suggested.     

An experimental and computational investigation on the fragmentation behavior of enaminones in electrospray ionization mass spectrometry

The dissociation pathways of protonated enaminones with different substituents were investigated by electrospray ionization tandem mass spectrometry (ESI‐MS/MS) in positive ion mode. In mass spectrometry of the enaminones, Ar? CO? CH?CH? N(CH₃)₂, the proton transfers from the thermodynamically favored site at the carbonyl oxygen to the dissociative protonation site at ipso‐position of the phenyl ring or the double bond carbon atom adjacent to the carbonyl leading to the loss of a benzene or elimination of C₄H₉N, respectively. And the hydrogen? deuterium (H/D) exchange between the added proton and the proton of the phenyl ring via a 1,4‐H shift followed by hydrogen ring‐walk was witnessed by the D‐labeling experiments. The elemental compositions of all the ions were confirmed by ultrahigh resolution Fourier transform ion cyclotron resonance tandem mass spectrometry (FTICR‐MS/MS). The enaminones studied here were para‐monosubstituted on the phenyl ring and the electron‐donating groups were in favor of losing the benzene, whereas the electron‐attracting groups strongly favored the competing proton transfer reaction leading to the loss of C₄H₉N to form a benzoyl cation, Ar‐CO⁺. The abundance ratios of the two competitive product ions were relatively well‐correlated with the σ_p⁺ substituent constants. The mechanisms of these reactions were further investigated by density functional theory (DFT) calculations. Copyright © 2010 John Wiley & Sons, Ltd.     

Thermally conductive cyanate ester nanocomposites filled with graphene nanosheets and multiwalled carbon nanotubes

In this work, dodecylamine‐modified graphene nanosheets (DA‐GNSs) and γ‐aminopropyl‐triethoxysilane‐treated multiwalled carbon nanotubes (f‐MWCNTs) are employed to prepare cyanate ester (CE) thermally conductive composites. By adding 5 wt% DA‐GNSs or f‐MWCNTs to the CE resin, the thermal conductivities of the composites became 3.2 and 2.5 times that of the CE resin, respectively. To further improve the thermal conductivity, a mixture of the two fillers was utilized. A remarkable synergetic effect between the DA‐GNSs and f‐MWCNTs on improving the thermal conductivity of CE resin composites was demonstrated. The composite containing 3 wt% hybrid filler exhibited a 185% increase in thermal conductivity compared with pure CE resin, whereas composites with individual DA‐GNSs and f‐MWCNTs exhibited increases of 158 and 108%, respectively. Moreover, the composite with hybrid filler retained high electrical resistivity. Scanning electron microscopy images of the composite morphologies showed that the modified graphene nanosheets (GNSs) and multiwalled carbon nanotubes (MWCNTs) were uniformly dispersed in the CE matrix, and a number of junction points among MWCNTs and between MWCNTs and GNSs formed in the composites with hybrid fillers. Generally, we can conclude that these composites filled with hybrid fillers may be promising materials of further improving the thermal conductivity of CE composites. Copyright © 2014 John Wiley & Sons, Ltd.     

The use of surfactants for dispersing carbon nanotubes and graphene to make conductive nanocomposites

Applications of composites based on carbon nanotubes and graphene require their exfoliation and dispersion in a polymer matrix. One of the main approaches to disperse and exfoliate carbon nanotubes and graphene is based on the use of surfactants. Here we review the surfactants utilized for dispersing carbon nanotubes and graphene, the mechanisms of filler stabilization and the methods for composite preparation based on the use of surfactants to get conductive polymer composites with minimum nanofiller loading.