Liquid sensing properties of melt processed polypropylene/poly(ε-caprolactone) blends containing multiwalled carbon nanotubes

The sensing properties of polypropylene (PP)/poly(ε-caprolactone) (PCL) blends containing multiwalled carbon nanotubes (MWNT) were studied in terms of their electrical resistance change in presence of liquids (solvents). The preparation of co-continuous blends based on the double percolation concept was done by melt mixing of electrically conductive PCL composites containing 3 wt.% MWNT and neat PP in ratios of 30:70, 40:60, and 50:50. The electrical resistance change of the PCL-MWNT composites and blends was monitored in a solvent immersion/drying cycle. Various solvents, such as n-hexane, ethanol, methanol, water, toluene, chloroform, and tetrahydrofuran were successfully detected, yielding different responses and reversibility of the resistance changes.PP and PCL were tested separately for solvent sorption using ethanol and n-hexane, both showing a low sorption of n-hexane. Ethanol sorption was large for PCL and almost absent for PP. The 50/50 blend composites with 3 wt.% MWNT in the PCL phase presented larger resistance changes for n-hexane, showing larger sensing ability for this solvent compared to PCL composites with 1 and 3 wt.% loadings. The opposite response was observed for immersion in ethanol where the PCL-MWNT composites showed larger changes than the blends. As the ratio of the conductive PCL phase over PP in the blend composition (i.e. the overall MWNT content) decreased, larger resistance changes were observed. The liquid sensing properties of compression-moulded discs and melt-drawn filaments were compared indicating higher responses for the discs.     

Morphological characterization and modelling of electrical conductivity of multi-walled carbon nanotube/poly(p-phenylene sulfide) nanocomposites obtained by twin screw extrusion

In this study, poly(p-phenylene sulfide) based nanocomposites containing multi-walled carbon nanotubes (MWNTs) were produced by dilution of a 15 wt.% MWNT/PPS masterbatch via twin screw extrusion process. The electrical conductivities of the nanocomposites were measured and percolation threshold was observed below 0.77 vol.% MWNTs. The state of dispersion and distribution quality of MWNTs was analyzed on macro- and nanoscale through transmission light and scanning electron microscopy (SEM). A good deagglomeration of primary macroagglomerates and a homogenous MWNT distribution on nanoscale was found. The dependence of conductivity on MWNT concentration was estimated using statistical percolation theory which matches the experimental data quite well. A new empirical equation was set up to fit the electrical conductivity using quantitative values of visible percolating MWNTs which were detected by charge contrast imaging in SEM.     

Percolation threshold of carbon nanotubes filled unsaturated polyesters

This paper reports on the development of electrically conductive nanocomposites containing multi-walled carbon nanotubes in an unsaturated polyester matrix. The resistivity of the liquid suspension during processing is used to evaluate the quality of the filler dispersion, which is also studied using optical microscopy. The electrical properties of the cured composites are analysed by AC impedance spectroscopy and DC conductivity measurements. The conductivity of the cured nanocomposite follows a statistical percolation model, with percolation threshold at 0.026 wt.% loading of nanotubes. The results obtained show that unsaturated polyesters are a matrix suitable for the preparation of electrically conductive thermosetting nanocomposites at low nanotube concentrations. The effect of carbon nanotubes reaggregation on the electrical properties of the spatial structure generated is discussed.     

Structure–property relationships in isotactic polypropylene/multi-walled carbon nanotubes nanocomposites

In this work, the influence of multi-walled carbon nanotubes (MWCNT) on electrical, thermal and mechanical properties of CNT reinforced isotactic polypropylene (iPP) nanocomposites is studied. The composites were obtained by diluting a masterbatch of 20 wt.% MWCNT with a low viscous iPP, using melt mixing. The morphology of the prepared samples was examined through SEM, Raman and XRD measurements. The effect of MWCNT addition on the thermal transitions of the iPP was investigated by differential scanning calorimetry (DSC) measurements. Significant changes are reported in the crystallization behavior of the matrix on addition of carbon nanotubes: increase of the degree of crystallinity, as well as appearance of a new crystallization peak (owing to trans-crystallinity). Dynamic mechanical analysis (DMA) studies revealed an enhancement of the storage modulus, in the glassy state, up to 86%. Furthermore, broadband dielectric relaxation spectroscopy (DRS) was employed to study the electrical and dielectric properties of the nanocomposites. The electrical percolation threshold was calculated 0.6–0.7 vol.% MWCNT from both dc conductivity and dielectric constant values. This value is lower than previous mentioned ones in literature in similar systems. In conclusion, this works provides a simple and quick way for the preparation of PP/MWCNT nanocomposites with low electrical percolation threshold and significantly enhanced mechanical properties.     

In situ thermal reduction of graphene oxide for high electrical conductivity and low percolation threshold in polyamide 6 nanocomposites

Electrically conductive and thermally stable polyamide 6 (PA 6) nanocomposites were prepared through one-step in situ polymerization of ε-caprolactam monomer in the presence of electrically insulating and thermally unstable graphene oxide (GO) nanosheets. These nanocomposites show a low percolation threshold of ∼0.41 vol.% and high electrical conductivity of ∼0.028 S/m with only ∼1.64 vol.% of GO. Thermogravimetric analysis and X-ray photoelectron spectroscopy results of GO before and after thermal treatment at the polymerization temperature indicate that GO was reduced in situ during the polymerization process. X-ray diffraction patterns and scanning electron microscopy observation confirm the exfoliation of the reduced graphene oxide (RGO) in the PA 6 matrix. The low percolation threshold and high electrical conductivity are attributed to the large aspect ratio, high specific surface area and uniform dispersion of the RGO nanosheets in the matrix. In addition, although GO has a poor thermal stability, its PA 6 nanocomposite is thermally stable with a satisfactory thermal stability similar to those of neat PA 6 and PA 6/graphene nanocomposite. Such a one-step in situ polymerization and thermal reduction method shows significant potential for the mass production of electrically conductive polymer/RGO nanocomposites.     

Electrical conductivity of ion-doped graphite/polyethersulphone composites

The electrical conductivity of polyethersulphone (PES) insulating polymer was improved by incorporation of electrically conductive graphite and ions. An initial conducting pathway of the PES/graphite composites was formed at lower than 3 wt.% of the filler content. LiCl was found to be an effective dopant for the improvement of the electrical conductivities of the PES/graphite composites. By doping with 0.06 wt.% of LiCl the electrical conductivity was enhanced by two orders of magnitude. The enhancement resulted from intercalation of Li⁺ ions into interlayer spaces of the graphite. Upon intercalation, an acceptor GIC, Li-GIC, was consequently formed. The stability of the improved electrical conductivities of the composites contributed with doped-ions was assessed. The electrical conductivity of both un-doped and doped graphite/PES composites slightly increased with increasing temperature and slightly decreased by physical ageing. The enhancement of the electrical conductivities by doping ions was stable at the high temperatures.     

Liquid sensing properties of fibres prepared by melt spinning from poly(lactic acid) containing multi-walled carbon nanotubes

Poly(lactic acid) (PLA)/multi-walled carbon nanotube (MWNT) composites were melt spun with different take-up velocities (max. 100 m/min) to obtain electrically conductive fibres. The incorporation of MWNT contents between 0.5 and 5.0 wt.% was realised in a previous melt mixing process using twin-screw extrusion. The relative resistance change of the fibres caused by contact with different solvents (water, n-hexane, ethanol, methanol) and solvent concentrations was used as liquid sensing response, whereas the time dependent resistance was recorded during immersion and drying cycles. Transmission electron microscopy and Raman spectroscopy indicated enhanced orientation of MWNT along the fibre axis with take-up velocity, resulting in decreased sensitivity during solvent contact. Additionally, sensitivity decreased as the weight content of MWNT increased and was furthermore dependent on the characteristics of used solvents. In context with the targeted application of leakage detection, fibres with low MWNT amount and low draw down ratio (as extruded fibres with 2 wt.% MWNT) are suitable, as they showed relative resistance changes of up to 87% after 10 min immersion in methanol even if the recovery upon drying was suppressed significantly.     

Dielectric properties of montmorillonite clay filled poly(vinyl alcohol)/poly(ethylene oxide) blend nanocomposites

Organic–inorganic nanocomposites of poly(vinyl alcohol) (PVA)–poly(ethylene oxide) (PEO) blend filled with montmorillonite (MMT) nanoclay up to 10 wt.% concentration were synthesized by aqueous solution-cast technique. The complex dielectric function, electrical conductivity, electric modulus and impedance spectra of the nanocomposites were measured in the frequency range 20 Hz–1 MHz at ambient temperature. A direct correlation was observed between the real part of dielectric function and the mean relaxation time of the polymer chain segmental dynamics, with the exfoliated and intercalated MMT clay structures, and the extent of miscibility between PVA and PEO due to hydrogen bonded bridging through exfoliated MMT clay nanosheets. The large increase of dielectric relaxation time revealed that the dispersed exfoliated nanoscale MMT clay in the polymers blend matrix produces a large hindrance to the polymer chain dynamics. Results confirm that the real part of dielectric function of the nanocomposites can be tailored by varying amount of MMT clay filler for their use as nanodielectric materials in the microelectronic technology.     

Enhancement of dielectric and electrical properties in BT/SiC/PVDF three-phase composite through microstructure tailoring

A polymer composite with high dielectric permittivity was prepared by embedding silicon carbide (SiC) whisker with an average diameter of 500 nm–1 μm in poly(vinylidene fluoride) (PVDF). However, the high dielectric loss and electrical conductivity of the two-phase composite prohibits its potential applications. Barium titanate (BT) particles with average diameter of 100 nm and 1 μm were incorporated as a third phase to fabricate a three-phase composite. The morphology structure, dielectric and electrical properties before and after the addition of BT particles were investigated. The three-phase composite exhibits largely suppressed dielectric loss and electrical conductivity without sacrificing the high dielectric permittivity, which was extremely hard to be realized for two-phase composite. It is also found that the nano-size BT is more favorable in achieving high dielectric permittivity than the micro-size BT, where their dielectric loss and electrical conductivity are similar. Furthermore, electric modulus analysis confirms the largely suppressed electron conduction process which results in the enhanced dielectric and electrical properties in three-phase composite.     

Influence of screw configuration,residence time,and specific mechanical energy in twin-screw extrusion of polycaprolactone/multi-walled carbon nanotube composites

Melt processing of thermoplastic-based nanocomposites is the favoured route to produce electrically conductive or electrostatic dissipative polymer composites containing carbon nanotubes (CNT). As these properties are desired at low filler fractions, a high degree of dispersion is required in order to benefit from the intrinsic CNT properties. This study discusses the influence of screw configuration, rotation speed, and throughput on the residence time and specific mechanical energy (SME) and the resulting macroscopic CNT dispersion in polycaprolactone (PCL) based masterbatches containing 7.5 wt.% multi-walled carbon nanotubes (MWNT) using an intermeshing co-rotating twin-screw extruder Berstorff ZE25.     

Rheological properties and electrical conductivity of irradiated MWCNT/PP nanocomposites

Novel rheological features and conductivity results of irradiated PP/MWCNT nanocomposites are presented. Elongational flow measurements reveal a strain hardening behaviour which is compatible with the creation of long chain branched macromolecules provoked by irradiation. However, oscillatory shear flow results suggest that irradiation does not affect interactions of MWCNTs with PP chains. The addition of carbon nanotubes brings about conductivities of the order of 10⁻² S/cm, but its scavenger effect reduces the number of radicals generated by irradiation, lessening the strain hardening effect. The employed mixing method provides a dispersion of MWCNTs in a PP matrix, which followed by an ad hoc irradiation, allows obtaining an electrical conductive polypropylene with a strain hardening behaviour. The obtained results open novel routes to conductive nanocomposites apt to be processed using methods discarded for linear PPs, such extrusion-blowing and others.     

Microstructural image analysis and structure–electrical conductivity relationship of single- and multiple-filler conductive composites

The electrical conductivity of polypropylene/graphite (PP/G) composites and polypropylene/graphite/carbon black (PP/G/CB) was investigated in this paper. The conductivity experimental data of PP/G composites was correlated to theoretical models, which exist in the literature, and the results showed higher values of the exponent t compared to the expected typical values. Moreover, these analytical models were unable to describe the electrical behaviour for multiple-filler conductive composites such as PP/G/CB composites. A 2D computer simulation to numerically compute the electrical conductivity based on digital image analysis was found to be somewhat useful to describe the mechanism of conduction in PP/G/CB composites and to determine the critical factors in developing high electrically conductive composites.     

Effect of carbon nanofibers (CNFs) content on thermal and mechanical properties of CNFs/SiC nanocomposites

Carbon nanofibers dispersed β-SiC (CNFs/SiC) nanocomposites were prepared by hot-pressing via a transient eutectic phase route at 1900 °C for 1 h under 20 MPa in Ar. The effects of additional CNFs content between 1 and 10 wt.% were investigated, based on densification, microstructure, thermal and mechanical properties. The CNFs/SiC nanocomposites by the CNFs contents below 5 wt.% exhibited excellent relative densities over 98% with well dispersed CNFs. However, the CNFs/SiC nanocomposites containing the CNFs of 10 wt.% possessed a relative density of 92%, accompanying CNFs agglomerates and many pores located inside the agglomerates. The three point bending strength gradually decreased with the increase of CNFs content, but the indentation fracture toughness increased to 5.7 MPa m^1/2 by the CNFs content of 5 wt.%. The thermal conductivity was enchanced with the increase of CNFs content and represented a maximum value of 80 W/mK at the CNFs content of 5 wt.%.     

Compatibilizing effect of acrylic acid modified polypropylene on the morphology and permeability properties of polypropylene/organoclay nanocomposites

This work dealt with the morphology and permeability properties of polypropylene/organoclay nanocomposites prepared using an acrylic acid grafted polypropylene (PP-g-AA) as compatibilizing agent. Two PP-g-AA containing the same acrylic acid content (6 wt.%) and having different molar masses were tested. The o-MMT content was 0, 1 or 5 wt.% and the PP-g-AA/o–MMT mass ratio was 0/1, 1/1, 2/1 or 5/1. Results of wide angle X-ray scattering (WAXS) and transmission electron microscopy (TEM) showed that without the PP-g-AA, the o-MMT was dispersed in the PP/o-MMT in a micrometer scale, similar to a conventional microcomposite. With the PP-g-AA, the o-MMT was much better dispersed and its interlayers were intercalated and partly exfoliated by the polymer chains. CO₂ permeability values decreased for all samples with the incorporation of the organoclay. The compatibilized samples showed a more significant reduction in CO₂ permeability, up to 50% when compared to the neat PP. In general, the PP-g-AA acted satisfactorily in compatibilizing PP/organoclay nanocomposites. Moreover, samples prepared with the compatibilizer/organoclay ratio of 5/1 had better barrier properties.     

Thermal conductivity and dielectric properties of Al/PVDF composites

Polymeric composites with relatively high thermal conductivity, high dielectric permittivity, and a low dissipation factor are obtained in the present study. Three types of core-shell-structured aluminum (Al) particles are incorporated in poly(vinylidene fluoride) (PVDF) by melt-mixing and hot-pressing processes. The morphological, thermal, and dielectric properties of the composites are characterized using thermal analysis, a scanning electron microscope, and a dielectric analyzer. The results indicate that the Al particles decrease the degree of crystallinity of PVDF, and that the particle size and shape of the filler affect the thermal conductivity and dielectric properties of Al/PVDF. No variation in the dissipation factor is observed up to 60 wt.% Al. Thermal conductivity and dielectric permittivity values as high as 1.65 W/m K and 230, respectively, as well as a low dissipation factor of 0.25 at 0.1 Hz, are realized for the composites with 80 wt.% spherical Al.     

Highly conducting poly(methyl methacrylate)/carbon nanotubes composites: Investigation on their thermal, dynamic-mechanical, electrical and dielectric properties

Nanocomposites of poly(methyl methacrylate) (PMMA) containing various multi-walled carbon nanotubes (MWCNT) contents were prepared using melt mixing. Several techniques were employed to study the influence of the MWCNT addition on the thermal, mechanical, electrical and dielectric properties of the PMMA matrix. The electrical percolation threshold (p_c) was found to be 0.5 vol.% by performing AC and DC conductivity measurements. Significantly high conductivity levels (σ_dc) were achieved: σ_dc exceeds 10⁻² S/cm already at 1.1 vol.%, the criterion for EMI shielding (σ_dc > 10⁻¹ S/cm) is fulfilled at 2.9 vol.%, and the highest loaded sample (5.2 vol.%) gave a maximum value of 0.5 S/cm. Dielectric relaxation spectroscopy measurements in broad frequency (10⁻¹−10⁶ Hz) and temperature ranges (−150 to 170 °C) indicated weak polymer-filler interactions, in consistency with differential scanning calorimetry and dynamic-mechanical analysis findings. Weak polymer-filler interactions and absence of crystallinity facilitate the achievement of high conductivity levels in the nanocomposites.     

Nanocomposites based on MWCNT and styrene–butadiene–styrene block copolymers: Effect of the preparation method on dispersion and polymer–filler interactions

Composites of Kraton-D® 1102 BT (a styrene–butadiene–styrene block copolymer) and multi-walled carbon nanotubes (MWCNTs) were prepared by melt mixing. The composites were characterized by electrical conductivity measurements (Coleman’s method), mechanical properties (DMA and stress–strain tests), thermal stability (thermogravimetry) and morphology of dispersion (SEM). Finally, the resulting composites were compared with those made by the solution casting method. The results showed a strong influence of the preparation methodology on the final properties of the composites due to changes in morphology. Composites prepared by casting showed a higher electrical conductivity than extruded ones; the composites with 6 wt.% of MWCNT prepared by extrusion presented conductivity of the same order of magnitude as the composite with 1 wt.% of MWCNT prepared by casting – 10⁻³ to 10⁻⁴ S cm⁻¹. However, the extruded samples presented better mechanical properties than the casting ones.     

Thermo-physical properties and TEM analysis of silver based MMCs utilizing metallized multiwall-carbon nanotubes

Metal matrix composites with embedded multiwall-carbon nanotubes (MWNT) are attractive because MWNTs exhibit high intrinsic thermal conductivity. Thus to improve the thermal conductivity of a metal matrix, silver matrix composites with MWNT were prepared by “chemical” mixing, different active elements were introduced enhancing the bonding between inclusions and matrix. The evolution of the thermal conductivity and the coefficient of thermal expansion CTE as a function of the MWNT concentration and the presence of active elements cobalt, molybdenum or nickel in the silver matrix in Ag–X/MWNT composites are presented. A transition from weak to strong matrix/MWNT bonding is observed by adding active elements, the latter leading concomitantly to an increase in thermal conductivity and a decrease in CTE. The thermal conductivity was found to increase by up to 10% for a composition of 0.2 wt.% MWNT and cobalt as active element and a 6% decrease in CTE compared to a pure silver reference.     

Polyethersulfone-expanded graphite nanocomposites: Charge transport and impedance characteristics

Polyethersulfone (PES)-expanded graphite nanocomposites have been prepared by solution blending route after sonicating expanded graphite in dichloromethane. It has been observed that ultrasonication results in nanosheets formation leading to a low percolation threshold of 3 wt.%. At 5 wt.% filler loading the conductivity is of the order of 10⁻² S/cm. Hopping type of charge transport occurs at 3.2 wt.% expanded graphite in PES below which capacitive effects couple. The effective dielectric constant at low frequency increases with filler concentration. Impedance measurement has been carried out to evaluate interfacial capacitance which, for 3.2 wt.% expanded graphite addition in PES, increases to 110 pF from 32 pF for 1 wt.% expanded graphite in the polymer. DSC analysis shows an increment of 12 °C in the T_g of PES with 3 wt.% expanded graphite suggesting interaction between the polymer and filler.     

Conductive network formation in the melt of carbon nanotube/thermoplastic polyurethane composite

This research concerns the effect of conductive network formation in a polymer melt on the conductivity of multi-walled carbon nanotube/thermoplastic polyurethane composite systems. An extremely low percolation threshold of 0.13 wt.% was achieved in hot-pressed composite film samples, whereas a much higher CNT concentration (3–4 wt.%) is needed to form a conductive network in extruded composite strands. This is explained in terms of the dynamic percolation behaviour of the CNT network in the polymer melt. The temperature and CNT concentration needed for dynamic percolation to take effect were studied by the conductivity versus temperature behaviour of extruded strands, in an attempt to optimise the processing conditions.