Filler dispersion and electrical properties of polyamide 12/MWCNT-nanocomposites produced in reactive extrusion via anionic ring-opening polymerization

The reactive extrusion of lauryl lactam to polyamide 12 (PA12) of controlled molar mass was successfully performed in a microcompounder. The maximum residual monomer content was less than 1%. The in-situ polymerization in the presence of 1–5 wt.% multiwalled carbon nanotubes (MWCNTs) was studied and the processing conditions were optimized with respect to the electrical resistivity and MWCNT dispersion. Runs which yielded in higher molar mass PA12 resulted in better dispersion of MWCNTs, whereas nanocomposites with lower molar mass PA12 had lower electrical percolation thresholds (MWCNT concentration ∼1 wt.%). A high screw speed of 200 rpm was identified to cause best dispersion and the lowest percolation threshold.     

Preparation and properties of poly (p-phenylene sulfide)/multiwall carbon nanotube composites obtained by melt compounding

In this paper, electrical and mechanical properties of Poly (p-phenylene sulfide) (PPS)/multi-wall carbon nanotubes (MWNTs) nanocomposites were reported. The composites were obtained just by simply melt mixing PPS with raw MWNTs without any pre-treatment. The dispersion of MWNTs and interfacial interaction were investigated through SEM &TEM and Raman spectra. The rheological test and crystallization behavior were also investigated to study the effects of MWNTs concentration on the structure and chain mobility of the prepared composites. Though raw MWNTs without any pre-treatment were used, a good dispersion and interaction between PPS and MWNTs have been evidenced, resulting in a great improvement of electrical properties and mechanical properties of the composites. Raman spectra showed a remarkable decrease of G band intensity and a shift of D bond, demonstrating a strong filler–matrix interaction, which was considered as due to π–π stacking between PPS and MWNTs. The storage modulus (G′) versus frequency curve presented a plateau above the percolation threshold of about 2–3 wt% with the formation of an interconnected nanotube structure, indicative of ‘pseudo-solid-like’ behavior. Meanwhile, a conductive percolation threshold of 5 wt% was achieved and the conductivity of nanocomposites increased sharply by several orders of magnitude. The difference between electrical and rheological percolation threshold, and the effect of critical percolation on the chain mobility, especially on crystallization behavior of PPS, were discussed. In summary, our work provides a simple and fast way to prepare PPS/MWNTs nanocomposites with good dispersion and improved properties.     

Influence of small scale melt mixing conditions on electrical resistivity of carbon nanotube-polyamide composites

Polyamide 6 (PA6) and polyamide 6.6 (PA66) were filled with multiwalled carbon nanotubes (MWNT) using small scale melt mixing under variation of processing conditions, including temperature, rotation speed, and mixing time. In PA66 an electrical percolation threshold of 1 wt% MWNT was found which is lower than that of PA6 at 2.5–4 wt%. In both cases mixing conditions influenced strongly the dispersion and distribution of CNT and the electrical volume resistivity, whereas crystallisation behaviour was only slightly changed. With increasing mixing energy input remaining agglomerates were less in number and smaller, leading to better dispersion. On the other hand, in samples containing 5 wt% MWNT in PA6 electrical volume resistivity showed a minimum at a quite low energy input and then increased considerably with further input of mixing energy. This increase may be related to MWNT breaking during mixing and encapsulation of MWNT by the polyamide chains.     

Electrical and thermal properties of polyamide 12 composites with hybrid fillers systems of multiwalled carbon nanotubes and carbon black

Hybrid filler systems of multiwalled carbon nanotubes (MWCNTs) and carbon black (CB) were incorporated into two types of polyamide 12 (PA12) using small-scale melt mixing in order to identify potential synergistic effects on the interaction of these two electrical conductive fillers. Although no synergistic effects were observed regarding the electrical percolation threshold, at loadings well above the percolation threshold higher volume conductivities were obtained for samples containing both, MWCNT and CB, as compared to single fillers. This effect was more pronounced when using a higher viscous PA12 matrix. The formation of a co-supporting network can be assumed. The combined use of CB and MWCNTs improved the macrodispersion of MWCNT agglomerates, which can be assigned as a synergistic effect. DSC measurements indicated an effect of the nanofiller on crystallisation temperatures of PA12; however this was independent of the kind or amount of the carbon nanofiller.     

Electrical and mechanical characterization of stretchable multi-walled carbon nanotubes/polydimethylsiloxane elastomeric composite conductors

Stretchable, elastomeric composite conductor made of multi-walled carbon nanotubes (MWNTs) and polydimethylsiloxane (PDMS) has been fabricated by simple mixing. Electrical percolation threshold, amount of filler at which a sharp decrease of resistance occurs, has been determined to be ∼0.6 wt.% of MWNTs. The percolation threshold composition has also been confirmed from swelling experiments of the composite; the equilibrium swelling ratio slightly increases up to ∼0.6 wt.%, then decreases at higher amount of filler MWNTs. Upon cyclic stretching/release of the composite, a fully reversible electrical behavior has been observed for composites having filler content below the percolation threshold value. On the other hand, hysteretic behavior was observed for higher filler amount than the threshold value, due to rearrangement of percolative paths upon the first cycle of stretching/release. Finally, mechanical moduli of the composites have been measured and compared by buckling and microtensile test. The buckling-based measurement has led to systematically higher (∼20%) value of moduli than those from microtensile measurement, due to the internal microstructure of the composite. The elastic conductor may help the implementation of various stretchable electronic devices.     

Influence of different carbon nanotubes on the electrical and mechanical properties of melt mixed poly(ether sulfone)-multi walled carbon nanotube composites

Commercial Udel® poly(ether sulfone) (PSU) was filled with three different commercially available multiwalled carbon nanotubes (MWCNTs) by small scale melt mixing. The MWCNTs were as grown NC 7000 and two of its derivatives prepared by ball milling treatment. One of them was unmodified (NC 3150); the other was amino modified (NC 3152). The main difference beside the reactivity was the reduced aspect ratio of NC 3150 and NC 3152 caused by ball milling process. All PSU/MWCNT composites with similar filler content were prepared under fixed processing conditions and comparative analysis of their electrical and mechanical properties were performed and were correlated with their microstructure, characterized by optical microscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). A non-uniform MWCNT dispersion was observed in all composites. The MWCNTs were present in form of agglomerates in the size of 10–60 μm whereas the deagglomerated part was homogeneously distributed in the PSU matrix. The differences in the agglomeration states correlate with the variations of properties between different PSU/MWCNT composites. The lowest electrical percolation threshold of 0.25–0.5 wt.% was observed for the shortened non-functionalized MWCNT composites and the highest for amine-modified MWCNT composites (ca. 1.5 wt.%). The tensile behavior of the three composites was only slightly altered with CNT loading as compared to the pure PSU. However, the elongation at break showed a reduction with MWCNT loading and the reduction was least for composite with best MWCNT dispersion.     

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.     

Morphology and electrical properties of polyamide 6/polypropylene/multi-walled carbon nanotubes composites

Morphology, electrical properties and conductive mechanisms of polyamide 6/polypropylene/muti-walled carbon nanotubes (PA6/PP/MWNTs) composites with varied compositions and different blending sequences were investigated. The MWNTs were found to be located preferentially in the PA6 phase in the composites, whatever the PA6 was continuous or dispersed phase. While the incorporation of MWNTs changed the dispersed PA6 phase from spherical to elongated or irregular shape. The PA6/PP/MWNTs (20/80/4) composite with a dispersed PA6 phase exhibited a higher electrical conductivity in comparison with the PA6/PP/MWNTs (50/50/4) composite which has a co-continuous phase and exhibits double percolation. This was due to the formation of a conductive MWNTs networks in the PA6/PP/MWNTs (20/80/4) composite as proved by means of field emission scanning electron microscopy and rheological measurements. The morphology and electrical properties of the PA6/PP/MWNTs (20/80/4) composites were significantly influenced by blending sequences. When blending 3.9 phr MWNTs with a pre-mixed PA6/PP/MWNTs (20/80/0.1) composite, the dispersed PA6 phase formed an elongated structure, which was beneficial to the electrical properties.     

Comparison of nanotubes produced by fixed bed and aerosol-CVD methods and their electrical percolation behaviour in melt mixed polyamide 6.6 composites

The electrical percolation behaviour of five different kinds of carbon nanotubes (CNTs) synthesised by two CVD techniques was investigated on melt mixed composites based on an insulating polyamide 6.6 matrix. The electrical percolation behaviour was found to be strongly dependent on the properties of CNTs which varied with the synthesis conditions. The lowest electrical percolation threshold (0.04 wt.%) was determined for as grown multi-walled carbon nanotubes without any purification or chemical treatment. Such carbon nanotubes were synthesised by the aerosol method using acetonitrile as ferrocene containing solvent and show relatively low oxygen content near the surface, high aspect ratio, and good dispersability. Similar properties could be found for nanotubes produced by the aerosol method using cyclohexane, whereas CNTs produced by the fixed bed method using different iron contents in the catalyst material showed much higher electrical percolation thresholds between 0.35 and 1.02 wt.%.     

Percolation behaviour of polypropylene glycol filled with multiwalled carbon nanotubes and Laponite

The percolation behaviour of the hybrid composites of polypropylene glycol (PPG) filled with multiwalled carbon nanotubes (MWCNTs) and Laponite RD (Lap), or with MWCNTs and organo-modified Laponite (LapO) was studied by wide angle X-ray diffraction (XRD), microscopic image analysis, and electrical conductivity measurements. Cetyltrimethylammoniumbromide (CTAB) was used as an organo-modifier of Laponite. The Lap and LapO were found to have rather different affinity to PPG. XRD data have evidenced finite PPG integration inside Lap and complete exfoliation of LapO stacks in a PPG matrix. In PPG + MWCNT composites containing no Lap or LapO, increase of MWCNT concentration above the critical value C_p ∼ 0.4 wt% resulted in percolation. The value of the percolation threshold, C_p, was practically the same for hybrid PPG + MWCNT + Lap composites. However, it noticeably decreased (C_p ∼ 0.2 wt%) in PPG + MWCNT + LapO materials. The observed behaviour of the percolation threshold may be attributed to the effects exerted by LapO on the size of MWCNT aggregates, state of their dispersion and homogeneity of their spatial distribution.     

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.     

Analysis of the electrical and rheological behavior of different processed CNF/PMMA nanocomposites

Carbon nanofiber (CNF)/poly(methyl methacrylate) (PMMA) nanocomposites were prepared via melt-compounding, solvent casting and in situ polymerization. Mechanical properties, rheological behavior and electrical resistivity were investigated in specimens with varying CNF loadings. The three processing techniques were compared. Improved properties were obtained in the solvent processed and in situ polymerized composites. The rheological and electrical percolation of these nanocomposites appeared in the same concentration set (between 1 and 5 wt%). No changes were found in melt-compounding, even by the addition of 10 wt% of CNFs. Electrical resistivity of the samples prepared by solvent casting was measured before and after pressing in the hot plate press. It is remarkable that in the non-pressed samples the CNFs formed an efficient 3-D conductive network, yielding composites with percolation thresholds even six orders of magnitude lower than after pressing, where this 3-D network was destroyed.     

Influence of dry grinding in a ball mill on the length of multiwalled carbon nanotubes and their dispersion and percolation behaviour in melt mixed polycarbonate composites

Ball milling of carbon nanotubes (CNTs) in the dry state is a common way to produce tailored CNT materials for composite applications, especially to adjust nanotube lengths. For Nanocyl^TM NC7000 nanotube material before and after milling for 5 and 10 h the length distributions were quantified using TEM analysis, showing decreases of the mean length to 54% and 35%, respectively. With increasing ball milling time in addition a decrease of agglomerate size and an increase of packing density took place resulting in a worse dispersability in aqueous surfactant solutions. In melt mixed CNT/polycarbonate composites produced using masterbatch dilution step, the electrical properties, the nanotube length distribution after processing, and the nano- and macrodispersion of the nanotubes were studied. The slight increase in the electrical percolation threshold in the melt mixed composites with ball milling time of CNTs can be assigned to lower nanotube lengths as well as the worse dispersability of the ball milled nanotubes. After melt compounding, the mean CNT lengths were shortened to 31%, 50%, and 66% of the initial lengths of NC7000, NC7000-5 h, and NC7000-10 h, respectively.     

Multi-walled carbon nanotube-reinforced silicon carbide fibers prepared by polymer-derived ceramic route

Multi-walled carbon nanotube (MWNT)-reinforced silicon carbide (SiC) ceramic fibers were successfully prepared by blending MWNTs (0-0.5 wt.%) with polycarbosilane, followed by melt spinning, curing, and pyrolysis. The MWNTs used in this study were modified with a chemical treatment. It was found that the MWNTs were well-dispersed in the matrix and aligned with the axis of the fibers after ultrasonic dispersion combined with melt spinning. Mechanical measurements revealed that significant improvement in Young’s modulus and tensile strength was achieved by incorporating MWNTs into the ceramic fibers. The addition of 0.5 wt.% MWNTs led to a 93.6% increase in the Young’s modulus and a 38.5% increase in the tensile strength.     

High electrical performance of carbon nanotubes/rubber composites with low percolation threshold prepared with a rotation-revolution mixing technique

The present study demonstrates a novel mixing approach for achieving a good dispersion of carbon nanotubes (CNTs) in a styrene-butadiene rubber (SBR), which leads to a significant improvement in electrical properties. Our mixing technique consists of (1) pretreatment by ultrasonication to disentangle the bundles of CNTs in organic solvent and (2) “rotation-revolution” mixing of the CNTs with SBR without mechanical shear, which prevents CNTs from collapsing during the mixing process. The present mixing method does not require the addition of any dispersing agents (amphiphilic molecules) or chemical modification of the CNTs to obtain a good dispersion. Compared with a conventional Banbury mixing technique, our method leads to a significant decrease in the percolation threshold (less than 1 phr), where the electrical conductivity suddenly increases due to the formation of percolation networks of CNTs in SBR. This is because the aspect ratio of the CNTs was maintained even after the mixing process, whereas CNTs were broken during the conventional Banbury mixing. The effect of using different types of CNTs on electrical conductivity was also investigated. The results show that the percolation threshold is largely related to the structural quality (graphitization) of the CNTs as well as their aspect ratio.     

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.     

Rubber composites based on graphene nanoplatelets,expanded graphite,carbon nanotubes and their combination: A comparative study

Solution styrene butadiene rubber (S-SBR) composites reinforced with graphene nanoplatelets (GnPs), expanded graphite (EG), and multiwalled carbon nanotubes (MWCNTs) were prepared and the electrical and various mechanical properties were compared to understand the specific dispersion and reinforcement behaviours of these nanostructured fillers. The electrical resistivity of the rubber composite gradually decreased with the increase of filler amount in the composite. The electrical percolation behaviour was found to be started at 15 phr (parts per hundred rubber) for GnP and 20 phr for EG filled systems, whereas a sharp drop was found at 5 phr for MWCNT based composites. At a particular filler loading, dynamic mechanical analysis and tensile test showed a significant improvement of the mechanical properties of the composites comprised of MWCNT followed by GnP and then EG. The high aspect ratio of MWCNT enabled to form a network at low filler loading and, consequently, a good reinforcement effect was observed. To investigate the effect of hybrid fillers, MWCNT (up to 5 phr) were added in a selected composition of EG based compounds. The formation of a mixed filler network showed a synergistic effect on the improvement of electrical as well as various mechanical properties.     

Study on dispersion and electrical property of multi-walled carbon nanotubes/low-density polyethylene nanocomposites

Sonication is one of the promising approaches to disperse nanoparticles into the base material thoroughly. Furthermore, coupling treatments for MWNTs and polymer matrix also contribute to homogenous dispersion of MWNTs among polymer matrix. In this paper, MWNTs and KH-550 were dispersed with acetone via sonication method, then, the MWNTs/low density polyethylene (LDPE) composites was prepared by using melt blending process. Effects of MWNTs and LDPE coupling treatment on dispersion and electrical property of the MWNTs/LDPE nanocomposites were investigated. SEM observation on fracture surfaces of the nanocomposites explained the functions of sonication and coupling treatment on the dispersion, and electrical conductivity of the nanocomposites was measured by four-contact scheme. The results displayed that the optimum sonication temperature was 70 °C and the optimum sonication amount of MWNTs particles in 200 ml KH-550 acetone solution was 20 g. Moreover, dispersion of the nanocomposites was improved with increasing sonication power amplitude. Furthermore, dispersion and electrical conductivity of the nanocomposites with coupling treatment LDPE were better than those of the nanocomposites with uncoupling treatment LDPE. The good dispersion and electrical conductivity enhancement are based on the strong bonding and coupling reaction of MWNTs and LDPE matrix, which associated greatly with sonication and coupling treatment.     

Texture,transport and mechanical properties of graphite nanoplatelet/silicone composites produced by three roll mill

Thermally conducting and highly compliant composites for thermal interface applications were developed by dispersing graphite nanoplatelets (GNPs) in silicone polymer using a three-roll mill process. X-ray diffraction and electron microscopy showed that the roll mill produces composites with better dispersion of GNPs than previously achieved by speed and mechanical mixing. The roll mill also allows production of a composite at 25 wt.% GNP loading. The thermal conductivities of the composites reached 1.03 and 3.15 W/m K at 8 and 25 wt.% of GNPs, respectively, compared to 0.17 W/m K for silicone. Compression testing showed that the composites’ moduli increase by 1.5 times up to 20 wt.% loading but the strength and strain to failure decrease. The Shore hardness was similar or slightly lower to that of silicone. The composites are thus promising alternatives to the commercial thermal interface materials currently available.