Design and preparation of graphene/poly(ether ether ketone) composites with excellent electrical conductivity

Graphene/poly(ether ether ketone) (m-TRG/PEEK) composites with excellent electrical conductivity were fabricated by hot pressing technique with thermally reduced graphene nanosheets (m-TRG) which were modified by poly(ether sulfone). Moreover, the conductive, thermal, and mechanical properties of PEEK/m-TRG composites were investigated by the precision impedance analyzer, thermal gravimetric analyzer, differential scanning calorimetry, and universal tester, respectively. The electrical conductivity of m-TRG/PEEK composites was greatly improved by incorporating graphene, resulting in a sharp transition from electrical insulator to semiconductor with a low percolation threshold of 0.76 vol.%. A high electrical conductivity of 0.18 S m^?1 was achieved with 3.84 vol.% of m-TRG. The data were compared with those of composites reduced chemically, and the results showed that thermal reduction was an effective method to acquire higher electrical conductive composites. The excellent electrical property should be attributed to the large specific surface area of m-TRG, well dispersion of m-TRG in PEEK matrix, and good compatibility of m-TRG with PEEK matrix, as proven by scanning electron microscope. Besides, m-TRG/PEEK composites also exhibited relatively good thermal and mechanical properties.     

Synergistic effects in network formation and electrical properties of hybrid epoxy nanocomposites containing multi-wall carbon nanotubes and carbon black

Epoxy nanocomposites including multi-wall carbon nanotubes (MWCNT) and carbon black (CB) were produced and investigated by means of electrical conductivity measurements and microscopical analysis. Varying the weight fraction of the nanoparticles, electrical percolation behaviour was studied. Due to synergistic effects in network formation and in charge transport the inclusion of both MWCNT and CB in the epoxy matrix leads to an identical electrical behaviour of this ternary nanocomposite system compared to the binary MWCNT-epoxy system. For both types of nanocomposites an electrical percolation threshold of around 0.025 wt% and 0.03 wt% was observed. Conversely, the binary CB nanocomposites exhibit a three-times higher percolation threshold of about 0.085 wt%. The difference between the binary MWCNT-epoxy and the ternary CB/MWCNT-epoxy in electrical conductivity at high filler concentrations (e.g. 0.5 wt%) turns out to be less than expected. Thus, a considerable amount of MWCNTs can be replaced by CB without changing the electrical properties.     

Cost-efficient high performance polyetheretherketone/expanded graphite nanocomposites with high conductivity for EMI shielding application

The cost efficient expanded graphite (EG) filled polyetheretherketone (PEEK) nanocomposites were prepared by hot pressing, which exhibited an electrical conductivity percolation threshold of 1.5 wt%. The electrical conductivity of the 1.5 wt% nanocomposite increased approximately eleven orders of magnitude than that of pure PEEK. The conductivities of 5 wt% and 10 wt% nanocomposites were increased to about 3.24 S cm⁻¹ and 12.3 S cm⁻¹, respectively. Scanning electron microscope showed 3-dimensional conductive network of EG across the PEEK matrix. The significant increase in electrical conductivity of the nanocomposites leads to the tremendous increase in electromagnetic interference shielding effectiveness.     

Comparison of rheological and electrical percolation phenomena in carbon black and carbon nanotube filled epoxy polymers

Epoxy nanocomposite suspensions including multi-wall carbon nanotubes (MWCNTs) and carbon black (CB) were produced and investigated by means of combined rheological and electrical analysis. The rheological percolation behaviour was compared to the electrical percolation behaviour. Due to similar dynamic agglomeration mechanisms the difference between the rheological and the electrical percolation threshold in the cured state is identical for MWCNT and CB filled systems. Non-covalent matrix–nanoparticle interactions in uncured epoxy suspensions are negligible since the onset of electrical and rheological percolation in the uncured state coincidence. Furthermore, the electrical percolation threshold in the cured state is always lower than in the uncured state because of the high tendency of CB and MWCNTs to form conductive networks during curing. The difference between rheological and electrical percolation threshold is dependent on the curing conditions. Thus, the rheological percolation threshold can be considered as an upper limit for the electrical percolation threshold in the cured state. Due to the formation of co-supporting networks multi-filler (MWCNTs and CB) suspensions exhibit a similar rheological behaviour as the binary MWCNT suspensions. For both types of suspensions a rheological percolation threshold of around 0.2 and 0.25 wt% was determined. Conversely, the binary CB nanocomposites exhibit a four-times higher percolation threshold of about 0.8 wt%. The difference between the binary MWCNT suspension and the ternary CB/MWCNT suspension in storage shear modulus at high filler concentrations (~0.8 wt%) turns out to be less than expected. Thus, synergistic effects in network formation are already present in the epoxy suspension and get more pronounced during curing.     

Preparation and characterization of sulfonated poly(1,3,4-oxadiazole)/multi-walled carbon nanotube composite films with high performance in electric heating and thermal stability

For manufacturing thermally stable electric heating composite films, a sulfonated poly(1,3,4-oxadiazole) (sPOD) was synthesized and it was composited with pristine MWCNT of 0.1–10.0 wt% by an ultrasonicated solution mixing and casting. SEM images revealed that the pristine MWCNTs were dispersed well in the composite matrix via π–π interaction between the MWCNTs and the aromatic rings of sPOD backbone. The electrical resistivity of the composite films decreased considerably from ∼10⁹ Ω cm to ∼10⁰ Ω cm with the increment of the MWCNT content by forming a percolation threshold at ∼0.026 wt%. The composite films with 5.0–10.0 wt% MWCNT contents, which had sufficiently low electrical resistivity of ∼10³–10⁰ Ω cm, exhibited excellent electric heating performance by attaining high maximum temperatures as well as electric energy efficiency. Since the dominant thermal decomposition of the composite films took place at ∼500 °C, sPOD/MWCNT composite films with low electrical resistivity could be used for high performance electric heating materials for advanced applications.     

Percolation threshold and morphology of composites of conducting carbon black/polypropylene/EVA

Conducting carbon black (CB), one of the intrinsic semi-conductors, was added into matrix polypropylene (PP) to prepare conducting composites by means of the melt processing method. Another component EVA was mixed into the composites in order to lower the percolation threshold. The percolation threshold of the ternary CB/PP/EVA composites was merely 3.8 vol%, while it was up to 7.8 vol% for the binary CB/PP composites without EVA. The conductivity of the ternary CB/PP/EVA composites was up to 10^–2 S/cm when the CB percentage was 5 vol%, while that of the binary CB/PP was lower than 10^–2 S/cm when the CB percentage was up to 10 vol%. DSC thermograms of the CB/PP/EVA composites showed that the melting peak shifted to low temperature with increasing CB content. The addition of CB and EVA resulted in the decrease of the crystallinity of PP in the ternary composites. The mechanical properties are also discussed. SEM and TEM were employed to study the morphology of the blend system. The results indicated that CB existed in the form of aggregations in the blend system. The smallest unit that formed a percolation network was grape-like aggregates with some small branches, which consisted of some CB particles, rather than the individual particles. This distribution was very valuable for forming conducting paths and for lowering the percolation value.     

Electrical conductivity and Raman imaging of double wall carbon nanotubes in a polymer matrix

Raman spectroscopy is used to access the dispersion state of DWNTs in a PEEK polymer matrix. The interaction of the outer tube with the matrix can be determined from the line shape of the Raman G band. This allows us to distinguish regions where the nanotubes are well dispersed and regions where the nanotubes are agglomerated. The percolation threshold of the electrical conductivity of the double wall carbon nanotubes (DWNTs)/PEEK nanocomposites is found to be at 0.2-0.3 wt%. We find a maximum electrical conductivity of 3 × 10⁻² S cm⁻¹ at 2 wt% loading. We detect nanotube weight concentrations as low as 0.16 wt% by Raman spectroscopy using a yellow excitation wavelength. We compare the Raman images with transmission electron microscopy images and electrical conductivity measurements. A statistical method is used to find a quantitative measure of the DWNTs dispersion in the polymer matrix from the Raman images.     

Effect of carbon nanotubes on the mechanical properties and crystallization behavior of poly(ether ether ketone)

Pristine carbon nanotubes (CNTs) and noncovalently functionalized carbon nanotubes (f-CNTs) were used to prepare poly(ether ether ketone) (PEEK) composites (CNTs/PEEK and f-CNTs/PEEK) via melt blending. Noncovalently functionalized multiwalled nanotubes were synthesized using hydrogen-bonding interactions between sulfonic groups of sulfonated poly(ether ether ketone) (SPEEK) and carboxylic groups of nanotubes treated by acid (CNTs–COOH). The effects of these two kinds of nanotubes on the mechanical properties and crystallization behavior of PEEK were investigated. CNTs improved mechanical properties and promoted the crystallization rate of PEEK as a result of heterogeneous nucleation. Better enhancement of mechanical properties appeared in the f-CNTs/PEEK composites, which is ascribed to the good interaction between f-CNTs and PEEK. However, the strong interaction of f-CNTs and PEEK chains decreased the crystallization rate of PEEK for high content of f-CNTs.     

Thermally reduced graphene oxide acting as a trap for multiwall carbon nanotubes in bi-filler epoxy composites

The effect of thermally reduced graphene oxide (TRGO) on the electrical percolation threshold of multi wall carbon nanotube (MWCNT)/epoxy cured composites is studied along with their combined rheological/electrical behavior in their suspension state. In contrast to MWCNT and carbon black (CB) based epoxy composites, there is no prominent percolation threshold for the bi-filler (TRGO–MWCNT/epoxy) composite. Furthermore, the electrical conductivity of the bi-filler composite is two orders of magnitude lower (∼1 × 10⁻⁵ S/m) than the pristine MWCNT/epoxy composites (∼1 × 10⁻³ S/m). This result is primarily due to the strong interaction between TRGO and MWCNTs. Optical micrographs of the suspension and scanning electron micrographs of the cured composites indicate trapping of MWCNTs onto TRGO sheets. A morphological model describing this interaction is presented.     

In situ microfibrillar morphology and properties of polypropylene/polyamide/carbon black composites prepared through multistage stretching extrusion

Isotactic polypropylene/polyamide/carbon black (PP/PA/CB) composites with microfibrillar morphology were designed and prepared using a multistage stretching extruder with an assembly of laminating-multiplying elements (LMEs). CB was selectively located in PA. With the increase of LME number from zero to seven, the conductive PA/CB phase was found to experience an elongating-breaking-elongating process. This morphological development resulted in the strong dependence of electrical resistivity on the LME number. When no LME was used, PP/PA/CB materials with 2.0, 3.0, or 4.0 wt% (1.0, 1.6, and 2.1 vol%) CB employed were insulators (resistivity: 10¹⁰ Ω cm) due to their droplet morphology. With the introduction of LMEs, a conductive network was formed because of the microfibrillation of the conductive PA/CB phase; these materials became conductors (resistivity: 10⁴–10⁶ Ω cm). The percolation threshold can lower to 1.5 wt% (0.9 vol%). The low resisticity and percolation threshold cannot be obtained through the conventional method.     

Carbon black reinforced C8 ether linked bismaleimide toughened electrically conducting epoxy nanocomposites

The present work deals with the toughening of brittle epoxy matrix with C8 ether linked bismaleimide (C8 e-BMI) and then study the reinforcing effect of carbon black (CB) in enhancing the conducting properties of insulating epoxy matrix. The Fourier transform infrared spectroscopy (FTIR) and Raman analysis indicate the formation of strong covalent bonds between CB and C8 e-BMI/epoxy matrix. The X-ray diffraction (XRD) and Field Emission Scanning Electron Microscope (FESEM) analysis indicate the event of phase separation in 5 wt% CB loaded epoxy C8 e-BMI nanocomposites. The impact strength increased up to 5 wt% of CB loading with particle pull and crack deflection to be driving mechanism for enhancing the toughness of the nanocomposite and beyond 5 wt% the impact strength started to decrease due to aggregation of CB. The dynamic mechanical analysis (DMA) also indicates the toughness of the nanocomposites was improved with 5 wt% of CB loading due to the phase segregation between epoxy and C8 e-BMI in the presence of CB. The electrical conductivity was also increased with 5 wt% of CB due to classical conduction by ohmic chain contact.     

Electrical, thermal, and mechanical properties of polyarylene ether nitriles/graphite nanosheets nanocomposites prepared by masterbatch route

Graphite nanosheets (GN) reinforced polyarylene ether nitriles (PEN) nanocomposites were successfully fabricated through masterbatch route and investigated for morphological, thermal electrical, mechanical, and rheological properties. The SEM images showed that GN were well coated by phthalonitrile prepolymer (PNP) and dispersed in the PEN matrix. Thermal degradation and heat distortion temperature of PEN/GN nanocomposites increased substantially with the increment of GN content up to 10 wt%. Electrical conductivity of the polymer was dramatically enhanced at low loading level of GN; the electrical percolation of was around 5 wt% of GN. The mechanical properties of the nanocomposites were also investigated and showed significant increase with GN loading. For 10 wt% of GN-reinforced PEN composite, the tensile strength increased by about 18%, the tensile modulus increased by about 30%, the flexural strength increased by about 25%, and the flexural modulus increased by 90%. Rheological properties of the PEN/GN nanocomposites also showed a sudden change with the GN loading content; the percolation threshold was in the range of 3–4 wt% of GN.     

Enhanced conductivity behavior of polydimethylsiloxane (PDMS) hybrid composites containing exfoliated graphite nanoplatelets and carbon nanotubes

Polydimethylsiloxane (PDMS) hybrid composites consisting of exfoliated graphite nanoplatelets (xGnPs) and multiwalled carbon nanotubes functionalized with hydroxyl groups (MWCNTs-OH) were fabricated, and the effects of the xGnP/MWCNT-OH ratio on the thermal, electrical, and mechanical properties of polydimethylsiloxane (PDMS) hybrid composites were investigated. With the total filler content fixed at 4 wt%, a hybrid composite consisting of 75% × GnP/25% MWCNT-OH showed the highest thermal conductivity (0.392 W/m K) and electrical conductivity (1.24 × 10⁻³ S/m), which significantly exceeded the values shown by either of the respective single filler composites. The increased thermal and electrical conductivity found when both fillers are used in combination is attributed to the synergistic effect between the fillers that forms an interconnected hybrid network. In contrast, the various different combinations of the fillers only showed a modest effect on the mechanical behavior, thermal stability, and thermal expansion of the PDMS composite.     

Electrical,rheological and morphological studies in co-continuous blends of polyamide 6 and acrylonitrile–butadiene–styrene with multiwall carbon nanotubes prepared by melt blending

Multiwall carbon nanotubes (MWNT) were incorporated in melt-mixed co-continuous blends of polyamide 6 (PA6) and acrylonitrile–butadiene–styrene (ABS) using a conical twin-screw microcompounder. The state of dispersion of MWNT in the blends was assessed through AC electrical conductivity measurements and melt-rheological investigations. The electrical and rheological percolation threshold in PA6/ABS blends was ～3–4 and ～1–2 wt% MWNT, respectively. A unique reactive modifier (sodium salt of 6-amino hexanoic acid, Na–AHA) was employed to facilitate ‘network-like’ structure of MWNT and to confine them in a specific phase. This was achieved by establishing specific interactions with the delocalized ‘π-electron’ clouds of MWNT and melt-interfacial reaction during melt-mixing. The electrical percolation threshold was significantly reduced in the blends (～0.25 wt%) in the presence of Na–AHA modified MWNT and even coincided with the rheological percolation threshold. Significant refinement in the co-continuous structure was also observed in the presence of Na–AHA modified MWNT.     

Effect of carbon nanotube type and functionalization on the electrical,thermal, mechanical and electromechanical properties of carbon nanotube/styrene–butadiene–styrene composites for large strain sensor applications

Thermoplastic elastomer tri-block copolymer, namely styrene–butadiene–styrene (SBS) composites filled with carbon nanotubes (CNT) are characterized with the main goal of obtaining electro-mechanical composites suitable for large deformation sensor applications. CNT/SBS composites with different filler contents and filler functionalizations are studied by morphological, thermal, mechanical and electrical analyses. It is shown that the different dispersion levels of CNT in the SBS matrix are achieved for pristine or functionalized CNT with strong influence in the electrical properties of the composites. In particular covalently functionalized CNTs show percolation thresholds higher than 8 weight percentage (wt%) whereas pristine CNT show percolation threshold smaller than 1 wt%. On the other hand, CNT functionalization does not alter the conduction mechanism which is related to hopping between the CNT for concentrations higher than the percolation threshold.Pristine single and multiwall CNT within the SBS matrix allow the preparation of composites with electro-mechanical properties appropriate for strain sensors for deformations up to 5% of strain, the gauge factor varying between 2 and 8. Composites close to the percolation threshold show larger values of the gauge factor.     

Complementary percolation characteristics of carbon fillers based electrically percolative thermoplastic elastomer composites

Electrically percolative composites of thermoplastic elastomers (TPE) filled with different concentrations of carbon nanotubes (CNT), carbon black (CB) and (CNT–CB) hybrid fillers were fabricated by melt blending. The effects of filler type and composition on the electrical properties of the percolative TPE composites were studied. Percolation threshold for CB-, CNT- and (CNT–CB)-based composites was found to be 0.06, 0.07 and 0.07 volume fraction respectively. Compared to CB-based composites and earlier reported results, CNT- and (CNT–CB)-based ones revealed an unexpectedly high percolation threshold, which otherwise considered an unwelcome phenomenon, lead to distinct and rare percolation characteristics of CNT filled percolative composites like per-percolation conductivity and a relatively steep percolation curves. CB-based composites showed a comparatively sharp insulator–conductor transition curve complementing the percolation characteristics CNT- and (CNT–CB)-based composites. Percolation threshold conductivity of the fillers was in the order of CB > CNT > (CNT–CB), while maximum attained conductivities followed the order of CNT > (CNT–CB) > CB. Conductivity order of fillers not only denied much reported synergic effect in (CNT–CB) filler but also highlighted the effect of percolation characteristics on the outcome of conductivity values. Results obtained were of theoretical as well as practical importance and were explained in the context of filler morphology and different dispersion characteristics of the carbon based fillers.     

Superior mechanical and electrical properties of multiwall carbon nanotube reinforced acrylonitrile butadiene styrene high performance composites

In-house synthesized multiwall carbon nanotubes (MWCNTs) have been dispersed in acrylonitrile butadiene styrene (ABS) using a micro twin-screw extruder with back flow channel. The electrical and mechanical properties of MWCNTs in ABS with different wt% have been studied. Incorporation of only 3 wt. % MWCNTs in ABS leads to significant enhancement in the tensile strength (up to 69.4 MPa) which was equivalent to 29% increase over pure ABS. The effect of MWCNTs on the structural behaviour of ABS under tensile loading showed a ductile to brittle transition with increase concentration of MWCNTs. The results of enhanced mechanical properties were well supported by micro Raman spectroscopic and scanning electron microscopic studies. In addition to the mechanical properties, electrical conductivity of these composites increased from 10⁻¹² to 10⁻⁵ Scm⁻¹ showing an improvement of ∼7 orders of magnitude. Due to significant improvement in the electrical conductivity, EMI shielding effectiveness of the composites is achieved up to −39 dB for 10 wt. % loaded MWCNTs/ABS indicating the usefulness of this material for EMI shielding in the Ku-band. The mechanism of improvement in EMI shielding effectiveness is discussed by resolving their contribution in absorption and reflection loss. This material can be used as high-strength EMI shielding material.     

Evaluation of thermal,mechanical, and electrical properties of PVDF/GNP binary and PVDF/PMMA/GNP ternary nanocomposites

Graphene nanoplatelet (GNP) was incorporated into poly(vinylidene fluoride) (PVDF) and PVDF/poly(methyl methacrylate) (PMMA) blend to achieve binary and ternary nanocomposites. GNP was more randomly dispersed in binary composites compared with ternary composites. GNP exhibited higher nucleation efficiency for PVDF crystallization in ternary composites than in binary composites. GNP addition induced PVDF crystals with higher stability; however, PMMA imparted opposite effect. The binary composite exhibited lower thermal expansion value than PVDF; the value further declined (up to 28.5% drop) in the ternary composites. The storage modulus of binary and ternary composites increased to 23.1% and 53.9% (at 25 °C), respectively, compared with PVDF. Electrical percolation threshold between 1 phr and 2 phr GNP loading was identified for the two composite systems; the ternary composites exhibited lower electrical resistivity at identical GNP loadings. Rheological data confirmed that the formation of GNP (pseudo)network structure was assisted in the ternary system.     

DC electrical conductivity of poly(methyl methacrylate)/carbon black composites at low temperatures

The study deals with the dc electrical conduction of poly(methyl methacrylate)/carbon black composites of different carbon black (CB) filler concentrations (2, 6, 12 wt%). The dc electrical conductivity was studied as a function of filler concentration, and temperature in the range (20–290 K). It was found that the composites exhibit negative temperature coefficient of resistivity (NTCR) at low temperatures and enhancement in the dc electrical conductivity with both temperature and CB concentration. The observed increase of conductivity with CB concentration was interpreted through the percolation theory. The dependence of the electrical conductivity of the composites in low temperatures was analyzed in term of a formula in consistence with Mott variable rang hopping (VRH) mechanism. The observed overall mechanism of electrical conduction has been related to the transfer of electrons through the carbon black aggregations distributed in the polymer matrix.     

Multi-step microwave reduction of graphite oxide and its use in the formation of electrically conductive graphene/epoxy composites

The multi-step MW reduction technique was developed in this study to obtain reduced graphene oxides; EG, RGO-1, and RGO-2 with MW irradiation time of 1, 2, and 3 min, respectively. Results of TGA, IR, and elemental analysis demonstrated that the degree of reduction of GO increased with increasing the MW irradiation time. Overall, 3 min of MW irradiation of GO in 3 steps was sufficient to obtain highly reduced GO (C/O ratio 10.38 by elemental analysis). The electrical percolation threshold of composites was observed as 1 wt% and 0.3 wt% for RGO-1 and RGO-2, respectively. Even at 0.5 wt% loading of RGO-2 in epoxy, the T_g value of the composite increased by 10 °C, indicating a strong interfacial interaction between graphene and epoxy resin.