Low percolation threshold and high electrical conductivity in melt‐blended polycarbonate/multiwall carbon nanotube nanocomposites in the presence of poly(ε‐caprolactone)

This study focuses on the electrical properties of polycarbonate (PC)/poly(ε‐caprolactone) (PCL)‐multiwall carbon nanotube (MWCNT) nanocomposites. MWCNTs were incorporated into thermoplastic PC matrix by simple melt blending using biodegradable PCL based concentrates with MWCNT loadings (3.5 wt%). Because of the lower interfacial energy between MWCNT and PCL, the nanotubes remain in their excellent dispersion state into matrix polymer. Thus, electrical percolation in PC/PCL‐MWCNT nanocomposites was obtained at lower MWCNT loading rather than direct incorporation of MWCNT into PC matrix. AC and DC electrical conductivity of miscible PC/PCL‐MWCNT nanocomposites were studied in a broad frequency range, 10¹?10⁶ Hz and resulted in low percolation threshold (p_c) of 0.14 wt%, and the critical exponent (t) of 2.09 from the scaling law equation. The plot of logσ_DC versus p^?1/3 showed linear variation and indicated the existence of tunneling conduction among MWCNTs. At low MWCNT loading, the influence of large polymeric gaps between conducting clusters is the reason for the frequency dependent electrical conductivity. Transmission electron microscopy and field emission scanning electron microscopy showed that MWCNTs were homogeneously dispersed and developed a continuous interconnected network path throughout the matrix phase and miscibility behavior of the polymer blend. POLYM. ENG. SCI., 54:646–659, 2014. © 2013 Society of Plastics Engineers     

Preparation, crystallization, electrical conductivity and thermal stability of syndiotactic polystyrene/carbon nanotube composites

A homogeneous dispersion of multi-walled carbon nanotubes (MWCNTs) in syndiotactic polystyrene (sPS) is obtained by a simple solution dispersion procedure. MWCNTs were dispersed in N-methyl-2-pyrrolidinone (NMP), and sPS/MWCNT composites are prepared by mixing sPS/NMP solution with MWCNT/NMP dispersion. The composite structure is characterized by scanning electron microscopy and transmission electron microscopy. The effect of MWCNTs on sPS crystallization and the composite properties are studied. The presence of MWCNTs increases the sPS crystallization temperature, broadens the crystallite size distribution and favors the formation of the thermodynamically stable β phase, whereas it has little effect on the sPS γ to α phase transition during heating. By adding only 1.0 wt.% pristine MWCNTs, the increase in the onset degradation temperature of the composite can reach 20 °C. The electrical conductivity is increased from 10^{−10∼−16} (neat sPS) to 0.135 S m⁻¹ (sPS/MWCNT composite with 3.0 wt.% MWCNT content). Our findings provide a simple and effective method for carbon nanotube dispersion in polymer matrix with dramatically increased electrical conductivity and thermal stability.     

Reduction of percolation threshold through double percolation in melt‐blended polycarbonate/acrylonitrile butadiene styrene/multiwall carbon nanotubes elastomer nanocomposites

We demonstrate a method that involves melt blending of polycarbonate (PC) and melt‐blended acrylonitrile butadiene styrene (ABS) with multiwall carbon nanotubes (MWCNTs) to prepare electrically conducting PC/MWCNT nanocomposites at significantly low MWCNT loading. The partial solubility of ABS in PC led to a selective dispersion of the MWCNTs in the ABS phase after melt‐blending PC and ABS. Thus, a sudden rise in electrical conductivity (∼10⁸ orders of magnitude) of the nanocomposites was found at 0.328 vol% of MWCNT, which was explained in terms of double percolation phenomena. By optimizing the ratio of PC and the ABS–MWCNT mixture, an electrical conductivity of 5.58 × 10⁻⁵ and 7.23 × 10⁻³ S cm⁻¹ was achieved in the nanocomposites with MWCNT loading as low as 0.458 and 1.188 vol%, respectively. Transmission electron microscopy revealed a good dispersion and distribution of the MWCNTs in the ABS phase, leading to the formation of continuous MWCNT network structure throughout the matrix even at very low MWCNT loading. Storage modulus and thermal stability of the PC were also increased by the presence of a small amount of MWCNTs in the nanocomposites.POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Influence of a cyclic butylene terephthalate oligomer on the processability and thermoelectric properties of polycarbonate/MWCNT nanocomposites

The thermoelectric properties of melt-processed nanocomposites consisting of a polycarbonate (PC) thermoplastic matrix filled with commercially available carboxyl (–COOH) functionalized multi-walled carbon nanotubes (MWCNTs) were evaluated. MWCNTs carrying carboxylic acid moieties (MWCNT-COOH) were used due the p-doping that the carboxyl groups facilitate, via electron withdrawing from the electron-rich π-conjugated system. Preliminary thermogravimetric analysis (TGA) of MWCNT-COOH revealed that the melt-mixing was limited at low temperatures due to thermal decomposition of the MWCNT functional groups. Therefore, PC was mixed with 2.5 wt% MWCNT-COOH (PC/MWCNT-COOH) at 240 °C and 270 °C. In order to reduce the polymer melt viscosity, a cyclic butylene terephthalate (CBT) oligomer was utilized as an additive, improving additionally the electrical conductivity of the nanocomposites. The melt rheological characterization of neat PC and PC/CBT blends demonstrated a significant decrease of the complex viscosity by the addition of CBT (10 wt%). Optical and transmission electron microscopy (OM, TEM) depicted an improved MWCNT dispersion in the PC/CBT polymer blend. The electrical conductivity was remarkably higher for the PC/MWCNT-COOH/CBT composites compared to the PC/MWCNT-COOH ones. Namely, the PC/MWCNT-COOH/CBT processed at 270 °C exhibited the best values with electrical conductivity; σ = 0.05 S/m, Seebeck coefficient; S = 13.55 μV/K, power factor; PF = 7.60 × 10⁻⁶μW/m K⁻², and thermoelectric figure of merit; ZT = 7.94 × 10⁻⁹. The PC/MWCNT-COOH/CBT nanocomposites could be ideal candidates for large-scale thermal energy harvesting, even though the presently obtained ZT values are still too low for commercial applications.     

Coupling activity of ionic liquids between diene elastomers and multi-walled carbon nanotubes

In order to ensure better rubber/multi-walled carbon nanotube (MWCNT) compatibility and to enhance the dispersibility, a series of ionic liquids has been tested in regard to an improved interaction between rubber and carbon nanotubes. We found that in the presence of especially one ionic liquid, namely, 1-allyl-3-methyl imidazolium chloride, for the blend of solution-styrene-butadiene and polybutadiene rubber, used as basic elastomer, a three fold increase of tensile strength was achieved with only ∼3 wt.% MWCNT loading. At this low concentration of MWCNTs the sample can be stretched up to 456% without mechanical failure. The use of this ionic liquid additionally results in higher electrical conductivity (10⁻² S cm⁻¹) at low concentration (<3 wt.%) of MWCNTs. Dynamic mechanical analysis confirmed the specific interaction of CNTs and diene rubber chains by showing an extra relaxation process at relatively higher temperature (∼T_g + 130 K) in the temperature sweep measurements. Raman spectroscopic analysis also supported the specific interaction between MWCNTs and rubber molecules with the help of 1-allyl-3-methyl imidazolium chloride. Transmission electron microscopic images confirm the good dispersion of the MWCNTs along with a ‘cellular’-like structure of the CNTs in the rubber matrix.     

Dielectric spectroscopy on melt processed polycarbonate—multiwalled carbon nanotube composites

Complex permittivity and related AC conductivity measurements in the frequency range between 10⁻⁴ and 10⁷ Hz are presented for composites of polycarbonate (PC) filled with different amounts of multiwalled carbon nanotubes (MWNT) varying in the range between 0.5 and 5 wt%. The composites were obtained by diluting a PC based masterbatch containing 15 wt% MWNT by melt mixing using a Micro Compounder. From DC conductivity measurements it was found that for samples processed at a mixing screw speed of 150 rpm for 5 min, the percolation occurs at a threshold concentration (p_c) between 1.0 and 1.5 wt% MWNT. For concentrations of MWNT near the percolation threshold, the processing conditions (screw speed and mixing time) were varied. The differences in the dispersion of the MWNT in the PC matrix could be detected in the complex permittivity and AC conductivity spectra, and have been explained by changes in p_c. The AC conductivity and permittivity spectra are discussed in terms of charge carrier diffusion on percolation clusters and resistor-capacitor composites.     

Low electrical conductivity threshold and crystalline morphology of single-walled carbon nanotubes - high density polyethylene nanocomposites characterized by SEM, Raman spectroscopy and AFM

The electrical conductivities (σ) of nanocomposites of single-walled carbon nanotubes (SWCNTs) and high density polyethylene (HDPE) have been studied for a large number of nanocomposites prepared in a SWCNT concentration range between 0.02 and 8 wt%. The values of σ obey a percolation power law with an SWCNT concentration threshold, p_c = 0.13 wt%, the lowest yet obtained for any kind of carbon-polyethylene nanocomposites. Improved electrical conductivities attest to an effective dispersion of SWCNT in the polyethylene matrix, enabled by the fast quenching crystallization process used in the preparation of these nanocomposites. Characterization by scanning electron microscopy (SEM) and Raman spectroscopy consistently points to a uniform dispersion of separate small SWCNT bundles at concentrations near p_c and increased nanotube clustering at higher concentrations. Near p_c, high activation energies and geometries of long isolated rods suggest that electron transport occurs by activated electron hopping between nanotubes that are close to each other but still geometrically separate. The degree of SWCNT clustering given by Raman spectroscopy and the barrier energy for electrical conductivity are highly correlated. The nanotubes act as nucleants in the crystallization of the polyethylene matrix, and change the type of supermolecular aggregates from spherulites to axialitic-like objects. The size of crystal aggregates decreases with SWCNT loading, however, in reference to the unfilled polyethylene, the three-dimensional growth geometry extracted from the Avrami exponents remains unchanged up to 2 wt%. Consistency between SEM, Raman and electrical transport behavior suggests that the electrical conductivity is dominated by dispersion and the geometry of the SWCNT in the nanocomposites and not by changes or lack thereof in the HDPE semicrystalline structure.     

SnO2-coated multiwall carbon nanotube composite anode materials for rechargeable lithium-ion batteries

SnO₂-coated multiwall carbon nanotube (MWCNT) nanocomposites were synthesized by a facile hydrothermal method. The as-prepared nanocomposites were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The SnO₂/MWCNT composites, when combined with carboxymethyl cellulose (CMC) as a binder, show excellent cyclic retention, with the high specific capacity of 473 mAh g⁻¹ beyond 100 cycles, much greater than that of the bare SnO₂ which was also prepared by the hydrothermal method in the absence of MWCNTs. The enhanced capacity retention could be mainly attributed to good dispersion of the tin dioxide particles in the matrix of MWCNTs, which protected the particles from agglomeration during the cycling process. Furthermore, the usage of CMC as a binder is responsible for the low cost and environmental friendliness of the whole electrode fabrication process.     

Rheology and properties of melt-processed poly(ether ether ketone)/multi-wall carbon nanotube composites

Poly(ether ether ketone) (PEEK)/multi-wall carbon nanotube (MWNT) composites containing up to 17 wt% filler were prepared using a twin screw extruder. Transmission electron microscopy (TEM) images reveal that the MWNTs were homogeneously dispersed in the PEEK matrix. Linear viscoelastic measurements show that both complex viscosity and moduli increase with increasing MWNT concentration. The storage modulus, G^′ exhibits a dramatic seven order increase in magnitude around 1 wt%, leading to a solid-like low-frequency behaviour at higher loadings; the effect can be attributed to network formation at a rheological percolation threshold. Rheotens measurements show that the melt strength also increases significantly on addition of nanotubes, however, the drawability decreases. An analytical Wagner model was used to calculate the apparent elongational viscosity over a wide range of elongational rates, and to reveal significant increases on addition of MWNTs, with a similar threshold behaviour. The electrical response is also dominated by percolation effects, increasing by nearly 10 orders of magnitude from 10⁻¹¹ to 10⁻¹ S/cm, on the addition of only 2 wt% MWNTs. In contrast, the thermal conductivity and tensile elastic modulus of the composites increased linearly with nanotube content, rising by 130% and 50%, at 17 wt% MWNTs, respectively.     

Electrical and rheological percolation in poly(vinylidene fluoride)/multi‐walled carbon nanotube nanocomposites

Nanocomposites of poly(vinylidene fluoride) (PVDF) and multi‐walled carbon nanotubes (MWCNTs) were prepared through melt blending in a batch mixer (torque rheometer equipped with a mixing chamber). The morphology, rheological behavior and electrical conductivity were investigated through transmission electron microscopy, dynamic oscillatory rheometry and the two‐probe method. The nanocomposite with 0.5 wt% MWCNT content presented a uniform dispersion through the PVDF matrix, whereas that with 1 wt% started to present a percolated network. For the nanocomposites with 2 and 5 wt% MWCNTs the formation of this nanotube network was clearly evident. The electrical percolation threshold at room temperature found for this system was about 1.2 wt% MWCNTs. The rheological percolation threshold fitted from viscosity was about 1 wt%, while the threshold fitted from storage modulus was 0.9 wt%. Thus fewer nanotubes are needed to approach the rheological percolation threshold than the electrical percolation threshold. Copyright © 2010 Society of Chemical Industry     

A facile route to develop electrical conductivity with minimum possible multi‐wall carbon nanotube (MWCNT) loading in poly(methyl methacrylate)/MWCNT nanocomposites

Today, we stand at the threshold of exploring carbon nanotube (CNT) based conducting polymer nanocomposites as a new paradigm for the next generation multifunctional materials. However, irrespective of the reported methods of composite preparation, the use of CNTs in most polymer matrices to date has been limited by challenges in processing and insufficient dispersability of CNTs without chemical functionalization. Thus, development of an industrially feasible process for preparation of polymer/CNT conducting nanocomposites at very low CNT loading is essential prior to the commercialization of polymer/CNT nanocomposites. Here, we demonstrate a process technology that involves in situ bulk polymerization of methyl methacrylate monomer in the presence of multi‐wall carbon nanotubes (MWCNTs) and commercial poly(methyl methacrylate) (PMMA) beads, for the preparation of PMMA/MWCNT conducting nanocomposites with significantly lower (0.12 wt% MWCNT) percolation threshold than ever reported with unmodified commercial CNTs of similar qualities. Thus, a conductivity of 4.71 × 10^?5 and 2.04 × 10^?3 S cm^?1 was achieved in the PMMA/MWCNT nanocomposites through a homogeneous dispersion of 0.2 and 0.4 wt% CNT, respectively, selectively in the in situ polymerized PMMA region by using 70 wt% PMMA beads during the polymerization. At a constant CNT loading, the conductivity of the composites was increased with increasing weight percentage of PMMA beads, indicating the formation of a more continuous network structure of the CNTs in the PMMA matrix. Scanning and transmission electron microscopy studies revealed the dispersion of MWCNTs selectively in the in situ polymerized PMMA phase of the nanocomposites. Copyright © 2012 Society of Chemical Industry     

Inter-tube bonding, graphene formation and anisotropic transport properties in spark plasma sintered multi-wall carbon nanotube arrays

Millimeter long, vertically oriented, multi-walled carbon nanotube (MWCNT) arrays were pre-aligned and densified using spark plasma sintering (SPS) technique to form aligned MWCNT bulk samples. The combined results of X-ray powder diffraction, Raman spectroscopy, scanning electron microscopy and high-resolution transmission electron microscopy show that the MWCNTs largely retain their orientation and individual tubular morphology in the aligned MWCNT bulk samples, and that the SPS process induces inter- and intra-tubular bonding as well as graphene formation. In view of the one-dimensional nature of individual MWCNTs, it is particularly noteworthy that the transverse electrical resistivity ρ_T is slightly lower than the longitudinal resistivity ρ_L, whereas the transverse thermal conductivity κ_T is ∼50% of κ_L. The room temperature κ_L is ∼31 W/(m K), one of the highest reported in MWCNT bulk samples. In addition, the thermopower measurements show anisotropy and features of phonon drag.     

Ionic conductivity in polyethylene-b-poly(ethylene oxide)/lithium perchlorate solid polymer electrolytes

The ionic conductivity and phase arrangement of solid polymeric electrolytes based on the block copolymer polyethylene-b-poly(ethylene oxide) (PE-b-PEO) and LiClO₄ have been investigated. One set of electrolytes was prepared from copolymers with 75% of PEO units and another set was based on a blend of copolymer with 50% PEO units and homopolymers. The differential scanning calorimetry (DSC) results, for electrolytes based on the copolymer with 75% of PEO units, were dominated by the PEO phase. The PEO block crystallinity dropped and the glass transition increased with salt addition due to the coordination of the cation by PEO oxygen. The conductivity for copolymers 75% PEO-based electrolyte with 15 wt% of salt was higher than 10⁻⁵ S/cm at room temperature and reached to 10⁻³ S/cm at 100 °C on a heating measurement. The blend of PE-b-PEO (50% PEO)/PEO/PE showed a complex thermal behavior with decoupled melting of the blocks and the homopolymers. Upon salt addition the endotherms associated with PEO domains disappeared and the PE crystals remained untouched. The conductivity results were limited at 100 °C to values close to 10⁻⁴ S/cm and at room temperature values close to 3 × 10⁻⁶ S/cm were obtained for the 15 wt% salt electrolyte. Raman study showed that the ionic association of the highly concentrated blend electrolytes at room temperature is not significant. Therefore, the lower values of conductivity in the case of the blend with 50% PEO can be assigned to the higher content of PE domains leading to a morphology with lower connectivity for ionic conduction both in the crystalline and melted state of the PE domains.     

Spectroscopic characterization of polyaniline formed in the presence of montmorillonite clay

This work shows the spectroscopic characterization of polyaniline-montmorillonite clay (PANI-MMT) composites prepared by polymerization of aniline in aqueous suspensions of montmorillonite clay and camphorsulfonic acid containing persulfate ions as oxidizing agent. X-ray diffraction, scanning electron microscopy, and X-ray absorption near Silicon K-edge data show that morphologies and structures of PANI-MMT nanocomposites depend on their relative amount. The electrical conductivity values of composites increase from 10⁻⁴ to 10⁻¹ S/cm⁻¹ when PANI-MMT ratio increases, and percolation threshold is observed when polymer/clay mass ratio is changed. Resonance Raman, UV-VIS-NIR spectroscopy, electron spin resonance (EPR) and X-ray absorption near Nitrogen K-edge data confirm that PANI has emeraldine salt form for all PANI-MMT materials prepared.     

Ultra-low electrical percolation threshold in carbon-nanotube-epoxy composites

Epoxy composites based on aligned CVD-grown multi-wall carbon nanotubes with weight fractions ranging from as low as 0.001 up to 1 wt% were produced. The resulting electrical properties were analysed by AC impedance spectroscopy. The composite conductivity σ follows a percolation scaling law of the form σ∝(p−p_c)^t with the critical mean concentration p_c to form a conductive network of approximately 0.0025 wt% and an exponent, t, of 1.2. The results are compared to previous studies investigating the percolation behaviour of entangled carbon nanotubes and spherical carbon black particles in the same matrix processed under similar conditions. The experimental percolation threshold for the aligned nanotubes used in this study represents the lowest threshold observed for carbon-nanotube-based polymer composites yet reported.     

Electrical conductivity behavior of epoxy matrix nanocomposites with simultaneous dispersion of carbon nanotubes and clays

In this work, nanocomposites with simultaneous dispersion of multiwalled carbon nanotubes (MWCNT) and montmorillonite clays in an epoxy matrix were prepared by in situ polymerization. A high energy sonication was employed as the dispersion method, without the aid of solvents in the process. The simultaneous dispersion of clays with carbon nanotubes (CNT) in different polymeric matrices has shown a synergic potential of increasing mechanical properties and electrical conductivity. Two different montmorillonite clays were used: a natural (MMT‐Na⁺) and an organoclay (MMT‐30B). The nanocomposites had their electrical conductivity (σ) and dielectric constant (ε_r) measured by impedance spectroscopy. The sharp increase in electrical conductivity was found between 0.10 and 0.25 wt% of the MWCNTs. Transmission electron microscopy (TEM) of the samples showed a lower tendency of MWCNT segregation on the MMT‐30B clay surface, which is connected to intercalation/exfoliation in the matrix, that generates less free volume available for MWCNTs in the epoxy matrix. Data from electrical measurement showed that simultaneously adding organoclay reduces the electrical conduction in the nanocomposite. Moreover, conductivity and permittivity dispersion in low frequency suggest agglomeration of nanotubes surrounding the natural clay (MMT‐Na⁺) particles, which is confirmed by TEM. POLYM. COMPOS., 37:1603–1611, 2016. © 2014 Society of Plastics Engineers     

Development of electrical conductivity with minimum possible percolation threshold in multi-wall carbon nanotube/polystyrene composites

A method is reported that involves the bulk polymerization of styrene monomer in the presence of multi-wall carbon nanotubes (MWCNTs) and polystyrene (PS) beads, for the preparation of MWCNT/PS conducting composites with a significantly lower (0.08 wt.% MWCNT) percolation threshold than previously reported. Thus, the conductivities of 7.62 × 10⁻⁵ and 1.48 × 10⁻³ S cm⁻¹ were achieved in the MWCNT/PS composites through homogeneous dispersion of 0.08 and 0.26 wt.% CNTs, respectively in the in situ polymerized PS region by using 70 wt.% PS beads during the polymerization. The extent of dispersion and location of the MWCNTs in the PS matrix has been investigated with a scanning and transmission electron microscopy. The conductivity of the composites was increased with increasing wt.% of the PS beads at a constant CNT loading, indicating the formation of a more continuous network structure of the CNTs in PS matrix.     

Low percolation thresholds of electrical conductivity and rheology in poly(ethylene terephthalate) through the networks of multi-walled carbon nanotubes

Coagulation method was first used to prepare nanocomposites of multi-wall carbon nanotubes (MWNT) and poly(ethylene terephthalate) (PET). The morphology of nanocomposites is characterized using transmission electronic microscopy and scanning electronic microscopy. A coating on MWNT by PET chains is observed by comparison of micrographs of purified MWNT and MWNT encapsulated by PET chains in the nanocomposites, and this coating is considered as evidence of interfacial interaction between MWNT and PET chains. Both electrical conductivity and rheological properties have been well characterized. With increasing MWNT loading, the nanocomposites undergo transition from electrically insulative to conductive at room temperature, while the melts show transition from liquid-like to solid-like viscoelasticity. The percolation threshold of 0.6 wt% (based on viscosity) for rheological property and 0.9 wt% for electrical conductivity has been found. The low percolation threshold results from homogeneous dispersion of MWNT in PET matrix and high aspect ratio of MWNT. The less rheological percolation threshold than electrical percolation threshold is mainly attributed to the fact that a denser MWNT network is required for electrical conductivity, while a less dense MWNT network sufficiently impedes PET chain mobility related to the rheological percolation threshold.     

High‐performance electromagnetic interference shielding material based on an effective mixing protocol

A facile and economic method is developed for the fabrication of new lightweight materials with high electromagnetic interference (EMI) shielding performance, good mechanical properties and low electrical percolation threshold through melt mixing. Electrical properties, DC conductivity, EMI shielding performance and mechanical properties of poly(trimethylene terephthalate) (PTT)/multiwalled carbon nanotube (MWCNT) nanocomposites with varying filler loading of MWCNTs were investigated. High‐resolution transmission electron microscopy was used to determine the distribution of MWCNTs in the PTT matrix. The newly developed nanocomposites show excellent dielectric and EMI shielding properties. Theoretical electrical percolation threshold was achieved at 0.21 wt% loading of MWCNTs, due to the high aspect ratio and the three‐dimensional network formation of MWCNTs. Experimental DC conductivity values were compared with those of theoretical models such as the Voet, Bueche and Scarisbrick models, which showed good agreement. The PTT/3% MWCNT composite showed an EMI shielding value of ～38 dB (99.99% attenuation) with a sample thickness of 2 mm. Power balance was used to determine the actual contribution of reflection, absorption and transmission loss to the total EMI shielding value. The nanocomposites showed good tensile and impact properties and the composite with 2% MWCNTs exhibited an improvement in tensile strength of as much as 96%. © 2018 Society of Chemical Industry     

Spray deposited fluoropolymer/multi-walled carbon nanotube composite films with high dielectric permittivity at low percolation threshold

High performance perfluoro alkoxy (PFA) and chemical vapor deposition-grown multi-walled carbon nanotube (MWCNT) composite films with thicknesses of 30 μm were prepared using a scalable spray deposition technique. A homogeneous distribution of MWCNTs within the PFA matrix was confirmed by electron and optical microscopy. Dielectric and AC conductivity measurements showed a significant enhancement of dielectric permittivity for PFA/MWCNT films at low frequencies, and a very weak dependence of dielectric permittivity on temperature in the range 25-230 °C. Very low percolation threshold volume fractions of ca. 0.0043 and 0.0017 were attained for MWCNTs with two different aspect ratios, which have been explained by an inherent feature of spray route, a microcapacitor model and percolation theory. The combination of PFA/MWCNT composites and the spray deposition route provides a promising approach for the fabrication of industrial scale composite films with well-controlled dielectric properties for micro-electronic and high temperature applications.