Aligned carbon cones in free‐standing UV‐Curable polymer composite

A concept where an alternating electric field (dielectrophoresis) is used to assemble and align carbon nanocone particles (CNCs) into microscopic wires in self‐supporting polymer films is demonstrated. The particle fraction is kept low (one‐tenth of the percolation threshold of isotropic mixture), which allows uniform dispersion and efficient UV curing. The alignment leads to the conductivity enhancement of three to four orders of magnitude (from ～10^?7 to ～10^?3 S/m) in the alignment direction. It does not require passing current so the material can be isolated from the alignment electrodes. This prevents electrodes attaching to the film, if the film is adhesive in nature. The alignment can be done using either in‐plane or out‐of‐plane geometries. It is proposed that this concept could be applied in areas such as electrostatic discharge applications where inexpensive conductive or dissipative materials and macroscopic uniformity are prerequisites. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Conductive mechanism of polymer/graphite conducting composites with low percolation threshold

Preparation of the conducting composites of polystyrene/expanded graphite via in situ polymerization and investigation of the conductive mechanism were carried out. They are characterized by high conductivity and a low percolation threshold. The electrical conductivity reached 10^?2 S/cm with 3.0 vol % expanded graphite content, whereas the percolation threshold was 1.0 vol %. Optical micrographs revealed the heterogeneous distribution of the graphite particles and the formation of a conductive network in the polymer matrix. A model of primary particle was proposed to interpret the conductive phenomena. The primary particle is the basic conductive unit in the composites that comprises three of the following parts: the graphite particle, the compact‐adsorbed layer, and the wrapping shell. Our model was also used to explain the experimental data in our previous studies on nylon‐6/expanded graphite composites. A low percolation threshold of conducting composites can be also explained according to the model of the primary particle. Furthermore, the theoretical line of conductivity versus primary particle content calculated from the revised Flory's theory fits the experimental data well. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 954–963, 2002     

Influence of polymer particle size on the percolation threshold of electrically conductive latex‐based composites

Monodispersed copolymer emulsions, each with a different polymer particle size, were used to investigate the effect of particle size on the electrical and thermomechanical properties of carbon black (CB)‐filled segregated network composites. These emulsions were synthesized with equal moles of methyl methacrylate and butyl acrylate, with latex particle size ranging from 83 to 771 nm. The electrical percolation threshold was found to decrease from 2.7 to 1.1 vol % CB as the latex particle size was increased. Microstructural images reveal diminished latex coalescence, and improved CB segregation, with increasing latex particle size. In general, coalescence is shown to increase for all systems with increasing CB concentration. Furthermore, all systems exhibited a similar maximum electrical conductivity plateau of 0.7 S cm^?1, albeit at lower concentration for larger latex particle size. This ability to tailor percolation threshold with latex particle size provides an important tool for manipulating electrical and mechanical properties of polymer nanocomposites. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1547–1554, 2011     

Novel phthalocyanine crystals as a conductive filler in crosslinked epoxy materials: Fractal particle networks and low percolation thresholds

Novel nanosized crystals of aquocyanophthalocyaninatocobalt (III) (Phthalcon 11) were used as a conductive filler in crosslinked epoxy materials. The crosslinked composite materials had a very low percolation threshold (φ_c ≈ 0.9 vol %). The relationship between the volume conductivity and the filler fraction follows the scaling law of the percolation theory and suggests that the conducting particle networks were formed by random percolation of primary aggregates. The occurrence of the low φ_c can be explained by the presence of a fractal Phthalcon 11 particle network formed from fractal aggregates during crosslinking. The position of the percolation threshold and the volume conductivity of these crosslinked materials were found to depend heavily on the processing conditions applied. These dependencies are explained in terms of specific particle–matrix interactions and the particle–particle interactions and by taking into account different mechanisms of particle network formation. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 33–47, 2006     

Electrical conducting behaviors in polymeric composites with carbonaceous fillers

Several kinds of polymer composites with carbonaceous fillers such as carbon black (CB), vapor‐grown carbon fiber (CF), and carbon nanotube (CNT) are prepared by a gelation/crystallization process or a melt mixing method. The electrical phenomena, changes of electrical conductivities with different filler's type, filler's concentration and temperatures, and the mechanism of electron transport in these carbon‐filled polymer composites are directly influenced by the geometric grain shape and aggregating morphology of the fillers dispersed in the polymer matrix. For the composites of CB and CF, long‐range macroscopic conduction are governed by the percolation phenomenon, the conduction is behaved through the conductive path formed by the conductors' contacting, and the thermal expansion changes the physical dimensions of the entire electrical network and leads to the changes in the electrical phenomenon. Microscopic conduction between conductive elements is influenced by the tunneling barrier or tunneling voltage, which varies with the temperature change, explaining the apparent observation of the temperature dependence of the composites. In comparison with fillers of CB and CF, the CNT performs unique electric properties for their nonspherical geometry and morphology as a three‐dimensional network (high structures), which has been visually proved by SEM photos in our former research, leading to the percolation threshold lower than 1% in the volume fraction and much less temperature dependence in its composites. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1037–1044, 2007     

Negative dielectrophoretic patterning with colloidal particles and encapsulation into a hydrogel

Microparticle patterns have been fabricated on a nonconductive glass substrate and a conductive indium tin oxide (ITO) substrate using negative dielectrophoresis (n-DEP). The patterned microparticles on the substrate were immobilized by covalent bonding or embedded into polymer sheets or strings. The patterning device consisted of an ITO interdigitated microband array (IDA) electrode as the template, a glass or ITO substrate, and a polyester film (10-microm thickness) as the spacer. A suspension of 2-microm-diameter polystyrene particles was introduced into the device between the upper IDA and the bottom glass or ITO support. An ac electrical signal (typically 20 Vpp, 3 MHz) was then applied to the IDA, resulting in the formation of line patterns with low electric field gradient regions on the bottom support. When the glass substrate was used as the bottom support, the particles aligned under the microband electrodes of the IDA within 5 s because the aligned areas on the support were regions with the weakest electric field; however, for the ITO support, the particles were directed to the regions under the electrode gap and aligned on the support because these regions had the weakest electric field. The width of the particle lines could be roughly controlled by regulating the initial concentration of the suspended particles. The particles forming the line and grid patterns with single-particle widths were immobilized by using a cross-linking reaction between the amino groups on the aligned particles and N-hydroxysuccinimide-activated ester on the glass substrate activated by succinimidyl 4-(p-maleimidophenyl)-butyrate (SMPB). The patterned particles were also embedded in a photoreactive hydrogel polymer. A prepolymer solution of poly(ethylene glycol) diacrylate (PEG-DA) was used as the suspension medium to maintain the particle patterns in the polymerized hydrogel sheet and string following photopolymerization. The hydrogel sheets with particle patterns were fabricated by ultraviolet (UV) irradiation through the ITO-IDA template for 120 s. Hydrogel strings with the aligned particles were fabricated by using a conductive ITO support and a Pt-IDA template. Pt-IDA was used as a template as well as a photomask to block UV transmission. The present procedure affords extremely simple, rapid, and highly reproducible fabrication of particle arrays. The reusability of the template IDA electrode is also a substantial advantage over previous methods.     

An approach to one‐dimensional conductive polymer composites

A substantial approach to one‐dimensional (1D) electrically conductive composites was proposed which was based on the thermodynamic analysis of electric‐field‐induced particle alignment in a nonpolar thermoplastic polymer matrix. The process condition window was based on the real‐time exploration of dynamic percolation under different electric fields with carbon black (CB)‐filled polyethylene as a model. The CB content was the main factor of the process condition. Its upper limit was set as the critical percolation concentration at the thermodynamic equilibrium state without an electric field to eliminate the possibility of conductive network formation perpendicular to the electric‐field direction, whereas its lower limit the critical percolation concentration at the thermodynamic equilibrium state under a critical electric field (E*). A composite with CB content in this window, isothermally treated in an electric field not less than E*, showed conductivity in the electric‐field direction about 10⁵ times larger than that in the perpendicular direction. A 1D cluster structure in the direction of the electric filed was confirmed with scanning electron microscopy morphology observations. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 184–189, 2005     

Percolation in carbon black filled epoxy resin

The conditions to form a conductive network in carbon black filled epoxy resin were examined. It was found that the formation is controlled by particle-particle interaction which can be influenced by shear forces or by the ionic concentration of the resin. Therefore the network morphology and thus the percolation threshold depends strongly upon the processing route. On best conditions the percolation threshold was reduced to 0.06 vol.-%. That a continuous network can form with such a low volume fraction can be explained by the fractal dimension of agglomerates the network is made of.     

Fundamental study of crystallization,orientation, and electrical conductivity of electrospun PET/carbon nanotube nanofibers

The morphology, structure, and properties of polyethylene terephthalate (PET)/Carbon Nanotubes (CNT) conductive nanoweb were studied in this article. Nanocomposite nanofibers were obtained through electrospinning of PET solutions in trifluoroacetic acid (TFA)/dichloromethane (DCM) containing different concentrations and types of CNTs. Electrical conductivity measurements on nanofiber mats showed an electrical percolation threshold around 2 wt % multi‐wall carbon nanotubes (MWCNT). The morphological analysis results showed smoother nanofibers with less bead structures development when using a rotating drum collector especially at high concentrations of CNTs. From crystallographic measurements, a higher degree of crystallinity was observed with increasing CNT concentrations above electrical percolation. Spectroscopy results showed that both PET and CNT orientation increased with the level of alignment of the nanofibers when the nanotube concentration was below the electrical percolation threshold; while the orientation factor was reduced for aligned nanofibers with higher content in CNT. Considerable enhancement in mechanical properties, especially tensile modulus, was found in aligned nanofibers; at least six times higher than the modulus of random nanofibers at concentrations below percolation. The effect of alignment on the mechanical properties was less important at higher concentrations of CNTs, above the percolation threshold. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 2052–2064, 2010     

Viscoelastic properties of ionic polymer composites reinforced by soy protein isolate

Both linear and nonlinear viscoelastic properties of ionic polymer composites reinforced by soy protein isolate (SPI) were studied. Viscoelastic properties were related to the aggregate structure of fillers. The aggregate structure of SPI is consisted of submicron size of globule protein particles that form an open aggregate structure. SPI and carbon black (CB) aggregates characterized by scanning electron microscope and particle size analyzer indicate that CB aggregates have a smaller primary particle and aggregate size than SPI aggregates, but the SPI composites have a slightly greater elastic modulus in the linear viscoelastic region than the CB composites. The composite containing 3–40 wt % of SPI has a transition in the shear elastic modulus between 6 and 8 vol % filler, indicating a percolation threshold. CB composites also showed a modulus transition at <6 vol %. The change of fractional free volume with filler concentration as estimated from WLF fit of frequency shift factor also supports the existence of a percolation threshold. Nonlinear viscoelastic properties of filler, matrix, and composites suggested that the filler‐immobilized rubber network generated a G′ maximum in the modulus‐strain curves and the SPI formed a stronger filler network than the CB in these composites. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3503–3518, 2005     

Filler size effects on the conductivity of polymer nanocomposites: Semiconductive phthalocyanine nanoparticles in epoxy matrices

Three Cobalt(III) phthalocyanine (Phthalcon) powders with different particle sizes and chemical compositions, but almost equal XRD spectra and powder conductivity were synthesized and used as conductive fillers in crosslinked epoxy matrices. Two of these Phthalcons are new compounds. The relation between the conductivity of the composites and the type and amount of filler used was determined. The influence of particle size and chemical composition on this relation appeared to be minimal. These composites had a percolation threshold of 0.9 vol % and a maximum volume conductivity of 10^?7 S/cm. Detailed analysis showed that the particle networks have very similar fractal structures and that they are likely to be formed by diffusion limited cluster‐cluster aggregation during processing. Evidence is presented that these particle networks are formed at an early stage of crosslinking and that the charge transfer between particles in the networks is neither limited by the Phthalcon particle size, nor by the presence of polymer matrix between the particles. The maximum volume conductivity of these composites is likely to be limited by the amount of filler used, the crystal structure defects on the particle surface, and the fractality and the imperfection of the particle networks. The impact of these findings on the conductivity of other polymer nanocomposites is discussed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1079–1093, 2008     

两种碳材料混合填充聚合物复合材料的导电特性及渗流阈值的计算模型

介绍了用碳纳米管与炭黑（或石墨）混合填充的聚合物复合材料的导电特性;阐述了混合填充聚合物体系的导电机理;介绍了基于线性混合规则和已占体积理论的渗流阈值的计算模型;分析了模型计算值与实验值的差异。利用已占体积理论,重新推导了混合填充体系渗流阈值的计算公式,并与文献公式做了比较。新公式表明：混合填充聚合物复合材料的渗流阈值...     

Reduced percolation thresholds of immiscible conductive blends

The DC conductivity of polymer blends composed of poly(ethylene‐co‐vinyl acetate) (EVA) and high density polyethylene (HDPE), where a conductive carbon black (CB) had been preferentially blended into the HDPE, were investigated to establish the percolation characteristics. The blends exhibited reduced percolation thresholds and enhanced conductivities above that of the individually carbon filled HDPE and EVA. The percolation threshold of the EVA/HDPE/CB composites was between 3.6 and 4.2 wt % carbon black, where the volume resistivity changed by 8 orders of magnitude. This threshold is at a significantly lower carbon content than the individually filled HDPE or EVA. At a carbon black loading of 4.8 wt %, the EVA/HDPE/CB composite exhibits a volume resistivity which is approximately 14 and 11 orders of magnitude lower than the HDPE/CB and EVA/CB systems, respectively, at the same level of incorporated carbon black. The dielectric response of the ternary composites, at a temperature of 23°C and frequency of 1 kHz, exhibited an abrupt increase of ca. 252% at a carbon concentration of 4.8 wt %, suggesting that the percolation threshold is somewhat higher than the range predicted from DC conductivity measurements. Percolating composites with increasing levels of carbon black exhibit significantly greater relative permittivity and dielectric loss factors, with the composite containing 6 wt % of carbon black having a value of ϵ′ ≈ 79 and ϵ″ ≈ 14. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1899–1910, 1999     

Enhanced Conductivity and mechanical properties of polyimide based nanocomposite materials with carbon nanofibers via carbonization of electrospun polyimide fibers

Carbon nanofibers (CNF) have been obtained by the thermal treatment of the electrospun polyimide fibers in our present work. The carbon structure and surface morphology of the as-received CNFs were investigated using X-ray diffraction, Raman spectroscopy, and scanning electron microscopy. Investigations of the nanocomposite materials fabricated using these CNFs as conductive fillers and polyimide as matrix show that the presence of CNFs can improve both the mechanical and electrical properties of the material. The conductivity of the nanocomposite films increases with increases in the CNF content and a percolation threshold of about 6.3 vol % (0.0785 in weight fraction) is calculated according to percolation theory.     

Structure and dynamics of carbon black‐filled elastomers

The linear and nonlinear melt viscoelastic properties for a series of carbon black‐filled polymer composites were studied. Complementary tapping‐mode atomic force microscopy (AFM) studies were used to examine the dispersion and structural correlations of the filler particles in these composites. The low‐frequency dependence of the linear viscoelastic moduli gradually changes from liquidlike behavior for the unfilled polymer to pseudosolid character for composites with more than 9 vol % carbon black filler. The plateau modulus, inferred from the linear viscoelastic response, exhibits a somewhat discontinuous change at about 9 vol % filler. On the basis of the linear viscoelastic response, we postulate that the carbon black filler forms a continuous percolated network structure beyond 9 vol % filler, considerably lower than that expected from theoretical calculations for overlapping spheres and ellipsoids. We suggest that the lower threshold for percolation is due to the polymer mediation of the filler structure, resulting from the low functionality of the polymer and, consequently, few strong polymer–filler interactions, allowing for long loops and tails that can either bridge filler particles or entangle with one another. Furthermore, the strain amplitude for the transition from linear behavior to nonlinear behavior of the modulus for the composites with greater than 9 vol % filler is independent of frequency, and this critical strain amplitude decreases with increasing filler concentration. Complementary AFM measurements suggest a well‐dispersed carbon black structure with the nearest neighbor distance showing a discontinuous decrease at about 9 vol % filler, again consistent with the formation of a filler network structure beyond 9 vol % carbon black. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 256–275, 2001     

Rheology,electrical conductivity,and the phase behavior of cocontinuous PA6/ABS blends with MWNT: Correlating the aspect ratio of MWNT with the percolation threshold

Multiwalled carbon nanotubes (purified, p‐MWNT and ～ NH₂ functionalized, f‐MWNT) were melt‐mixed with 50/50 cocontinuous blends of polyamide 6 (PA6) and acrylonitrile–butadiene–styrene in a conical twin‐screw microcompounder to obtain conductive polymer blends utilizing the conceptual approach of double‐percolation. The state of dispersion of the tubes was assessed using AC electrical conductivity measurements and melt‐rheology. The rheological and the electrical percolation threshold was observed to be ～ 1–2 wt % and ～ 3–4 wt %, respectively, for blends with p‐MWNT. In case of blends with f‐MWNT, the rheological percolation threshold was observed to be higher (2–3 wt %) than p‐MWNT but the electrical percolation threshold remained almost same. However, the absolute values were significantly lower than blends with p‐MWNT. In addition, significant refinement in the cocontinuous morphology of the blends with increasing concentration of MWNT was observed in both the cases. Further, an attempt was made to understand the underlying concepts in relation to cocontinuous morphologies that how the geometrical percolation threshold which adversely suffered because of the attrition of tubes under prolonged shear contributed further in retaining the rheological percolation threshold. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1619–1631, 2008     

Temperature-resistivity characteristics of a segregated conductive CB/PP/UHMWPE composite

A carbon black (CB)/polypropylene (PP)/ultrahigh-molecular-weight polyethylene (UHMWPE) composite with a segregated structure was fabricated by using binary polymer granules as matrices. In preparation, an ethanol-assisted dispersion method was employed to disperse CB particles on the surface of the two polymer granules. The segregated conductive network was then constructed by hot compaction based on the volume exclusion effect of the polymer matrices. The conductive composite shows an ultralow percolation threshold of 0.34 vol.%. In temperature-resistivity test, a double positive temperature coefficient (PTC) effect was observed. In addition, the negative temperature coefficient (NTC) effect was eliminated significantly. These interesting temperature-resistivity behaviors were ascribed to the introduction of the binary polymer matrices and the mobility limitation of CB particles located at the PP/UHMWPE interface. These characteristics were probed by in situ morphology observation in heating process. The present paper provides a novel route for preparing conductive composites with an ultralow percolation threshold, a wider PTC region, and a zero NTC effect.     

Effects of thermal volume expansion on positive temperature coefficient effect for carbon black filled polymer composites

Polymeric positive temperature coefficient (PTC) materials have been prepared by incorporating carbon black (CB) into two different polymer matrices, crystalline high density polyethylene (HDPE) and amorphous polystyrene (PS). The effects of thermal volume expansion on the electrical properties of conductive polymer composites were studied. The volume fraction of conductive particles behaves like a switch from insulator to conductor in the polymeric PTC composite. Our mathematical model and experimental model have proved that the abrupt resistivity increase at PTC transition range and at the percolation curve close to the critical volume fraction for both polymeric PTC composites have the same conductive mechanism. The thermal expansion is one of the key factors responsible for the PTC effect and can be seen by comparing the PTC transition curves from model predictions and experiment. Furthermore, the model predicts PTC curves of CB/PS composite more successfully than it does for the CB/HDPE composite, and the reasons for this are also discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3078–3083, 2007     

Charge transport properties in carbon black/polymer composites

The charge transport properties of polymer matrix–carbon black composites are investigated in this study. Direct current conductivity is examined with varying parameters: the temperature and the conductive filler content. Conductivity data are analyzed by means of percolation theory, and both percolation threshold and critical exponent are determined at each of the examined temperatures. The temperature dependence of conductivity and the agreement of experimental results with the variable range hopping model reveal hopping conduction as the predominant transport mechanism, below and in the vicinity of the critical concentration of carbon black particles. At higher concentrations, the contribution of hopping transport to the overall conductivity is reduced and a balance between hopping and conduction via geometrical contact occurs. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2535–2545, 2007     

A Novel Method for Preparing Polyurethane Based Conductive Composites with Low Percolation Threshold

A novel method for preparing conductive carbon black filled polymer composites with low percolation threshold from polyurethane emulsion are reported in this paper. The experimental results indicate that with a rise in carbon black concentration the insulator-conductor transition in the emulsion blended composites occurs at 0.8-1.4vol%. In contrast, the solution blended composites exhibit drastic increase in conductivity at conducting filler fraction as high as 12.3-13.3vol%. It is demonstrated that the composites microstructure rather than chemical structure of the matrix polymer predominantly determines the electrical conduction performance of the composites.