Electroconductive nylon 6 and copper composites

A study is reported on the effect of the filler size and concentration on the electrical resistivity, density, and hardness of composites made of copper powder embedded in nylon 6 matrix by means of compression molding. The electrical resistivity of the composites is > 10¹¹ ohm·cm unless the metal content reached the percolation threshold, beyond which the resistivity decreased markedly by as much as 10¹². The percolation concentration was found to decrease with a decrease in the average particle diameter. The density of the composites was measured and compared with values calculated assuming different void levels within the samples. However, there is no sharp variation in the density due to the onset of percolation. Furthermore, it is shown that a percolation concentration can be also defined in the hardness/metal concentration curves as the intercept of linear regression curves of the low and high metal content regimes, respectively.     

Conducting polymer composites of zinc‐filled nylon 6

The present work is concerned with the effect of processing variables and filler concentration on the electrical conductivity, hardness, and density of composite materials prepared by compression molding of a mixture of zinc powder and nylon 6 powder. The electrical conductivity of the composites is <10^?12 S/cm, unless the metal content reaches the percolation threshold at a volume fraction of about 0.18, beyond which the conductivity increases markedly by as much as 10 orders of magnitude. The density of the composites was measured and compared with values calculated by assuming different void levels within the samples. Furthermore, it is shown that the hardness increases with the increase of metal concentration, but for values of filler volume fraction higher than about 0.30 the hardness of samples remains almost constant. Two parameters of molding process, temperature and time, were shown to have a notable effect on the conductivity of composites, whereas pressure has no influence on this property in the pressure range considered. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1449–1454, 2001     

Electrical conductivity of urea–formaldehyde–cellulose composites loaded with copper

This work is concerned with the preparation and characterization of composite materials prepared by compression molding of mixtures of copper powder and a commercial grade thermosetting resin of urea–formaldehyde filled with α‐cellulose in powder form. The electrical conductivity of the composites is <10⁻¹² S/cm, unless the metal content reaches the percolation threshold of 24.0 vol %, beyond which the conductivity increases markedly by as much as 11 orders of magnitude, indicating an insulator–conductor phase transition. The homogeneity of these composites was checked by the morphologies of the constituents (filler and matrix) and the composites characterized by optical microscopy. The density of the composites was measured and compared with values calculated assuming different void levels within the samples to discuss the porosity effect. Finally, the obtained results on electrical conductivity have been well interpreted with the statistical percolation theory. The deduced critical parameters, such as the threshold of percolation, V_f*, the critical exponent, t, and the packing density coefficient, F, were in good accord with earlier studies. In addition, the hardness of samples remained almost constant with the increase of metal concentration. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Conducting polymer composites of zinc‐filled urea–formaldehyde

This article is concerned with the preparation and characterization of composite materials prepared by the compression molding of mixtures of zinc powder and urea–formaldehyde embedded in cellulose powder. The morphologies of the constituent, filler, and matrix were investigated by optical microscopy. The elaborated composites were characterized by density, which was compared with calculated values, and the porosity rate was deduced. Further, the hardness of samples remained almost constant with increasing metal concentration. The electrical conductivity of the composites was less than 10^?11 S/cm unless the metal content reached the percolation threshold at a volume fraction of 18.9%, beyond which the conductivity increased markedly, by as much as eight orders of magnitude. The obtained results interpreted well with the statistical percolation theory. The deduced critical parameters, such as the threshold of percolation, the critical exponent t, and the packing density coefficient were in good accord with earlier studies. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2011–2015, 2005     

Electrically conductive composites of poly(urea‐formaldehyde) and cellulose filled with aluminum

This article addresses the preparation and characterization of composite materials obtained with compression molding of mixtures of aluminum powder and a commercial grade thermosetting resin of poly(urea‐formaldehyde) filled with α‐cellulose in powder form. The homogeneity of these composites was checked by the morphologies of the constituents (filler and matrix) by optical microscopy. The density of the composites was measured and compared with values calculated by assuming different void levels within the samples, to discuss the porosity effect, in connection with optical microscopy observations. Then, the dependence of electrical conductivity of the composites on volume fraction of the metal filler was investigated. The conductivity of the composites is <10⁻¹² S/cm unless the metal content reaches the percolation threshold at a volume fraction of V_c = 38.6 vol%, beyond which the conductivity increases markedly by as much as nine orders of magnitude, indicating an insulator–conductor phase transition. The obtained results on electrical conductivity have been well interpreted with the statistical percolation theory. The deduced critical parameters, such as the threshold of percolation, V_c, the critical exponent, t, and the packing density coefficient, F, were in good accord with earlier studies. In addition, the hardness of samples remained almost constant with the increase of metal concentration. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Polymer composites prepared by compression molding of a mixture of carbon black and nylon 6 powder

The results of an experimental study on the effect of processing variables and filler concentration on the electrical resistivity of conductive composites based on nylon 6 filled with carbon black are reported. A typical percolation behavior in the effect of electroconductive filler content on the resistivity was found. The electrical resistivity of the composites is > 10¹² ohm°Cm unless the carbon black content reaches the percolation threshold at ∼9 wt%, beyond which the resistivity decreases markedly by as much as twelve orders of magnitude. Two parameters of molding process—temperature and time—were shown to have a notable effect on the resistivity of composites, whereas pressure has no influence on this property in the pressure range considered. There is no sharp variation in the density due to the onset of percolation, and the hardness of samples is not influenced by the presence of the filler.     

Non‐linear electrical conductivity of urea‐formaldehyde‐cellulose loaded with powders of different carbon fillers

This article reports on the making and characterization of composite materials prepared by compression molding of a commercial grade thermosetting resin of urea‐formaldehyde filled with α‐cellulose in powder form mixed successively with carbon black, synthetic graphite, and activated carbon. The morphology of the constituents and the composites has been characterized by optical microscopy. The porosity effect has been discussed from density measurements. Furthermore, it has been shown that the hardness of the samples remains almost constant with the increase of filler concentration. The electrical conductivity shows clearly a non‐linear behavior. The observed values are lower than 10^?11 S/cm, unless the filler content reaches the percolation threshold beyond which the conductivity increases markedly by as much as ten orders of magnitude, indicating insulator‐conductor phase transition. The conduction threshold depends on the filler nature. The results have been interpreted by means of the statistical percolation theory. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 990–996, 2005     

Nonlinear electrical conductivity of tin‐filled urea‐formaldehyde‐cellulose composites

This work reports on the elaboration and characterization of composite materials prepared by compression molding of mixtures of tin powder and a commercial grade thermosetting resin of urea‐formaldehyde filled with alpha‐cellulose in powder form. The morphology of constituents and composites has been characterized by optical microscopy. The porosity rate of the composites has been determined from density measurements. These results show that the composites are homogeneous. Furthermore, it has been shown that the hardness of samples remains almost constant with the increase of metal concentration. The electrical conductivity of the composites is <10⁻¹¹ S/cm unless the metal content reaches the percolation threshold at a volume fraction of 18.6%, beyond which the conductivity increases markedly by as much as 11 orders of magnitude. The results have been well interpreted in the statistical percolation theory frame. POLYM. COMPOS., 26:401–406, 2005. © 2005 Society of Plastics Engineers     

Electrical conductivity and percolation threshold of hybrid carbon/polymer composites

The electrical conductivity and percolation threshold of single and hybrid carbon filled composites are experimentally investigated. Polystyrene, carbon fiber (CF) and carbon black (CB) at three CF/CB ratios of 1.67, 3.33, 6.67 were compounded in a twin screw extruder micro‐compounder and compression molded into sheets. The through‐plane and in‐plane electrical conductivity of the composites are measured by 2 and 4 probe techniques. The percolation threshold of the single filler and hybrid composites are determined from the experimental results using a percolation model. The hybrid composites have a higher value of electrical conductivity and lower percolation threshold than the single CF filler composite except for the CF/CB ratio of 6.67. The percolation threshold for the cases of single filler and hybrid composites are modeled. The hard core / soft shell model is used and it is assumed that the percolation in a particle filled system depends on the ratio of tunneling distance to particle diameter. This ratio is determined by modeling single filler composites using the experimental data and kept constant in the modeling of the hybrid system. Finite size scaling is used to determine the percolation threshold for the infinite size hybrid system containing (nanosize) particles and micron size fibers for three CF/CB ratios. The simulation results show that the percolations of hybrid composites have the same trends observed in the experimental results. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41744.     

Investigation of electrically conductive acrylonitrile‐butadiene rubber

Electrically conductive acrylonitrile‐butadiene rubbers (NBRs) containing carbon black (CB) as conductive filler were prepared in order to investigate their electrical and mechanical properties. The effects of conductive CB loading, temperature, acrylonitrile content, crosslinking density of vulcanizates, and plasticizer on conductivity were studied. The change in electrical conductivity of NBRs with different amounts of CB showed that there is a certain critical point (percolation threshold) where a significant decrease in electrical resistivity (increase in conductivity) is observed. Mechanical properties such as tensile strength, elongation to break, and surface hardness of vulcanized NBRs were measured. It was found that the percolation threshold was 5 phr of CB for the NBR/CB composites. J. VINYL ADDIT. TECHNOL., 13:71–75, 2007. © 2007 Society of Plastics Engineers.     

Electrical conductivity and mechanical strength of composites consisting of phenolic resin,carbon fibers,and metal particles

Composites of phenolic resin of novolac type as matrix, with metal particles of Zn as conducting filler, without or with 15% v/v carbon fibers were manufactured by hot pressing. The porosity ratio, the hardness, the flexural and shear strength, and the electrical conductivity of the composites were determined. The percolation threshold was determined based on two models of electrical conductivity versus the content of metal particles of Zn, namely, an analogous to polymer gelation model and the other based on the power law. The composites of carbon fibers combined with Zn particles have higher electrical conductivity than the corresponding without carbon fibers and high strength, lower than that of the composite reinforced with carbon fibers without Zn particles, but still acceptable. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effects of filler geometry on internal structure and physical properties of polycarbonate composites prepared with various carbon fillers

BACKGROUND: The effects of filler geometry are important for understanding the internal structure and physical properties of polymer composites. To investigate the effects of filler geometry on electrical conductivity as well as morphological and rheological properties, three types of polycarbonate (PC) composites were prepared by melt compounding with a twin‐screw extruder. RESULTS: The electrical conductivity of PC/carbon black (CB) and PC/graphite (carbon) nanofibre (CNF) composites did not show a percolation threshold through the entire filler loading ranges. However, PC‐blend‐carbon nanotube (CNT) composites showed a percolation electrical threshold for a filler loading of 1.0 to 3.0 wt% and their maximum electrical conductivity approached 10^?3 S m^?1. PC‐blend‐CB and PC‐blend‐CNF composites showed Newtonian behaviour like pure PC matrix, but PC‐blend‐CNT composites showed yield stress as well as increased storage modulus and strong shear thinning behaviour at low angular frequency and shear rate due to strong interactions generated between CNT–CNT particles as well as PC molecules and CNT particles on the nanometre scale. CONCLUSIONS: The electrical conductivity of the PC composites with different carbon constituents was well explained by the continuous network structure formed between filler particles. The network structure was confirmed by the good dispersion of fillers as well as by the yield stress and solid‐like behaviour observed in steady and dynamic shear flows. Copyright © 2009 Society of Chemical Industry     

Shielding effectiveness density theory for carbon fiber/nylon 6,6 composites

We present a simple density theory based on first principles that predicts the shielding effectiveness of composite matrix materials at filler loadings near or above the percolation threshold. Such a model has practical applications in electromagnetic interference and radio frequency interference, and is validated here for Fortafil 243 carbon fiber within nylon 6,6. In brief, the theory predicts that the most important parameter on the shielding effectiveness of a sample is the carbon fiber volume percent. At very high filler loadings, experimental results show a weak dependence on the frequency of the wave to be shielded, which may be attributed to enhanced reflection from multiple, coherent scatterers (carbon fiber network). These effects are not considered in our model. Nevertheless, advantages of this model are ease of use and improved predictive capabilities when compared to models previously reported in the literature. Our model performs very well over an electrical resistivity range from 10¹⁵ ohm‐cm (at low filler loading levels below the percolation threshold) down to 10⁻¹ ohm‐cm (at high filler loading levels well above the percolation threshold), and can be used to determine filler loadings needed to provide a certain level of shielding of electromagnetic waves. POLYM. COMPOS. 26:671–678, 2005. © 2005 Society of Plastics Engineers     

Comparison of electrical properties between multi-walled carbon nanotube and graphene nanosheet/high density polyethylene composites with a segregated network structure

Multi-walled carbon nanotube (MWCNT)/high density polyethylene (HDPE) and graphene nanosheets (GNS)/HDPE composites with a segregated network structure were prepared by alcohol-assisted dispersion and hot-pressing. Instead of uniform dispersion in polymer matrix, MWCNTs and GNSs distributed along specific paths and formed a segregated conductive network, which results in a low electrical percolation threshold of the composites. The electrical properties of the GNS/HDPE and MWCNT/HDPE composites were comparatively studied, it was found that the percolation threshold of the GNS/HDPE composites (1 vol.%) was much higher than that of the MWCNT/HDPE composites (0.15 vol.%), and the MWCNT/HDPE composite shows higher electrical conductivity than GNS/HDPE composite at the same filler content. According to the values of critical exponent, t, the two composites may have different electrical conduction mechanisms: MWCNT/HDPE composite represents a three-dimensional conductive system, while the GNS/HDPE composite represents a two-dimensional conductive system. The improving effect of GNSs as conducting fillers on the electrical conductivity of their composites is far lower than theoretically expected.     

Development of an additive equation for predicting the electrical conductivity of carbon‐filled composites

The electrical conductivity of polymeric materials can be increased by the addition of carbon fillers. The resulting composites can be used in applications such as electrostatic dissipation and interference shielding. Electrical conductivity models are often proposed to predict the conductivity behavior of these materials. The electrical conductivity of carbon‐filled polymers was studied here by the addition of three single fillers to nylon 6,6 and polycarbonate in increasing concentrations. The fillers used in this project were carbon black, synthetic‐graphite particles, and milled pitch‐based carbon fibers. Materials were extruded and injection‐molded into test specimens, and then the electrical conductivity was measured. Additional material characterization tests included optical microscopy for determining the filler aspect ratio and orientation. The filler and matrix surface energies were also determined. An updated model developed by Mamunya and others and a new additive model (including the constituent conductivities, filler volume fraction, percolation threshold, constituent surface energies, filler aspect ratio, and filler orientation) fit the electrical conductivity results well. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2280–2299, 2003     

Electrical and thermal properties of polyethylene/silver nanoparticle composites

The concentration dependence of specific heat, electrical and thermal conductivities of nanocomposites based on high‐density polyethylene (HDPE) filled with silver nanoparticles have been investigated. The composites filled with high filler content show high electrical and thermal conductivities. The dielectric relaxation spectroscopy was used to investigate the electrical properties in the studied systems. The scaling law of electrical percolation was used for an exact estimation of the percolation threshold (P_c). A low electrical percolation threshold was found in the investigated composites. The rule of mixture was sufficient for the prediction of the specific heat dependence of HDPE–Ag nanocomposites as a function of the weight filler content. The basic models of the thermal conductivity have a tendency to underestimate the measured values for the low and high filler concentrations. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Evaluation of the rheological and electrical percolation of high-density polyethylene/carbon black composites using mathematical models

In this work, conductive polymer composites (CPCs) of bio-based polyethylene (BioPe) containing different concentrations of carbon black (CB) were developed. By using oscillatory rheology analysis, a Newtonian plateau was observed in BioPe, and all BioPe/CB composites had a behavior of a pseudo-solid and that composites with volume fractions ranging from 0.24 to 0.56 presented higher viscosity, storage, and loss modulus. This suggests the formation of a percolated network and by using the power-law models, it was observed that the electrical percolation threshold was higher than the rheological percolation threshold. The electrical conductivity was measured using the four-point probe method and a sigmoid model was used to predict the CPCs' electrical conductivity percolation threshold. The results indicated that the four-point probe method presented satisfactory results according to the calculated standard deviations and voltage–current characteristics for each round of measurements considering the same ranging as used in rheology analysis. The analytical model used showed a coefficient of determination (R²) higher than 95%, allowing the prediction of the electrical conductivity of the CPC and the percolation threshold as a function of the volumetric fraction of the CB.     

Rheological and conductive percolation laws for syndiotactic polystyrene composites filled with carbon nanocapsules and carbon nanotubes

Semicrystalline syndiotactic polystyrene (sPS) composites with carbon nanocapsule (CNC) and carbon nanotube (CNT) fillers were prepared and good filler dispersion confirmed by electron microscopy. Their rheological and electrical properties were investigated to reveal the effect of filler aspect ratio. Amorphous atactic polystyrene (aPS) was used to prepare composites with a CNT filler to elucidate the effect of matrix tacticity. Percolation scaling laws are applied and the threshold concentration and exponent are determined. Above a threshold, the magnitudes of storage modulus (G′) and conductivity are related to the level of percolation network as well as the intrinsic properties of the matrix and filler. Master curves are obtained provided that an appropriate percolation function is selected. Different scaling laws are validated for the G′ and conductivity results.Composites with CNTs show a much lower threshold than those with CNCs. A lower threshold is derived from the G′ results compared to that obtained from the conductivity data regardless of the filler aspect ratio and matrix tacticity. Owing to the pronounced nucleating effects of CNT, crystalline sPS composites exhibit a four times larger conductivity threshold compared to their amorphous aPS counterparts, although their rheological thresholds are similar.     

Percolation phenomena in polymers containing dispersed iron

Metal‐polymer composites based on polyethylene (PE), polyoxymethylene (POM), polyamide (PA) and a PE/POM blend as matrix and dispersed iron (Fe) as filler have been prepared by extrusion of the appropriate mechanical mixtures, and their electrical conductivity, dielectric properties and thermal conductivity have been investigated. The filler spatial distribution is random in the PE‐Fe, POM‐Fe and PA‐Fe composites. In the PE/POM‐Fe composite the polymer matrix is two‐phase and the filler is contained only in the POM phase, resulting in an ordered distribution of dispersed Fe in the volume of polymer blend. The transition through the percolation threshold ?_c is accompanied by a sharp increase of the values of conductivity σ, dielectric constant ε′ and dielectric loss tangent tan δ. The critical indexes of the equations of the percolation theory are close to the theoretical ones in the PE‐Fe and POM‐Fe composites, whereas they take unusually high values in the PE/POMFe composite. Thus, t in the equation σ ～ (φ – φ_c)^t is 2.9–3.0 in the systems characterized by random distribution of dispersed filler and 8.0 in the PE/POM‐Fe system. The percolation threshold φ_c depends on the kind of polymer matrix, becoming 0.21, 0.24, 0.29 and 0.09 for the composites based on PE, POM, PA and PE/POM, respectively. Also the thermal parameters of the PE/POM‐Fe composite are different from those of all other composites. A model explaining the unusual electrical characteristics of the composite based on the polymer blend (PE/POM‐Fe) is proposed, in agreement with the results of optical microscopy.     

Preparation of conductive polylactic acid/high density polyethylene/carbon black composites with low percolation threshold by locating the carbon black at the Interface of co-continuous blends

In the current study, polylactic acid/high density polyethylene/carbon black (PLA/HDPE/CB) composites are prepared via a two-step method. A double percolation network with co-continuous structure and filler distribution at the interface is constructed to design conductive polymer composites with low percolation threshold. The controllable distribution of CB at the interface is achieved by appropriate processing procedures involved mixing sequence and mixing time by taking advantage of the migration of CB from the unfavorable PLA phase to the favorable HDPE phase. Morphology characterization reveals that when the mixing time of the added HDPE is 3 min, the formation of co-continuous structure of PLA/HDPE (60/40, w/w) is observed, and CB particles migrate to the co-continuous interface. The electrical conductivity measurement shows that such double percolation conductive network reduces the percolation threshold of PLA/HDPE/CB to 2.42 wt%. The rheological property proves the establishment of particle percolation network, and the rheological percolation threshold is determined as 1.20 wt%. The prepared PLA/HDPE/CB composite by the two-step method displays a notably low percolation threshold than that prepared by one-step simultaneous mixing. Moreover, this strategy presents a high potential application in the fabrication of conductive polymer composites involving other miscible multiphase systems.