Effect of nanostructures of modified clay–carbon black on physico‐mechanical,electrical, and acoustic properties of elastomer‐based composites

Elastomeric composites based on nitrile rubber (NBR), carbon black (CB), and organically modified nanoclay (NC) were prepared using a laboratory two‐roll mixing mill. Influences of the hybrid filler system (CB+NC) on various properties of NBR compound were analyzed. It was found that the addition of hybrid filler (CB+NC) over only carbon black enhances various properties. It was also found that the addition of nanoclay to the rubber matrix effectively improved key properties. Acoustics and electrical properties were modified with reduced water absorption because of layered clay platelets. The lower volume resistivity of NBR composites reflected better electrical conductivity attributed to the presence of nanoclay leading to effective filler connectivity. X‐ray diffraction and transmission electron microscopy measurements revealed that nanoclays were mostly intercalated and were uniformly dispersed. Use of calcium stearate facilitated dispersion of nanoclay in the rubber matrix which was observed through the formation of nanostructures including “nano” and “halo” units. Time temperature superposition in dynamic mechanical analysis test of the composites indicated lower mechanical loss in the frequency range of interest. The advantages accruing due to overall property enhancement, including lower water absorption, and better electrical and excellent acoustic properties of NBR composites make it suitable as underwater acoustic transparent materials for transducer encapsulation application. POLYM. COMPOS., 37:1786–1796, 2016. © 2014 Society of Plastics Engineers     

Effects of size and shape originated synergism of carbon nano fillers on the electrical and mechanical properties of conductive polymer composites

In this study, microstructural features, mechanical properties, and electrical conductivity behaviors of thermoplastic composites prepared by using of cyclic olefin copolymer (COC) as matrix and various types of carbon nano materials, expanded graphite (EG), carbon nanofiber (CNF), and multi walled carbon nanotubes (CNT) as conductive fillers were investigated. Effects of using of double and triple filler combinations on the electrical properties of composites were also quantified in detail by measuring the bulk resistance of samples under alternating current with an impedance spectrometer. The electrical percolation values of fillers were found to be 20, 10, and 5 phr for the series of composites prepared with the EG, CNF, and CNT, respectively. It was obtained that the bulk resistances of percolated samples were dramatically decreased from 10¹⁴ ohm.cm to 10³?10⁴ ohm.cm. On the other hand, it was also found that the using of double and triple filler combinations provided much lower (about 10¹ ohm.cm) bulk resistance which corresponded to higher conductivity values than the highly filled composites including of 30 and 40 phr of EG. Based on the DMA measurements and the quantifying of elastic modulus values of composites in the rubbery region, it was found that the reinforcing effects of carbon nano fillers on the elastic modulus of composites decreased in the order of CNT>CNF>EG, depending on the aspect ratio (A_f) values of fillers into the matrix. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42313.     

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.     

Electrical conductivity modeling of carbon‐filled liquid‐crystalline polymer composites

Electrically conductive resins are needed for bipolar plates used in fuel cells. Currently, the materials for these bipolar plates often contain a single type of graphite powder in a thermosetting resin. In this study, various amounts of two different types of carbon, carbon black and synthetic graphite, were added to a thermoplastic matrix. The resulting single‐filler composites were tested for electrical conductivity, and electrical conductivity models were developed. Two different models, the Mamunya and additive electrical conductivity models, were used for both material systems. It was determined how to modify these models to reduce the number of adjustable parameters. The models agreed very well with experimental data covering a large range of filler volume fractions (from 0 to 12 vol % for the carbon black filled composites and from 0 to 65 vol % for the synthetic graphite filled composites) and electrical conductivities (from 4.6 × 10^?17 S/cm for the pure polymer to 0.5 S/cm for the carbon black filled composites and to 12 S/cm for the synthetic graphite filled composites). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3293–3300, 2006     

Electrical and thermal conductivity and tensile and flexural properties: Comparison of carbon black/polycarbonate and carbon nanotube/polycarbonate resins

Adding conductive carbon fillers to thermoplastic polymers increases the resulting composite's electrical conductivity. Carbon black (CB) is very effective at increasing composite electrical conductivity at low loading levels. In this study, varying amounts (2 to 10 wt %) CB were added to polycarbonate (PC) and the resulting composites were tested for electrical conductivity (1/electrical resistivity), thermal conductivity, and tensile and flexural properties. These results were compared with prior work done for carbon nanotubes (CNT) in polycarbonate. The percolation threshold was ～ 2.3 vol % CB compared to between 0.7 and 1.4 vol % CNT. At 8 wt % filler, the CNT/PC composite had an electrical resistivity of 8 ohm‐cm compared to 122 ohm‐cm for the CB/PC composite. The addition of CB to polycarbonate increased the composite electrical and thermal conductivity and tensile and flexural modulus. The 8 wt % (5.5 vol %) CB in polycarbonate composite had a good combination of properties for semiconductive applications. Ductile tensile behavior is noted in pure polycarbonate and in samples containing up to 8 wt % CB. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The production of soft, durable, and electrically conductive polyester multifilament yarns by dye-printing them with carbon nanotubes

Carbon nanotube based dyestuffs were prepared by dispersing aggregates of multiwalled carbon nanotubes in water using a blend of zwitterionic surfactants with anionic surfactants. Using a dye-printing approach, the carbon nanotubes were directly applied to polyester multifilament yarns to form an electrically conductive layer over each filament of the multifilament yarn. Yarns having electrical resistivity ranging from 10³ to 10⁹ ohm/cm were obtained. Yarn with a resistivity of 10³ ohm/cm could be used to form flat, soft, and portable electrical heaters by vertically weaving the yarns into fabrics. The 10⁵ ohm/cm yarns could be used for anti-static clothing, and the 10⁹ ohm/cm level yarns for brushes for photocopying machines.     

Factorial design approach applied to electrically and thermally conductive nylon 6,6

Increasing the thermal and electrical conductivity of typically insulating polymers, such as nylon 6,6, opens new markets. A thermally conductive resin can be used for heat sink applications. An electrically conductive resin can be used in static dissipative and Electromagnetic Interference/Radio Frequency Interference shielding applications. This research focused on performing compounding runs followed by injection molding and testing (tensile properties, volumetric electrical resistivity, and through‐plane thermal conductivity) of carbon filled nylon 6,6. The four carbon fillers investigated included a PAN‐based carbon fiber (milled, 200μ long), an electrically conductive carbon black, vapor grown graphitic nanotubes, and Thermocarb (high quality synthetic milled graphite). Formulations were produced and tested that contained varying amounts of a single carbon filler. Combinations of fillers were also investigated via conducting half of a 2⁴ factorial design. It was determined that Thermocarb has the largest effect on the thermal conductivity. Increasing Thermocarb increases thermal conductivity. For conductive resins containing only a single filler type, nanotubes caused the electrical resistivity (ER) to decrease the most. For the half fraction factorial design formulations that contain at least one filler type at the higher level, the ER of the conductive resin ranged from 0.1 to 0.3 ohm‐cm.     

Effect of incorporating ethylene‐ethylacrylate copolymer on the positive temperature coefficient characteristics of carbon black filled HDPE systems

In order to study the effect of introducing ethylene‐ethylacrylate copolymer (EEA) in carbon black‐HDPE composite systems, two HDPE‐EEA composites prepared by pre‐blending and masterbatch‐blending processes were compared with HDPE and EEA composites in terms of positive temperature coefficient (PTC) characteristics and percolation threshold. The percolation threshold of masterbatch‐blended composites occurred at the lowest carbon black concentration among four kinds of composites. The conduction path in the masterbatch‐blended composite is effectively formed as a result of the localization of carbon black distribution predominantly in the EEA phase, resulting in an increase of conductivity. I_peak values, the resistivity ratio of the peak to 25°C, of two blend composites were lower than those of HDPE composites. The I₈₅ values, the resistivity ratio of 85°C to 25°C, of masterbatch‐blended composites were higher than those of pre‐blended as well as HDPE composites. It is evident that since most carbon black is dispersed in the EEA phase of the masterbatch‐blended composites, the conduction networks are mainly broken by the crystal melting of EEA before the temperature reaches the crystal melting temperature of HDPE.     

Influences of polymer matrix melt viscosity and molecular weight on MWCNT agglomerate dispersion

In order to study the influence of melt viscosity and molecular weight on nanotube dispersion and electrical volume resistivity, three different polycarbonates (PCs) varying in molecular weight were melt compounded with 1 wt% multiwalled carbon nanotubes (MWCNTs, Baytubes^® 150 HP) using a small-scale compounder. The experiments were performed at constant melt temperature but at varying mixing speeds, thereby applying different magnitudes of shear stress. Light transmission microscopy was used to access the state of agglomerate dispersion, and electrical resistivities of the composites were measured on pressed plates. The results indicate that with increasing matrix viscosity the agglomerate dispersion gets better when using constant mixing conditions but worse considering comparable shear stress values. To study the effect of molecular weight, in a second set of experiments melt temperatures were adjusted so that all PCs had similar viscosity and mixing was performed at constant mixing speed. As investigated on two viscosity levels, the composites based on the low molecular weight matrix showed smaller sized un-dispersed primary agglomerates as compared to composites with higher molecular weight matrices, highlighting the role of matrix infiltration into primary nanotube agglomerates as the first step of dispersion. The resistivity values of composites prepared using low viscosity matrices were lower than those of composites from high viscosity matrix.     

Preparation of conductive polyphenylene sulfide/polyamide 6/multiwalled carbon nanotube composites using the slow migration rate of multiwalled carbon nanotubes from polyphenylene sulfide to polyamide 6

Conductive polyphenylene sulfide (PPS)/polyamide 6 (PA6)/multiwalled carbon nanotube (MWCNT) composites having 10–30 wt % PA6 and 1 wt % MWCNTs are prepared by melt mixing at 300°C for 8 min using a high concentration PPS/MWCNT masterbatch approach, and the migration kinetics of MWCNTs from thermodynamically unfavored PPS to favored PA6 was investigated. The morphology of the composites was investigated by field emission scanning electron microscopy and transmission electron microscopy, showing the localization of most MWCNTs in the PPS phase and at the interface, being different from the case of direct melt mixing where non‐conductive materials were obtained with most MWCNTs found in the PA6 phase and at the interface. The electrical resistivity and morphology of the materials as a function of time were investigated, showing that the conductive materials can be prepared within a mixing time of 4–16 min because of the slow migration rate of MWCNTs from PPS toward PA6, and MWCNTs can eventually migrate into the PA6 phase after a long mixing time of 30 min. The slow migration rate of MWCNTs was attributed to the high viscosity ratio of the two phases. This article shows a good example where the migration of MWCNTs was slow enough to control and can be used to prepare conductive polymer blends. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42353.     

Synergistic effects of carbon fillers in electrically and thermally conductive liquid crystal polymer based resins

Adding conductive carbon fillers to insulating thermoplastic resins increases composite electrical and thermal conductivity. Often, as much of a single type of carbon filler is added to achieve the desired conductivity, while still allowing the material to be molded into a bipolar plate for a fuel cell. In this study, varying amounts of three different carbons (carbon black, synthetic graphite particles, and carbon fiber) were added to Vectra A950RX Liquid Crystal Polymer. The resulting single filler composites were tested for electrical resistivity (1/electrical conductivity) and thermal conductivity. In addition, the effects of single fillers and combinations of two different carbon fillers were studied via a factorial design. The results indicated that for the composites containing only single fillers, synthetic graphite, followed by carbon fiber, cause a statistically significant decrease in composite electrical resistivity. Composites containing only synthetic graphite, followed by carbon black, and then carbon fiber cause a statistically significant increase in thermal conductivity. For the combinations of two different fillers, the composites containing carbon black/synthetic graphite and synthetic graphite/carbon fiber had a statistically significant and positive effect on thermal conductivity. It is possible that thermally conductive pathways are formed that “link” these carbon fillers, which results in increased composite thermal conductivity. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

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     

Effect of some service conditions on the electrical resistivity of conductive styrene–butadiene rubber–carbon black composites

Conductive polymer composites were prepared using vulcanized styrene–butadiene rubber as a matrix and conductive carbon black as a filler. The filler loading was varied from 10 to 60 phr. The volume resistivity was measured against the loading of the carbon black to verify the percolation limit. The electrical conductivity of filled polymer composites is attributed to the formation of some continuous conductive networks in the polymer matrix. These conductive networks involve specific arrangements of conductive elements (carbon black aggregates) so that the electrical paths are formed for free movement of electrons. The effects of temperature and pressure on the volume resistivity of the composites were studied. The volume resistivity of all the composites increased with increase in temperature, and the rate of increase in the resistivity against temperature depended on the loading of carbon black. The change in volume resistivity during the heating and cooling cycle did not follow the same route, leading to the phenomena of electrical hysteresis and electrical set. It was found that the composites with 40 and 60 phr carbon black become more conductive after undergoing the heat treatment. Generally, all the composites showed a positive temperature coefficient of resistivity. The volume resistivity of all the composites decreased with increase in pressure. The relaxation characteristic of the volume resistivity of the composites was studied with respect to time under a constant load. It was found that the volume resistivity of the compressed specimen of the composites decreased exponentially with time. It was observed that initially a faster relaxation process and later a slower relaxation process occurred in these composites. Some mechanical properties of these composites were also measured to confirm the efficacy of these composites for practical applications. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2179–2188, 2004     

Elastomeric conductive composites based on conducting polymer–modified carbon black

Thermally stable elastomeric composites were prepared via melt processing from poly(styrene-b-ethylene-co-butylene-b-styrene) (SEBS) and conducting polymer-modified carbon black (CPMCB) additives. CPMCB additives represent a novel thermally stable conductive compound made via “in-situ” deposition of polyaniline or polypyrrole on carbon black particles. Incorporating CPMCB is advantageous to the melt processing of composites, as it reduces the melt viscosity in comparison to the use of pure carbon black. Thermogravimetric analyses (TGA) showed that the composites are thermally stable with no appreciable degradation at temperatures as high as 300°C. In addition, the electrical conductivity of the composites was found to be very stable at high temperatures. Polym. Compos. 25:617–621, 2004. © 2004 Society of Plastics Engineers.     

Graphene/carbon black/natural rubber composites prepared by a wet compounding and latex mixing process

The extensively used latex mixing approach to prepare graphene can improve the graphene dispersion but meets some challenges in the preparation of high content carbon black filled rubber system like a rubber tire. Owing to the high melt viscosity of the rubber/graphene masterbatch, the dispersion of carbon black is not perfect during twin-roll mixing and some aggregates will be formed. Here we proposed a wet compounding process, combined with ultrasonically assisted latex mixing, named as the WCL method to prepare reduced graphene oxide/carbon black/natural rubber (rGO/CB/NR) composites. The morphological observations confirmed that both graphene and carbon black can be evenly dispersed in the rubber composites. The incorporation of rGO also improves the hardness, thermal conductivity and anti-aging properties of the composites. The rGO/CB/NR composites prepared by the WCL method possess better mechanical properties compared to conventional latex mixing. The entanglement-bound rubber tube model was utilised to understand the reinforcing mechanism.     

聚合物基导热复合材料的性能及导热机理

采用不同品种、粒径的导热填料和基体树脂,以熔融共混方法制备聚合物/填料体系导热功能复合材料。研究了复合材料热导率λ和体积电阻率ρ_v随不同填料、粒径等因素的变化规律及其内在原因。不同填充体系的热导率均随填料粒径的减小而降低,而电导率则相反;复合体系热导率随填料含量的增加始终呈逐步上升趋势,未表现出电导率那样的急剧变化。研究表明：复合体系热导率和电导率变化的差异主要是由于二者具有不同的传导机理;复合材料热导率的变化规律可以用热弹性复合增强机制进行合理解释。     

Effect of the processing parameters on the surface resistivity of acrylonitrile–butadiene rubber/multiwalled carbon nanotube nanocomposites

In this study, acrylonitrile–butadiene rubber (NBR) was melt‐mixed with multiwalled carbon nanotubes (MWCNTs). Because the electrical conductivity and mechanical properties of composites are strongly influenced by the filler's state of dispersion and the extent of filler breakage during processing, the processing conditions are very important parameters. The effects of the mixing time, rotor speed, cooling rate, and sulfur concentration on the surface resistivity were investigated. Increasing the rotor speed from 20 to 60 rpm at mixing times of 15 and 30 min led to an increase in the surface resistivity from around 10⁴ to 10¹¹ Ω/square. However, at a mixing time of 7 min, the surface resistivity slightly decreased with increasing rotor speed. When slow cooling was applied, a surface resistivity of 10⁴ Ω/square was obtained at around 2‐phr MWCNTs. However, when the fast cooling was applied, a surface resistivity of 10⁶ Ω/square was obtained at 5‐phr MWCNTs. The tensile strength and tensile modulus at 300% elongation were improved with the addition of MWCNTs into NBR. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Aspects of producing hydrogenated nitrile butadiene rubber (HNBR) nanocomposites by melt compounding processing

Industry is constantly demanding for materials with differential properties that explores nanoscale fillers functionality. Unfortunately, most of the papers present processing methods that are hard to scale up. Effects in addition different amounts of multiwall carbon nanotubes (MWCNT) and few-layer graphene (FLG) on cure behaviour, viscoelastic, mechanical and electrical properties of a hydrogenated nitrile butadiene rubber (HNBR) are investigated and compared with those composites having carbon black (CB) as filler. Looking for scale up the produced nanocomposites, rubber composites were produced in a closed mixing chamber by melt mixing with unmodified fillers. Addition of nanotubes reduces curing time. Microstructural analyses indicate that FLG cannot be easily dispersed by this methodology. Significant improvement in mechanical properties is observed with MWCNT addition, with 940% modulus increment regarding to the pure polymer and also, in lower intensity, in HNBR/FLG composites. Moreover, HNBR/MWCNT composites presented a sharp reduction in electrical resistivity at low loading level.     

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     

Time–temperature dependence of the electrical resistivity of high‐density polyethylene/carbon black composites

Several carbon blacks with surface areas from 105 to 1353 m²/g were used to produce composites through melt compounding with a high‐density polyethylene matrix. The electrical behavior of the obtained composites was investigated by the measurement of their resistivity as a function of the carbon black content and type at various temperatures and times during isothermal annealing treatments. The percolation threshold markedly decreased as the carbon black surface area increased, reaching a minimum value of 1.8 vol % for the carbon black with a surface area of 1353 m²/g. The resistivity passed through a maximum as the test temperature increased. Moreover, the analysis of the experimental data evidenced that the host high‐density polyethylene matrix and the conductive carbon black network rearranged during the isothermal thermal treatments, causing a resistivity decrease. This rearrangement became less and less important as the carbon black surface area increased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007