Dielectric and microwave properties of carbon nanotubes/carbon black filled natural rubber composites

Abstract

Natural rubber (NR) based nanocomposites containing a constant amount (50 phr) of standard furnace carbon black and carbon nanotube (CNT) at a concentration from 1 to 5 phr have been prepared. Their dielectric (dielectric permittivity and dielectric loss) and microwave properties (coefficients of absorption and reflection of the electromagnetic waves and electromagnetic interference shielding effectiveness) have been investigated in the 1–12 GHz frequency range. The results achieved allow recommending CNTs as second filler for NR based composites to afford specific absorbing properties.     

Effect of carbon black on the mechanical and dielectric properties of rubber ferrite composites containing barium ferrite

Fine particles of barium ferrite (BaFe₁₂O₁₉) were synthesized by the conventional ceramic technique. These materials were then characterized by the X‐ray diffraction method and incorporated in the natural rubber matrix according to a specific receipe for various loadings of ferrite. The rubber ferrite composites (RFC) thus obtained have several applications, and have the advantage of molding into complex shapes. For applications such as microwave absorbers, these composites should have an appropriate dielectric strength with the required mechanical and magnetic properties. The N330 (HAF) carbon black has been added to these RFCs for various loadings to modify the dielectric and mechanical properties. In this article we report the effect of carbon black on the mechanical and dielectric properties of these RFCs. Both the mechanical and dielectric properties can be enhanced by the addition of an appropriate amount of carbon black. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 769–778, 2003     

Resistivity and thermal reproducibility of carbon black and metallic powder filled silicone rubber heaters

Flexible heaters were prepared by extruding platinum‐catalyzed silicone rubber composites with conductive carbon black (CB) and metallic fillers. The conductor resistivity of the extruded heaters decreased in order of conductive titanium dioxide (TiO₂) > aluminum powder ≈ zinc powder > copper powder. Thermoelectric switching phenomena were investigated for the silicone rubber/CB/metallic powder systems. The positive temperature coefficient effect was dependent mainly on the CB content rather than on the content of the metallic powders. Resistivity and thermal reproducibility of the extruded heaters were also investigated by periodically applying AC voltage of 110 V. The heaters containing copper and TiO₂ powders exhibited excellent electrical reproducibility. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1122–1128, 2005     

Study of the thermomechanical and electrical properties of conducting composites containing natural rubber and carbon black

This work describes the preparation and characterization of composite materials obtained by the combination of natural rubber (NR) and carbon black (CB) in different percentages, aiming to improve their mechanical properties, processability, and electrical conductivity, aiming future applications as transducer in pressure sensors. The composites NR/CB were characterized through optical microscopy (OM), DC conductivity, thermal analysis using differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMA), thermogravimetry (TGA), and stress–strain test. The electrical conductivity varied between 10^?9 and 10 S m^?1, depending on the percentage of CB in the composite. Furthermore, a linear (and reversible) dependence of the conductivity on the applied pressure between 0 and 1.6 MPa was observed for the sample with containing 80 wt % of NR and 20% of CB. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Modification of rubber powder with peroxide and properties of polypropylene/rubber composites

Waste tire powder was functionalized in the presence of various concentrations of allylamine and benzoyl peroxide. Fourier transform infrared spectroscopy studies confirmed the presence of allylamine on the surface of the rubber powder. The surface energy of the functionalized rubber powder revealed that the introduction of allylamine onto the rubber powder surface increased the surface activity. Improvements in the tensile strength, elongation at break, and storage modulus were observed for polypropylene/modified rubber powder/maleic anhydride grafted polypropylene, and this was attributed to an improvement in the compatibility due to the chemical interaction between the rubber powder and compatibilizer. Evidence for the reaction between the rubber surface and compatibilizer was observed in Fourier transform infrared studies. This peroxide‐initiated monomer‐grafting technique is feasible for large‐scale processes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2237–2243, 2007     

Aluminum powder filled nitrile rubber composites

Effect of aluminum powder on the properties of nitrile rubber (NBR) composites and the role of bonding agent viz. hexamethylene tetramine‐resorcinol has been investigated. Shore A hardness of the aluminum powder filled composites is lower than that of high abrasion furnace (HAF) and acetylene black (ACB) filled nitrile rubber composites and can be increased by the addition of bonding agent. Equilibrium swelling decreased considerably by the use of hexamethylene tetramine‐resorcinol, suggesting an improved nitrile rubber–aluminum powder adhesion. A marked increase in thermal conductivity is obtained with the incorporation of aluminum powder. Increased thermal conductivity reduced the additional time needed for the vulcanization of thick rubber articles and imparted uniform curing throughout the material. In nitrile rubber, the modulus and tensile strength followed the order HAF > ACB > aluminum powder. Combination of HAF and aluminum powder in NBR gave composites with good thermal conductivity and mechanical properties. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3156–3161, 2004     

Microwave absorbing properties of ternary linear low‐density polyethylene/carbonyl iron powder/carbon black composites

Linear low‐density polyethylene (LLDPE) was used as polymer matrix, carbonyl iron powder (CIP) and carbon black (CB) were used as fillers, and ternary composites with microwave absorbing properties were prepared by melt blending. Transmission electron microscopy was used to characterize the prepared samples. The absorbing ability (reflection loss) of the prepared composites was measured using the arch method, and the electromagnetic parameters of composites were determined by the transmission/reflection method. The filler contents of CIP and CB have effects on the absorbing peak positions and reflection loss, and there is the optimum filler content in composites to obtain the maximum microwave absorbing. The microwave absorption of LLDPE/CIP/CB composites comes from the combining contributions of the dielectric loss and the magnetic loss. The synergistic effects of CIP and CB effectively improve the microwave absorbing properties of polymer composites. CIP and CB are uniformly distributed in the polymer matrix. The theoretical calculation results of the absorbing ability are in agreement with the experimental results using the transmission line theory. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Electromagnetic interference shielding effectiveness of ethylene vinyl acetate based conductive composites containing carbon fillers

Conductive polymeric based composites were derived from ethylene vinyl acetate rubber filled with Vulcan XC‐72, short carbon fiber (SCF), and their blends. The electromagnetic interference (EMI) shielding effectiveness (SE), return loss, and reflection coefficient were studied. The measurements of the SE of the composites were carried out in two different frequency ranges of 100–2000 MHz and 8–12 GHz (X band). It was observed that the SE of the composites was frequency dependent and it increased with increasing frequency. The increasing of filler loading also enhanced the SE of the composites. The 100% SCF filled composites showed a higher SE compared to that of the filler blend or purely carbon black filled composites. The correlation between the SE and bulk conductivity of various composites was also discussed. The compromise between EMI SE, electrical conductivity, and mechanical properties was obtained when the composites contained both types of filler like particulate carbon black and SCF. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1601–1608, 2001     

Synergistic effects of carbon nanotubes and carbon black on the fracture and fatigue resistance of natural rubber composites

The quasi‐static fracture and dynamic fatigue behaviors of natural rubber composites reinforced with hybrid carbon nanotube bundles (CNTBs) and carbon black (CB) at similar hardness values were investigated on the basis of fracture mechanical methods. Mechanical measurement and J‐integral tests were carried out to characterize the quasi‐static fracture resistance. Dynamic fatigue tests were performed under cyclic constant strain conditions with single‐edged notched test pieces. The results indicate that synergistic effects between CNTBs and CB on the mechanical properties, fracture, and fatigue resistance were obtained. The composite reinforced with 3‐phr CNTBs displayed the strongest fatigue resistance. The synergistic mechanisms and dominating factors of quasi‐static and dynamic failure, such as the dispersion state of nanotubes, hybrid filler network structure, strain‐induced crystallization, tearing energy input, and viscoelastic hysteresis loss, were examined. The weakest fatigue resistance of the composite filled with 5‐phr CNTBs was ascribed to its strikingly high hysteresis, which resulted in marked heat generation under dynamic fatigue conditions. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42075.     

Microwave absorbing properties of carbon black/silicone rubber blend

In the frequency range of 2–18 GHz, the microwave absorbing properties of a carbon black/silicone rubber blend were investigated by changing the carbon black content and the thickness. The real part (ε′) and the imaginary part (ε″) of permittivity of the blends were calculated from the S‐parameters measured by a network analyzer. The reflection loss was simulated by using ε′ and ε″. The reflection loss less than ?10 dB could be obtained in the frequency range of 9.6ε13.5 GHz from the sample with 10 wt% of carbon black at 1.9 mm of thickness.     

改性粉煤灰填充废胶粉复合材料研究

以废胶粉（URP）为基体相,粉煤灰（FA）为增强相,烷偶联剂为相容性制备了粉煤灰/废胶粉复合材料。研究了废胶粉和粉煤灰的最佳用量和偶联剂的用量,混合方式和最佳的硫化条件。通过扫描电镜（SEM）和红外光谱（FT-IR）分析了粉煤灰/废胶粉试样的结构和形貌。结果表明：用Si-69对粉煤灰的改性效果好于KH-550。废胶粉最佳用量为100份,粉煤灰40份,Si-69 1.0份。最佳的初混方式为热混,偶联剂先与粉煤灰混合,而后再与废胶粉混合。最佳硫化条件为：温度160℃,压力8MPa,时间25 min。Si-69/FA/URP比KH-550/FA/URP的相容性要好。硅烷偶联剂中的Si—OH和粉煤灰表面的—OH发生脱水缩合,形成了Si—O键;偶联剂的有机端和废胶粉形成了C—H键,从而改善了FA/URP复合材料相容性和力学性能。     

Effects of substitution for carbon black with graphene oxide or graphene on the morphology and performance of natural rubber/carbon black composites

In this study, nanosheets including graphene oxide (GO) and reduced graphene oxide (rGO), were incorporated into natural rubber (NR), to study the effects of substituting GO or rGO for carbon black (CB) on the structure and performance of NR/CB composites. The morphological observations revealed the dispersion of CB was improved by partially substituting nanosheets for CB. The improvements in static and dynamic mechanical properties were achieved at small substitution content of GO or rGO nanosheets. With substitution of rGO nanosheets, significant improvement in flex cracking resistance was achieved. NR/CB/rGO (NRG) composites has a much lower heat build‐up value compared with NR/CB/GO (NG) composites at a high load of nanosheets. However, both GO and rGO tended to aggregate at a high concentration, which led to the poor efficiency on enhancing the dynamic properties, or even deteriorate the performance of rubber composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41832.     

Ablation properties of zinc borate and aluminum hypophosphite filled silicone rubber composites

The ablative properties of epoxy modified silicone rubber composites filled with zinc borate (ZB) and aluminum hypophosphite (AHP) were studied. The decomposition of the added fillers and covering connection of residual on the substrate contribute to the improvement of heat insulation. The ablation test shows that the formation of a dense char layer with certain strength is key to improving the ablative properties. The optimal ablative performance is achieved when the concentration of ZB and AHP is 10 and 5 phr, respectively. Under such circumstances, the linear ablation rate is as low as 0.032 mm/s, which is about 61% lower than the pure silicone rubber. Furthermore, the structure and composition of the formed char layer were analyzed using X-ray diffraction analysis, scanning electron microscopy, and Fourier transform infrared spectroscopy.     

Piezoresistivity of silicone‐rubber/carbon black composites excited by Ac electrical field

Flexible conductive composites were prepared using liquid silicone rubber as a matrix and conductive carbon black (CCB) as a filler, and the filler loading was varied from 1 to 15 phr in mass ratio. The surface conductivity was studied as a function of CCB concentration (1, 5, 10, 15 wt %), frequency in the range from DC to 1 MHz. The AC resistivity of the composites with low CCB concentration was found to be frequency dependent, whereas the composites with high CCB concentration was almost frequency independent. The resistance/impedance drift of the composites with time decreases sharply with the increase of frequency of applied electrical field. The piezoresistivity of the composite with 5 wt % CCB concentration (the upper percolation limit) was studied. It is found that the composite exhibits prominent positive piezoresistivity coefficient effect through the measurement frequency, and the sensitivity becomes steeper with the increase of exciting frequency. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Comparison of physical and mechanical properties of NR/carbon black/reclaimed rubber blends vulcanized by conventional thermal and microwave irradiation methods

This work experimentally monitored the physical and mechanical properties of natural rubber/carbon black/reclaimed rubber blends vulcanized by microwave (MW) irradiation and conventional thermal (CT) systems, and the curing mechanisms are addressed in conjunction with the vulcanizate properties. The microwave oven for rubber blend vulcanization was specially designed and constructed in this work. The results suggested that the tensile modulus and the hardness of the vulcanizates could be enhanced by increasing the reclaimed rubber (RR) content, whereas the tensile stress, elongation at break, and tear strength decreased with the RR loading. The mechanical properties of the vulcanizates from the CT method were higher than those from the MW method. The vulcanizates from the MW method had higher resistance to toluene penetration than those from the CT method. The differences in the properties of the vulcanizates from the CT and MW methods became smaller at higher RR contents. The sensitivity in property changes of the vulcanizates due to addition of the RR content was greater for the CT method than for the MW method. The differences in the results between these two curing systems could be explained in terms of the density and the types of crosslinks present in the vulcanizates. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 5039–5048, 2006     

Viscoelastic properties of natural rubber composites reinforced by defatted soy flour and carbon black co‐filler

Filler mixtures of defatted soy flour (DSF) and carbon black (CB) were used to reinforce natural rubber (NR) composites and their viscoelastic properties were investigated. DSF is an abundant and renewable commodity and has a lower material cost than CB. Aqueous dispersions of DSF and CB were first mixed and then blended with NR latex to form rubber composites using freeze‐drying and compression molding methods. A 40% co‐filler reinforced composite with a 1 : 1 DSF : CB ratio exhibited a 90‐fold increase in the rubber plateau modulus compared with unfilled NR, showing a significant reinforcement effect by the co‐filler. The effect, however, is lower than that observed in the carboxylated styrene–butadiene rubber composites reported earlier, indicating a significant effect from the rubber matrix. The co‐filler composites have elastic moduli between those of DSF and CB reinforced composites. Stress softening and recovery experiments indicated that the co‐filler composites with a higher CB content tend to have a better recovery behavior; however, this can not be simply explained from the recovery behaviors of the single filler (DFS and CB) composites. CB composites prepared by freeze‐drying show a strain‐induced reorganization of fillers. Strain sweep experiment data fit with the Kraus model indicates the co‐filler composites with a higher CB content are more elastic, which is consistent with the recovery experiments. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Ablation properties of aluminum silicate ceramic fibers and calcium carbonate filled silicone rubber composites

The ablative performance of aluminum silicate ceramic fiber (ASF) and calcium carbonate (CaCO₃) filled silicone rubber composites prepared through a two‐roll mill was examined. The properties of the composites were investigated by thermogravimetry, thermal conductivity measurements, and oxyacetylene torch testing. After the material was burnt, the structure and composition of the char were analyzed by Fourier transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscopy (SEM). The results of the ablation test showed that the ablation resistance improved greatly in an appropriate filler scope. Combined with SEM, it was proven that a firm, dense, and thermal insulation layer, which formed on the composites surface during the oxyacetylene torch test, was a critical factor in determining the ablation properties. Thermogravimetric analysis revealed that the thermal stability of the composites was enhanced by the incorporation of ASF and CaCO₃. The thermal conductivity measurements showed that the silicone rubber composites had a very low thermal conductivity ranging from 0.206 to 0.442 W m^?1 K^?1; this significantly prevented heat from transferring into the inner matrix at the beginning of the burning process. The proportion of 20/40 phr (ASF/CaCO₃) was optimum for improving the ablation resistance of the silicone rubber composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41619.     

Physical properties and cure characteristics of natural rubber/nanoclay composites with two different compatibilizers

The effects of epoxidized natural rubber (ENR) and maleic anhydride‐grafted polybutadiene (PB‐g‐MA) as compatibilizers to rubber formulations with and without organo‐modified layered silicates are investigated. The physical properties and curing characteristics of composites are studied by moving die rheometer, rubber process analyzer, tensile, tear, and hardness testing. The state of organoclay intercalation was determined by X‐ray diffraction method. The addition of compatibilizers, especially ENR 50, results in further intercalation or exfoliation of the organoclay that increased the clay dispersion in the rubber matrix. ENR 50 with organo‐modified clay improves the physical properties and changes the curing profile. The addition of PB‐g‐MA without organoclay increases the tensile strength (σ_max) by increasing the stock viscosity of the rubber compound. Interestingly, simultaneous increase in hardness and σ_max is achieved in the presence of both compatibilizers, a characteristic that is difficult to achieve and sometimes required in rubber processing. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of carbon black/natural rubber latex masterbatch in bead form

Carbon black/natural rubber latex masterbatch in the form of spherical beads was prepared according to the acid-precipitation method. High-loading carbon black (40 phr) was incorporated in natural rubber with the aid of a nonionic surfactant (Nonidet P40). Shearing the beads in an internal mixer provided good integration of carbon black in the rubber matrix and hence the high bound rubber content. Results confirmed the contribution of chemical interaction to the bound rubber content. By an oxidation process, the size of modified carbon black was reduced, whereas the large agglomeration took place in the case of partially graphitized carbon black. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 489–498, 2001     

A comparative study of short nylon fiber—Natural rubber composites prepared from dry rubber and latex masterbatch

A novel method for the preparation of short nylon fiber–natural rubber composites was developed in which short fibers chopped to approximately 6 mm were incorporated in the latex stage and processed into sheet form. By this method, mixing cycle time was reduced without compromising the fiber dispersion. Fiber breakage during mixing was reduced. The new composites when compounded with a dry bonding system based on hexamethylenetetramine, resorcinol and hydrated silica (HRH) showed improved modulus, tensile strength and abrasion resistance compared to conventional composites. Tear strength, resilience, and compression set were similar to the conventional composites. SEM analysis indicated better interaction between matrix and fibers in the case of latex master batch. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008