Surface modification of carbon black to facilitate suspension polymerization of styrene and carbon black

To carry out suspension polymerization of styrene in the presence of carbon black, an effective method was introduced to modify carbon black using nitric acid for oxygen treatment. The surface modification of carbon black with oxidation was confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy (SEM), which demonstrated that the chemical structure of carbon black has clearly changed. Compared with pristine carbon black (CB), SEM illustrates that the aggregation phenomenon of modified carbon black (MCB) was clearly weakened. After modification, the aggregation and inhibition effects of MCB on the polymerization of polystyrene/modified CB (PS/MCB) composite particles are obviously weakened. The lipophilicity of CB after modification was also increased during the synthesis of PS/MCB. The oxidized CB was successfully dispersed by polystyrene using in situ suspension polymerization. The dispersion and dosage of MCB in PS/MCB composite particles was greatly improved over that of CB in PS/CB composite particles. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46387.     

Influence of morphology on positive temperature coefficient effect for conductive polymer composites with carbon black dispersed at interface

Selective localization of carbon black (CB) at the interface of polymer blends was achieved by the method that EBA‐g‐MAH was first reacted with CB, and then blended with poly(ethylene‐co‐butyl acrylate)/nylon6 (EBA/PA6). In CB‐filled EBA/PA6 blends, EBA and PA6 phases formed cocontinuous morphology and CB was localized in PA6 phase. The percolation threshold was 5 wt%. A single PTC (positive temperature coefficient) effect was observed in this composite. The appearance of PTC effect was originated from the thermal expansion of EBA phase. In the EBA‐g‐MAH filled EBA/PA6 blends, TEM results showed that CB particles were induced by EBA‐g‐MAH to localize at the interface, resulting that the percolation threshold was much lower than that of EBA/PA6/CB. Influence of morphology on PTC effect of EBA/PA6/EBA‐g‐MAH/CB composites was studied. In the composites with sea‐island morphology, the conductive network was fabricated by dispersed phase and CB at the interface. Thermal expansion of matrix interrupted the contact of dispersed phases and conductive network formed by CB particles at the interface, resulting in the double PTC effect. The composites with co‐continuous morphology exhibited single PTC effect due to the fact that conductive network was only fabricated by CB localized at the interface. POLYM. ENG. SCI., 53:2640–2649, 2013. © 2013 Society of Plastics Engineers     

Electrical percolation of silicone rubber filled by carbon black and carbon nanotubes researched by the Monte Carlo simulation

Electrical percolation of carbon black (CB) and carbon nanotubes (CNTs) filled into silicone rubber (SR) is analyzed by the three-dimensional (3D) Monte Carlo simulation. First, the 3D models and simulation parameters of CB and CNTs are researched to narrow the deviation between simulation and experimental results of CB/SR and CNTs/SR. The degree of agglomeration is the most important parameter in simulation for CB. The 3D model of CNTs is the most important factor in simulation for CNTs. Then, the 3D Monte Carlo simulation for CB/CNTs/SR is developed based on the optimized 3D models and parameters of CB and CNTs. The results yielded by the simulation with optimized parameters are similar to the experiments and synergistic conductive effect of two hybrid fillers in nanocomposites exists. This work has demonstrated that the quantification of the electrical percolation of two hybrid fillers in nanocomposites by Monte Carlo simulation is feasible. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48222.     

Crystallinity,thermal diffusivity,and electrical conductivity of carbon black filled polyamide 46

Polyamide 46 (PA 46) with carbon black (CB) has been subjected to a heat treatment. Crystallinity, specific heat capacity, crystalline melting peak temperature, thermal diffusivity, and electrical conductivity were measured. The crystallinity increases with duration of thermal treatment. The maximum value is dependent on the filler fraction. A lower CB content leads to a higher crystallinity at maximum tempering time. The crystalline melting peak temperature increases with decreasing filler fraction and duration of thermal treatment due to different crystal types and/or diverging geometric forms of the crystals. Thermal diffusivity and electrical conductivity act positively proportional to each other and increase with CB content and tempering time. The thermal diffusivity decreases with increasing temperature. The volume resistance of PA 46 is lowered by heat treatment. By CB addition in combination with a tempering process, the PA 46 can be transferred into a conductor. CB is moved by PA 46 crystals into amorphous regions forming conductive pathways. © 2019 The Authors. Journal of Applied Polymer Science published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48882.     

Influence of carbon nanotubes with different functional groups on the morphology and properties of PPO/PA6 blends

Carbon nanotubes with different functional groups were prepared and then incorporated into the poly(2,6‐dimethyl‐1,4‐phenylene oxide)/polyamide 6 (PPO/PA6) blend via melt blending. The influence of different carbon nanotubes on the morphology and properties of the blend was studied. The results show that addition of pristine CNTs, CNTs‐OH, CNTs‐NH₂ leads to the evolution of the phase structure of PPO/PA6 (mass ratio: 60/40) blend from sea‐island to cocontinuous, whereas incorporation of CNTs‐COOH does not change the blend morphology due to serious aggregation of the carbon nanotubes. Incorporating different CNTs into PPO/PA6 blend increases the tensile modulus and storage modulus of the blends, whereas decreases slightly the tensile strength. At the same time, the glass transition temperatures (T_g) of PA6 and PPO are enhanced. ΔT_g, the gap between the T_g of PA6 and PPO, decreases with the addition of carbon nanotubes due to the stronger interaction of carbon nanotubes with PA6 than PPO. A similar tendency was found in the storage modulus (G′) and complex viscosity (η*) of the composites. The dispersion state of different carbon nanotubes and their interaction with polymer components are different, which causes the different confinement effect to the macromolecular chains. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effects of hybrid filler networks of carbon nanotubes and carbon black on fracture resistance of styrene‐butadiene rubber composites

In this study, influences of hybrid filler networks of carbon nanotubes (CNTs) and carbon black (CB) on fracture resistance of styrene‐butadiene rubber (SBR) composites were well investigated. The spherical CB was partially substituted by fibrous CNTs in two different ways: unequal replacement (1 phr CNTs replacing 4 phr CB) and equal replacement (1 phr CNTs replacing 1 phr CB). The J‐integral tests were employed to evaluate the crack initiation and propagation resistance. The strain amplification and distribution near the crack tip was measured by digital image correlation to explore the fracture resistance mechanism. Results revealed that the fracture resistance was effectively improved by unequal replacement. Meanwhile, for unequal replacement, higher content of CNTs resulted in a weaker strain amplification factor and larger amplification area near the crack tip, which contributed to the improved fracture resistance. However, opposite trends were observed for equal replacement. A synergistic effect in fracture resistance of SBR composites between CB and CNTs was realized for unequal replacement. POLYM. ENG. SCI., 56:1425–1431, 2016. © 2016 Society of Plastics Engineers     

Electrical conductivity and electromagnetic interference shielding effectiveness of carbon black/sisal fiber/polyamide/polypropylene composites

The effects of hybrid fillers on the electrical conductivity and electromagnetic interference (EMI) shielding effectiveness (SE) of polyamide 6 (PA6)/polypropylene (PP) immiscible polymer blends were investigated. Carbon black (CB) and steam exploded sisal fiber (SF) were used as fillers. CB was coated on the surface of SF, and this was exploded by water steam to form carbon black modified sisal fiber (CBMSF). CB/SF/PA6/PP composites were prepared by melt compounding, and its electromagnetic SE was tested in low‐frequency and high‐frequency ranges. We observed that SF greatly contributed to the effective decrease in the percolation threshold of CB in the PA6/PP matrix and adsorbed carbon particles to form a conductive network. Furthermore, an appropriate CB/SF ratio was important for achieving the best shielding performance. The results indicate that CBMSF was suitable for use as electronic conductive fillers and the CB/SF/PA6/PP composites could be used for the purpose of EMI shielding. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42801.     

Electric Conductivity and Thermorheology Properties of Polyacrylonitrile/Nylon6 Composites Filled with Carbon Black

The electric conductive polymer composites, which were made of carbon black particles through dispersing in mixtures of polyacrylonitrile (PAN)/nylon6 (PA6), were prepared in a Haake Thermo-mixer. The morphology, conductivity, thermorheology properties and their relationships were studied. Microphase separations and partial miscibility were confirmed when a small mass of PAN was introduced into PA6/CB composites. A part of CB particles could be attracted by PAN, and transferred to the interface of PA6 and PAN, leading to an increase of electric conductivity. Results also indicated that the introduction of PAN in the PA6/CB composite improved its elastic modulus as well as the thermal stability of its electric conductivity.     

Formation and evolution of the carbon black network in polyethylene/carbon black composites: Rheology and conductivity properties

We report a detailed investigation on the effect of carbon black (CB) morphology on network formation and evolution in high‐density polyethylene/CB composites. There were three types of networks in our study, the electrical network in the solid state and the electrical and rheological networks in the melt state. The evolution of the network in the polymer melt was traced by simultaneous electrical resistivity (R) and dynamic rheology testing. An oscillation strain sweep was used to investigate the network stability with a large strain. We found that with high‐structure CB with a branched morphology, it was easier to form a filler–polymer or filler–filler network than with low‐structure CB with a spherical morphology in the composite melt. The high‐structure CB network was more stable with a large strain compared to the low‐structure one. Meanwhile, the low‐structure CB aggregates had stronger capability of movement and re‐aggregation in the polymer melt. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39953.     

The cutting of multi-walled carbon nanotubes and their strong interfacial interaction with polyamide 6 in the solid state

The cutting of multi-walled carbon nanotubes (MWCNTs) using solid state shear milling (S³M) method and their strong interfacial interaction with polyamide 6 (PA6) in the solid state were studied. Transmission electron microscopy showed that after milling, the CNTs were greatly reduced in length, and disentangled, being straighter with open ends. Fourier transform infrared spectra and differential scanning calorimeter analysis indicated the existence of strong interfacial interactions between MWCNTs and PA6 of the pan-milled PA6/CNTs powder. It was further quantified by thermogravimetric analysis that about 30 wt.% of PA6 formed a strong combining force with CNTs after pan-milling. The mechanism of cutting CNTs and the reason for their strong interfacial interactions with PA6 in the solid state were discussed. A fine and homogeneous dispersion of CNTs throughout PA6 matrix was observed by scanning electron microscopy. The tensile properties of the composites prepared by the S³M method were significantly improved compared to those of pure PA6 and composites prepared by conventional melt mixing. Upon incorporation of only 1.5 wt.% MWCNTs, the tensile modulus of PA6 was enhanced from 2448 MPa to 4439 MPa, by about 80%, and the tensile strength was increased by about 23%.     

碳纳米管/NR复合材料的硫化特性

对机械混合制备的碳纳米管(CNTs)／NR复合材料硫化性能进行研究。结果表明，与炭黑补强胶料相比，加入CNTs后，NR胶料的焦烧时间略有延长，硫化返原现象减轻。应用几种不同工艺预处理的CNTs进行试验发现，除经混酸氧化处理CNTs对NR硫化产生明显迟滞效应外，其它几种CNTs填充胶料的硫化特性变化不大。应用CNTs填充橡胶材料，混炼胶中硫黄的用量应适当增大。     

Studies of nanocomposites based on carbon nanomaterials and RTV silicone rubber

The mechanical and electrical properties were investigated for nanocomposites based on carbon nanotubes (CNTs) and conductive carbon black (CB). Solution room‐temperature‐vulcanized silicone rubber was used as a matrix. Vulcanizates based on CNTs and CB was prepared by solution mixing. With the addition of 2 phr of CNTs to the rubber matrix, the Young's modulus increased by 272% and reached as high as ～706% at 8 phr, whereas the modulus increased only 125% for CB specimens at 10 phr. Similarly, the electrical properties at 5 phr content of CNT were ～0.7 kΩ against ～0.9 kΩ at 20 phr CB. The Kraus plot from equilibrium swelling tests shows that the high properties for CNT specimens are due to high polymer–filler interfacial interactions, the small particle size that improves the distribution of the filler in a highly exfoliated state, and high electrical connective networks among the filler particles. These improvements can especially influence medical products such as feeding tubes, seals and gaskets, catheters, respiratory masks and artificial muscles. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44407.     

Effect of the carbon black content on the thermal,rheological and mechanical properties of thermoplastic polyurethanes

Different mixtures of thermoplastic polyurethane (PU) with different amounts of nanometric carbon black (CB) were prepared by mechanical stirring in organic solvent, and their thermal, rheological, viscoelastic and mechanical properties were investigated. The rheology of the PU–CB mixtures in methyl ethyl ketone was optimized, allowing good dispersion of the CB in the polyurethane matrix once the solvent was removed; an increase in the number and size of carbon black aggregates in the polyurethane matrix was obtained by increasing the carbon black loading. Addition of carbon black improved the rheological and viscoelastic properties of the polyurethane, and the larger was the carbon black content, the higher was the storage modulus and the lower was the tanδ value. Moreover, the addition of higher amounts of CB changed the viscoelastic behaviour of the polyurethane, which became mainly elastic over all temperature range. On the other hand, the addition of CB loadings up to 12 wt% increased the thermal stability of the polyurethanes and increased the elongation-at-break without noticeable reduction in the tensile strength.     

Synergistic effects of hybrid carbon nanomaterials in room‐temperature‐vulcanized silicone rubber

This work examines nanocomposites based on nanofillers and room‐temperature‐vulcanized silicone rubber. The carbon nanofillers used were conductive carbon black (CB), carbon nanotubes (CNTs) and graphene (GE). Vulcanizates for CB, GE, CNTs as the only filler and hybrid fillers using CNTs, CB and GE were prepared by solution mixing. The elastic modulus for CNT hybrid with CB at 15 phr (4.65 MPa) was higher than for CB hybrid with GE (3.13 MPa) and CNTs/CB/GE as the only filler. Similarly, the resistance for CNT hybrid with CB at 10 phr (0.41 kΩ) was lower than for CB (0.84 kΩ) at 20 phr and CNTs as the only filler. These improvements result from efficient filler networking, a synergistic effect among the carbon nanomaterials, the high aspect ratio of CNTs and the improved filler dispersion in the rubber matrix. © 2016 Society of Chemical Industry     

Slipping of carbon nanotubes in a rubber matrix

The interactions of carbon nanotubes (CNTs) and carbon black (CB) with rubber matrices are of great interest. Although both belong to the carbon filler family, their interactions are different. In this study the adhesion of CNTs, if any, with natural rubber (NR) was examined. Scanning electron microscopy examinations made on cryogenically fractured surfaces of a crosslinked NR sample containing 7% by weight of CNTs showed that the CNT bundles emerged from the side surface (narrowed by Poisson's ratio) and slowly slid back in when the deformation was removed. The protruded lengths were many times larger than the nanotube bundle diameters. This extensive slipping out of CNTs from the rubber matrix suggests that interfacial interactions between CNTs and NR are quite weak. In contrast, relatively strong interactions were found between CB and rubber, indicated by the large amount of bound rubber formation. Reinforcement of rubber by CNTs is therefore attributed to the large aspect ratio of CNT bundles. Physical entanglement with rubber molecules is then able to generate effective load transfer, replacing the strong adhesion found with CB. Copyright © 2010 Society of Chemical Industry     

Developing electrically conductive polypropylene/polyamide6/carbon black composites with microfibrillar morphology

We have established that the PP/PA6/CB composite with 3D microfibrillar conducting network can be prepared in situ using melt spinning process. CB particles preferably were localized at the interface between polypropylene as the matrix and PA6 microfibrils, which act as the conducting paths inside the matrix. The percolation threshold of the system reduced when aspect ratio of the conducting phase was increased by developing microfibrillar morphology. The effect of annealing process on the conductivity of PP/PA6/CB composite with co‐ continuous and microfibrillar morphologies was studied. It was observed that, annealing process forces CB particles towards the interface (2D space) of PP and PA6 co‐continuous phases, and percolation threshold and critical exponent of classical percolation theory will be decreased, while the conductivity of conducting composite with microfibrillar morphology was not affected considerably by annealing process at temperatures either higher or lower than the melting point of the PA6 microfibrils. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Nylon 6 induced morphological developments and electrical conductivity improvements of polypropylene/carbon black composites

In this study, a polar conductive filler [carbon black (CB)], a nonpolar polymer [polypropylene (PP)], and a polar polymer [nylon 6 (PA6)] were chosen to fabricate electrically conductive polymer composites by melt blending and compression molding. The morphological developments of these composites were studied. Scanning electron microscopy results showed that in a CB‐filled PP/PA6 (CPA) composite, CB particles were selectively dispersed in PA6 phases and could make the dispersed particles exist as microfiber particles, which could greatly improve the electrical conductivity. The PA6 and CB contents both could affect the morphologies of these composites. The results of electrical resistivity measurements of these composites proved the formation of conductive networks. The resistivity–temperature behaviors of these composites were also studied. For CB‐filled PP (CP) composites, there were apparent positive temperature coefficient (PTC) and negative temperature coefficient (NTC) effects and an unrepeatable resistivity–temperature characteristic. However, for CPA composites, there were no PTC or NTC effects from room temperature to 180°C, and the resistivity–temperature behavior showed a repeatable characteristic; this proved that CB particles were selectively dispersed in the PA6 phase from another point of view. All experimental results indicated that the addition of PA6 to a CP composite could lead to an expected morphological structure and improve the electrical conductivity of the CP composite. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Carbon nanotubes/carbon black synergistic reinforced natural rubber composites

Abstract

Carbon black (CB) and carbon nanotubes (CNTs) filled natural rubber (NR) composites were prepared. In order to overcome the dispersion of CNTs in rubber matrix, the surface modification of CNTs with bis-(γ-triethoxysilylpropyl)-tetrasulphide (Si-69) was undertaken, and a two-step mixing process, i.e. the use of twin roll mill followed by mixing in a Haake Banbury mixer (TR-THM) was used. The structure and mechanical properties were investigated. The results show that the Si-69 treated CNTs (S-CNTs) were dispersed in the rubber matrix uniformly. Compared with CB/NR composites without CNTs, the S-CNTs/CB/NR composites have better mechanical properties. When the ratio of S-CNTs/CB/NR was 5 : 20 : 100, the tear strength was improved by ～60%, and the mechanical properties reached a maximum. Dynamical mechanical analysis (DMA) reveals that with increasing content of CNT, the elastic modulus of composites at room temperature increases, and the maximum loss tangent and the corresponding glass transition temperature of composites decrease.     

Sensing of damage in carbon nanotubes and carbon black‐embedded epoxy under tensile loading

In situ sensing of damage in epoxy embedded separately with carbon nanotubes (CNTs) and carbon black (CB) microparticles is investigated under quasi‐static uniaxial tensile loading. Three different weight fractions of CNTs (0.1, 0.3%, and 0.5%) and one‐weight fraction of CB (10%) are used to generate a conductive network in epoxy. A modified four circumferential ring probes technique is employed and a constant current was applied through the outer probes. The resulting voltage drop between the inner probes is measured using a high‐resolution electrometer‐based system to determine the resistance change associated with nonlinear deformation, damage initiation, and growth in the material. As the generated conductive network is different with changing weight fractions of CNTs, the resulting electrical response was identified to be significantly different between composites. The nonlinear deformation associated with the unfolding of entangled polymer chains and further straightening of them, decreased the distance between neighboring CNTs, resulting in improved electron hopping. For CB‐embedded epoxy, a very high percentage increase in resistance is noticed when compared to CNTs case owing to induced microcracks associated with agglomerated CB particles. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Effect of morphology on the electric conductivity of binary polymer blends filled with carbon black

Several carbon black (CB)‐filled binary polymer blends were prepared in Haake rheometer. Distribution states of CB and effect of morphology on the electric conductivity of different ternary composites were investigated. Under our experimental condition CB particles located preferentially at the interface between polymethyl methacrylate (PMMA) and polypropylene (PP) in PMMA/PP/CB composites, in high‐density polyethylene (HDPE) phase in PP/HDPE/CB composites, and in Nylon6 (PA6) phase in polystyrene (PS)/PA6/CB, PP/PA6/CB, PMMA/PA6/CB, and polyacrylonitrile (PAN)/PA6/CB composites; the ternary composites in which CB particles locate at the interface of two polymer components have the highest electric conductivity when the mass ratio of the two polymers is near to 1 : 1. The ternary composites in which CB particles located preferentially in one polymer have the highest electric conductivity usually when the amount of the polymer component having CB particles is comparatively less than the amount of the polymer component not having CB particles; if the formulations of PS/PA6/CB, PP/PA6/CB, and PMMA/PA6/CB composites equaled and PA6/CB in them is in dispersed phase, PS/PA6/CB composites have the highest electric conductivity and PP/PA6/CB composites have the lowest electric conductivity; suitable amount of PS or PAN in PA6/CB composites increase the electric conductivity due in the formation of a parallel electrocircuit for electrons to transmit. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007