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     

Effect of coal gangue/carbon black/multiwall carbon nanotubes hybrid fillers on the properties of natural rubber composites

The objective of this study was to investigate three kinds of filler with completely different morphology on mechanical properties of natural rubber (NR). Coal gangue (CG) are derived from natural deposits are composed principally by illite and quartz. CG, carbon black (CB), and multiwalled carbon nanotube (CNT) were used as hybrid fillers in NR. CNTs were dispersed into NR latex by ultrasonic irradiation and then the mixed latex were coagulated to obtain the CNTs/NR masterbatch, then mechanical mixing method was employed to prepare the CG/CB/CNTs/NR composites. The addition of CG, CB, and CNTs to NR was varied with the total filler loading fixed at 35 phr. The mechanical properties of NR composites were studied in terms of tensile and dynamic mechanical analysis (DMA). The results showed that the tensile strength and modulus 300% (M300) of all hybrid samples were higher than the composites only loaded CG; and the highest tensile strength of NR loaded with hybrid fillers achieved at sample of loading amount of CG 17.5, CB 15.5, and CNTs 2 phr, whose M300 and elongation at break was obviously higher than that of only CB loaded NR composites; The inclusion CG improves the tensile strength of NR without the sacrifice of its extensibility, while CB and CNTs brings together the enhancement in the ultimate strength and the reduction in the extensibility. DMA results revealed that the existence of CG can improve the dispersion of CB and CNTs in NR matrix. POLYM. COMPOS., 37:3083–3092, 2016. © 2015 Society of Plastics Engineers     

炭黑/煤矸石/碳纳米管复合填料体系对天然橡胶性能的影响研究*

利用硝酸氧化法对碳纳米管(CNTs)进行纯化,并用环氧天然橡胶(ENR)进行改性处理。结合胶质量分数测定结果表明, ENR用量15%(质量)时效果最佳。采用胶乳凝聚法制备CNTs/天然橡胶(NR)母料。煤矸石粉(CG)经高温煅烧和表面改性处理。 将CNTs/天然橡胶(NR)母料、CG和炭黑(CB)通过机械混炼法与天然橡胶及配合剂混合,制备CB/CG/CNTs/NR复合材料,并对复合材料进行硫化特性及物理机械性能。结果表明： CNTs延迟硫化效应明显;相比炭黑,CG对硫化具有促进作用。硫化特性和甲苯溶胀法测定结果表明,在填料份数相同的条件下,单独由CB填充的NR有最大的交联密度,CNTs对交联密度影响不明显。物理机械性能测试结果表明,当CG：CB：CNTs=17.5:16.5:1(Phr)时,NR硫化胶的300%定伸应力和扯断伸长率明显高于单独由CB填充NR,而拉伸强度与之接近,复合填料样填充NR具有较好的综合性能。扫描电镜测试结果表明,复合填料在NR基体中分布均匀。     

The reinforcing mechanism study of carbon nanotube in the NR matrix

The reinforcement mechanism of CNT in rubber matrix is an important and interesting subject. In this paper, carboxyled multi-walled carbon nanotubes (CNT) were used to prepare natural rubber (NR) nanocomposites (CNT/NR). CNT/NR composites were formed by mechanical blending method and the properties such as tensile strength, tensile modulus, tear strength, elongation at break and hardness were studied. The results of Mechanical property show that the physical property of NR filled with 9 phr CNT (CNT/NR-9) is similar to that with 30 phr carbon black (CB) (CB/NR-30). In addition, the dispersion and interaction between CNT and NR were also studied by scanning electron microscope, transmission electron microscope, dynamic mechanical testing system and bound-rubber analysis. According to the results, CNT is considered to exhibit random orientations and form “string bag” structure in rubber matrix and the reinforcement mechanism of CNT is different to that of CB.     

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.     

Electrical,rheological and electromagnetic interference shielding properties of thermoplastic polyurethane/carbon nanotube composites

Electrically conducting rubbery composites based on thermoplastic polyurethane (TPU) and carbon nanotubes (CNTs) were prepared through melt blending using a torque rheometer equipped with a mixing chamber. The electrical conductivity, morphology, rheological properties and electromagnetic interference shielding effectiveness (EMI SE) of the TPU/CNT composites were evaluated and also compared with those of carbon black (CB)‐filled TPU composites prepared under the same processing conditions. For both polymer systems, the insulator–conductor transition was very sharp and the electrical percolation threshold at room temperature was at CNT and CB contents of about 1.0 and 1.7 wt%, respectively. The EMI SE over the X‐band frequency range (8–12 GHz) for TPU/CNT and TPU/CB composites was investigated as a function of filler content. EMI SE and electrical conductivity increased with increasing amount of conductive filler, due to the formation of conductive pathways in the TPU matrix. TPU/CNT composites displayed higher electrical conductivity and EMI SE than TPU/CB composites with similar conductive filler content. EMI SE values found for TPU/CNT and TPU/CB composites containing 10 and 15 wt% conductive fillers, respectively, were in the range ?22 to ?20 dB, indicating that these composites are promising candidates for shielding applications. © 2013 Society of Chemical Industry     

Optimized process for the inclusion of carbon nanotubes in elastomers with improved thermal and mechanical properties

The effects of addition of reinforcing carbon nanotubes (CNTs) into hydrogenated nitrile–butadiene rubber (HNBR) matrix on the mechanical, dynamic viscoelastic, and permeability properties were studied in this investigation. Different techniques of incorporating nanotubes in HNBR were investigated in this research. The techniques considered were more suitable for industrial preparation of rubber composites. The nanotubes were modified with different surfactants and dispersion agents to improve the compatibility and adhesion of nanotubes on the HNBR matrix. The effects of the surface modification of the nanotubes on various properties were examined in detail. The amount of CNTs was varied from 2.5 to 10 phr in different formulations prepared to identify the optimum CNT levels. A detailed analysis was made to investigate the morphological structure and mechanical behavior at room temperature. The viscoelastic behavior of the nanotube filler elastomer was studied by dynamic mechanical thermal analysis (DMTA). Morphological analysis indicated a very good dispersion of the CNTs for a low nanotube loading of 3.5 phr. A significant improvement in the mechanical properties was observed with the addition of nanotubes. DMTA studies revealed an increase in the storage modulus and a reduction in the glass‐transition temperature after the incorporation of the nanotubes. Further, the HNBR/CNT nanocomposites were subjected to permeability studies. The studies showed a significant reduction in the permeability of nitrogen gas. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Investigation of silicone rubber composites reinforced with carbon nanotube,nanographite, their hybrid,and applications for flexible devices

New technology is constantly required for updating new generation flexible devices, such as stretchable sensors, flexible electronics, and actuators. In the present study, a stretchable strain sensor, and actuator were developed based on room-temperature-vulcanized (RTV) silicone rubber reinforced with carbon nanotubes (CNTs), nanographite (GR), and CNT-GR hybrids. A CNT-based strain sensor developed for RTV silicone rubber showed improved stiffness and brittleness. For example, at 5 phr of filler loading, the compressive and tensile modulus for the CNT-reinforced RTV silicone matrix improved by 287% and 240%, respectively. Similarly, the improvements in the compressive and tensile modulus were moderate for the CNT-GR hybrid (210% and 235%) and low for GR (135% and 125%). The improved brittleness resulted in a higher fracture strain of 170% and 155% for the CNT-GR hybrid and GR, respectively. The improved mechanical properties were tested in real-life applications of actuation. The actuation displacement at a filler loading of 2 phr increased to 1.65 mm (CNT), 1.25 mm (CNT-GR), and 0.08 mm (GR). From 2 to 8 kV, the actuation displacement increased by 825% (CNT), 830% (CNT-GR), and 32% (GR). The strain sensor showed a stretchability of >100% (CNT) and >100% (CNT-GR). In addition, the gauge factor was higher for the CNT-GR hybrid composites. The durability measurements showed that the change in resistance was negligible for up to 5000 cycles in both the CNT and CNT-GR rubber composites. A series of experiments confirmed that compared to the composite based on RTV silicone rubber and CNT, the CNT-GR hybrid showed a robust flexibility and stretchability as a piezo-resistive strain sensor and actuator.     

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     

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     

Enhancement of electrical conductivity and other related properties of epoxidized natural rubber/carbon nanotube composites by optimizing concentration of 3‐aminopropyltriethoxy silane

Carbon nanotube (CNT)‐filled epoxidized natural rubber (ENR) composites were prepared by mixing in an internal mixer and thereafter on a two‐roll mill. Silane coupling agent, namely 3‐aminopropyltriethoxy silane (APTES), was directly incorporated in the ENR‐CNT composites during mixing of rubber and CNTs in the mixer, to perform in situ functionalization. It was found that pre‐crosslinking of ENR and APTES occurred especially at high APTES concentrations, such as 0.06 mL/(g of CNTs) and caused strong CNT agglomeration in the ENR matrix. However, the pre‐crosslinking could be reduced or avoided by decreasing the APTES concentration. In the concentration range 0.01–0.015 mL/(g of CNTs) of APTES, the APTES molecules were grafted on the CNT surfaces and generated new chemical linkages with the ENR. This improved the CNT dispersion in the ENR matrix and enhanced the composite properties. A very low approximately 0.5 phr of CNT threshold concentration for electric percolation was achieved in this type of composites. Also, three‐dimensional connected CNT networks were found to form in the ENR matrix at very low APTES levels. Thus, the electrical conductivity achieved in these composites reached the level required of conductive materials. POLYM. ENG. SCI., 57:381–391, 2017. © 2016 Society of Plastics Engineers     

混炼方式对螺旋纳米碳纤维增强天然橡胶复合材料力学性能的影响

采用干法和湿法两种混炼工艺制备了螺旋纳米碳纤维(HCNFs)/炭黑(CB)/天然橡胶(NR)复合材料,通过扫描电镜、拉伸试验机和应变扫描仪分别对所制备复合材料的界面形貌、力学性能和Payne效应进行了测试分析,考察了混炼方式对复合材料宏观力学性能及Payne效应的影响。结果表明,与纯CB填料相比,在干湿两种混炼方式下,添加适量的HCNFs(1～6份)能提高HCNFs/CB/NR复合材料的300%定伸应力、扯断伸长率、拉伸强度和硬度。与干法混炼相比,湿法混炼能明显增强HCNFs/CB/NR复合材料的Payne效应,并提升在HCNFs高添加量(2～6份)条件下的拉伸强度和扯断伸长率,这主要源于湿法混炼能够有效改善HCNFs在橡胶基质中的分散性。     

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.     

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     

Effects of in‐situ functionalization of carbon nanotubes with bis(triethoxysilylpropyl) tetrasulfide (TESPT) and 3‐aminopropyltriethoxysilane (APTES) on properties of epoxidized natural rubber–carbon nanotube composites

Composites of carbon nanotubes (CNT) and epoxidized natural rubber (ENR) were prepared by in‐situ functionalization of CNT with two alternative silane coupling agents: bis(triethoxysilylpropyl) tetrasulfide (TESPT) and 3‐aminopropyltriethoxysilane (APTES). The reactions of ENR molecules with the functional groups on CNT surfaces and with the silane molecules were characterized by Fourier transform infrared. Furthermore, cross‐link density, relaxation behaviors, curing, mechanical, electrical, and morphological properties of pristine ENR and the ENR composites were investigated. Very low percolation thresholds, at CNT concentrations as low as 1 phr, were observed in the ENR–CNT and the ENR–CNT–TESPT composites. This might be attributed to improvements in the chemical linkages between ENR molecules and functional groups on CNT surfaces that led to a homogenous dispersion of CNTs in the ENR matrix, with loose CNT agglomerates. POLYM. ENG. SCI., 55:2500–2510, 2015. © 2015 Society of Plastics Engineers     

Effect of modification conditions of coal gangue on properties of natural rubber composites

The purpose of this work is to study the reinforcement effect of modified coal gangue (CG) on natural rubber (NR); carbon black (CB) was taken as reference filler. The addition of CG and CB to NR with the total filler loading fixed at 35 phr. The orthogonal experiment was employed to reveal the modification conditions on reinforcing properties. The results show that modification conditions such as weight ratio of coupling agent (CA), calcining temperature (CT), and calcining time (CM) affect the strengthening properties of CG, and CA is the most important factor influencing the tensile strength of NR, the order of influence can be expressed as CA > CT > CM. The optimum modification conditions are CT 800°C, CM 1 hr, and CA 2%. 300% modulus of NR composites filled with modified CG (17.5 phr)/CB (17.5phr) hybrid filler is similar to NR filled with CB alone at same filler loading, while elongation at break increases significantly for existent of CG. The effect of heat treatment and modification conditions of CG were tested by particle size distribution, scanning electron microscopy, Fourier transform infrared spectra, and X‐ray diffraction. The results show that the specific surface area of CG increased and hydroxyl group in crystal structure of CG removed under heat treatment. Dynamic mechanical analysis results show that the storage modulus and tan δ of CG filled NR composites are higher while T_g is less than that of CB, indicating the existence of a strong and stiff interface between filler and NR matrix. POLYM. COMPOS., 35:1911–1917, 2014. © 2014 Society of Plastics Engineers     

Electrical and mechanical properties of carbon nanotube‐epoxy nanocomposites

In this work, electrical conductivity and thermo‐mechanical properties have been measured for carbon nanotube reinforced epoxy matrix composites. These nanocomposites consisted of two types of nanofillers, single walled carbon nanotubes (SW‐CNT) and electrical grade carbon nanotubes (XD‐CNT). The influence of the type of nanotubes and their corresponding loading weight fraction on the microstructure and the resulting electrical and mechanical properties of the nanocomposites have been investigated. The electrical conductivity of the nanocomposites showed a significantly high, about seven orders of magnitude, improvement at very low loading weight fractions of nanotubes in both types of nanocomposites. The percolation threshold in nanocomposites with SW‐CNT fillers was found to be around 0.015 wt % and that with XD‐CNT fillers around 0.0225 wt %. Transmission optical microscopy of the nanocomposites revealed some differences in the microstructure of the two types of nanocomposites which can be related to the variation in the percolation thresholds of these nanocomposites. The mechanical properties (storage modulus and loss modulus) and the glass transition temperature have not been compromised with the addition of fillers compared with significant enhancement of electrical properties. The main significance of these results is that XD‐CNTs can be used as a cost effective nanofiller for electrical applications of epoxy based nanocomposites at a fraction of SW‐CNT cost. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Hybrid composites of ABS with carbonaceous fillers for electromagnetic shielding applications

This work evaluates the influence of two types of carbonaceous fillers, carbon black (CB) and carbon nanotubes (CNTs), on the electrical, electromagnetic, and rheological properties of composites based on poly(acrylonitrile‐co‐butadiene‐co‐styrene) (ABS) prepared by the melt mixing. Electrical conductivity, electromagnetic shielding efficiency (EMI SE) in the X‐band frequency range (8–12.4 GHz), and melt flow index (MFI) results showed that ABS/CNT composites exhibit higher electrical conductivity and EMI SE, but lower MFI when compared to ABS/CB composites. The electrical conductivity of the binary composites showed an increase of around 16 orders of magnitude, when compared to neat ABS, for both fillers. Binary composites with 5 and 15 wt % of filler showed an EMI SE of, respectively, ?44 and ?83 dB for ABS/CNT, and ?9 and ?34 dB for ABS/CB. MFI for binary composites with 5 wt % were 15.45 and 0.55 g/10 min for CB and CNT, respectively. Hybrid composites ABS/CNT.CB with 3 wt % total filler and fraction 50:50 and 75:25 showed good correlation between EMI SE and MFI. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46546.     

Preparation and properties of carbon nanotube/binary‐polymer composites with a double‐segregated structure

A carbon nanotube (CNT)/poly(methyl methacrylate) (PMMA)/ultrahigh molecular weight polyethylene (UHMWPE) composite containing a double‐segregated structure was formalized by means of a facile mechanical mixing technology. In the composite, the CNTs were decorated on the surfaces of PMMA granules, and the CNTs decorated granules formed the continuous segregated conducting layers at the interfaces between UHMWPE particles. Morphology observations confirmed the formation of a specific double‐segregated CNT conductive network, resulting in an ultralow percolation threshold of ～0.2 wt %. The double‐segregated composite containing only 0.8 wt % CNT loading exhibited a high electrical conductivity of ～0.2 S m^?1 and efficient electromagnetic shielding effectiveness of ～19.6 dB, respectively. The thermal conductivity, temperature‐resistivity behaviors, and mechanical properties of the double‐segregated composites were also studied. This work provided a novel conductive network structure to attain a high‐performance conducting polymer composite at low filler loadings. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39789.