Effect of phenol functionalization of carbon nanotubes on properties of natural rubber nanocomposites

This paper reports the results of studies on the effect of phenol functionalization of carbon nanotubes (CNTs) on the mechanical and dynamic mechanical properties of natural rubber (NR) composites. Fourier transform infrared spectrometry (FTIR) indicates characteristic peaks for ether and aromatic rings in the case of phenol functionalized CNT. Although differential scanning calorimetric (DSC) studies show no changes in the glass‐rubber transition temperature (T_g) of NR in the nanocomposites due to surface modification of CNT, dynamic mechanical studies show marginal shifting of T_g to higher temperature, the effect being pronounced in the case of functionalized CNT. Stress‐strain plots suggest an optimum loading of 5 phr CNT in NR formulations and the phenolic functionalization of CNT does not affect significantly the stress‐strain properties of the NR nanocomposites. The storage moduli register an increase in the presence of CNT and this increase is greater in the case of functionalized CNT. Loss tangent showed a decrease in the presence of CNT, and the effect is more pronounced in the case of phenol functionalized CNT. Transmission electron microscopy (TEM) reveals that phenol functionalization causes improvement in dispersion of CNT in NR matrix. This is corroborated by the increase in electrical resistivity in the case of phenol functionalized CNT/NR composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of carbon black/nanoclay hybrid filler on the dynamic properties of natural rubber vulcanizates

In this study, natural rubber (NR) nanocomposites based on carbon black (CB) and two poly(ethylene glycol) (PEG)‐modified clay hybrid filler were fabricated. The morphology and mechanical properties were studied. The dynamic properties of NR vulcanizates were investigated over a range of strain amplitude at two temperatures. It was found that NR with hybrid filler exhibits superior mechanical properties over that with CB as single phase filler. The hybrid filler causes a significant alteration in the dynamic properties of rubber. The Payne effect becomes more pronounced in rubber with modified clay. A decrease in loss factor (tanδ) was observed for rubber with hybrid filler also. The results revealed that the inclusion of nanoclay (NC) could induce a stronger and more developed filler network. Because of the anisotropy of the nanolayers, NC would depress the reconstruction of filler network, or lower the reformation rates when broken down under deformation, giving rise to lower tanδ value at broad temperature range as well as strain amplitude. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of surface modification of silicon carbide nanoparticles on the properties of nanocomposites based on epoxidized natural rubber/natural rubber blends

Improvement of the properties of rubber nanocomposites is a challenge for the rubber industry because of the need for higher performance materials. Addition of a nanometer‐sized filler such as silicon carbide (SiC) to enhance the mechanical properties of rubber nanocomposites has rarely been attempted. The main problem associated with using SiC nanoparticles as a reinforcing natural rubber (NR) filler compound is poor dispersion of SiC in the NR matrix because of their incompatibility. To solve this problem, rubber nanocomposites were prepared with SiC that had undergone surface modification with azobisisobutyronitrile (AIBN) and used as a filler in blends of epoxidized natural rubber (ENR) and natural rubber. The effect of surface modification and ENR content on the curing characteristics, dynamic mechanical properties, morphology and heat buildup of the blends were investigated. The results showed that modification of SiC with AIBN resulted in successful bonding to the surface of SiC. It was found that modified SiC nanoparticles were well dispersed in the ENR/NR matrix, leading to good filler‐rubber interaction and improved compatibility between the rubber and filler in comparison with unmodified SiC. The mechanical properties and heat buildup when modified SiC was used as filled in ENR/NR blends were improved. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45289.     

Electrical and thermal properties of silicone rubber composites filled with Cu-coated carbon fibres and functional carbon nanotubes

ABSTRACT

The thermal and electrical conductivities of SR composites containing Cu-CFs and f-MWNTs were studied. The Cu-CFs and f-MWNTs were prepared by chemical deposition and the coupling method, respectively. Both the fillers were characterised by FT-IR, XRD and SEM and the results showed that the Cu layers were deposited on the surface of the CFs and the MWNTs were successfully modified. In addition, the results of thermal and electrical conductivities for SR composites showed that the hybrid fillers system exhibited a better enhancement on thermal and electrical conductivities for SR composites than the single filler system. The maximum thermal conductivity and the least volume resistivity of SR/Cu-CFs/f-MWNTs composites could reach 3.86?W (m?K)^?1 and 3.5?×?10³?Ω?cm, respectively. Based on the experimental results, we recognised the improvement of intrinsical thermal and electrical conductivities of CFs and the good dispersion of MWNTs contributed to the formation of densified 3D conducting networks. Thus, the hybrid fillers system could synergistically enhance the thermal and electrical conductivities of SR composites. We believe, this study could provide an effective way for the design of high conductive polymer composites.     

不同粒径的碳纳米管补强天然橡胶

以2种不同型号的短多壁碳纳米管（管径OD20-30nm和30-50nm,长度告为0.5-2μm）与炭黑N330混合成复合填料,采用混炼法讨论其对天然橡胶的补强作用。结果表明／碳纳米管对橡胶的拉伸强度、定伸应力、硬度等方面有着显著的影响;不同管径的碳纳米管由于其自身性能的差异,对天然橡胶的性能有不同的影响;碳纳米管的不同添加量对天然橡胶补强的各性能有非常大的影响。     

Polypropylene/multiwall carbon nanotubes nanocomposites: Nanoindentation,dynamic mechanical,and electrical properties

Polypropylene (PP)/Multiwall carbon nanotubes (MWCNTs) nanocomposites were fabricated via melt compounding that utilizes a corotating twin‐screw extruder. Two commercially available MWCNTs, Baytubes C150P and C70P, were incorporated into PP matrix at concentration of 3 wt %. The nanocomposites samples were analyzed using scanning electron microscopy, dynamic mechanical analysis (DMA), nanoindentation test, and picoammeter. It was found that both MWCNTs types were well distributed and dispersed in the PP matrix and no agglomeration of MWCNTs was observed. The DMA analysis results showed that the incorporation of MWCNTs enhanced the storage modulus and thermal stability of the PP matrix. Whereas, nanoindentation creep results showed that the creep rate and displacement of the PP/MWCNTs nanocomposites was lower than the neat PP, in which C70P < C150P < PP. The reduction of creep rate and creep displacement was associated to the improvement of creep resistance. There were also improvements on hardness and stiffness of the nanocomposites. Additionally, the electrical resistivity of the neat PP decreased with the incorporation of MWCNTs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45293.     

碳纳米管增强天然橡胶复合材料的制备与性能研究

碳纳米管以其特殊的结构与优异的性能成为橡胶的理想填料。本文分别采用四种不同牌号(分别为Flotube7000 9000 9011 9400)的碳纳米管为实验原料,制备了碳纳米管/天然橡胶复合材料,并对其性能进行了研究探讨。结果发现,碳纳米管的加入能显著提高复合材料的力学性能和热导率,具有一维取向排列且长径比较大的Flotube7000(以下简称7000)对力学性能的提高程度最大,Flotube7000以及经过酸处理的表面具有-OH、–COOH官能团的Flotube9011(以下简称9011)对导热性能提高程度最为明显。     

Improvement of the mechanical and electrical properties of waste rubber with carbon nanotubes

The effect of carbon nanotubes (CNTs) on the stability of the mechanical and electrical properties of recycled waste rubber was experimentally investigated. The stress–strain curves of the composites were studied. The results show that the toughness, the area under the stress–strain curve, of the recycled rubber increased monotonically as a result of the addition of CNTs. The modulus of the nanocomposites increased by 28 times when only 5 wt % CNTs was added to the recycled rubber matrix. The effects of the cyclic fatigue and hysteresis for the composites were also examined. The strain energy density, dissipation energy, and linear damage accumulation versus the number of cycles are discussed for all of the samples. The analysis of the results showed that the strain energy density increased by 15 times at a CNT concentration of 5 wt %. The electrical properties were measured for all of the samples. The results indicate that the addition of CNTs to the recycled rubber improved its electrical conductivity by more than two orders. © 2011 Wiley Periodicals, Inc. J Polym Sci, 2011     

Structure and properties of hollow carbon black and filled rubber nanocomposites

Abstract

Hollow carbon black (HCB) is introduced in this work. It has a special hollow structure, high specific surface area, high structure and high electric conductivity. Hollow carbon black is used to fill styrene–butadiene rubber (SBR). The bound rubber test results show that the bound rubber of SBR/HCB can be measured when the HCB content reaches 25 phr because a strong filler network is formed, which indicates good electric conductivity of SBR/HCB. In comparison, the bound rubber of SBR/N330 can not be measured even when the N330 content is 40 phr. The mechanical measurements show that HCB has very good reinforcing effect on SBR especially when the filler content is low. The electric conductivity and thermal conductivity increase with the increase in filler content. At the same filler content, the properties of SBR/HCB nanocomposites are better than those of SBR/N330 nanocomposites, which suggests that HCB has good application potential.     

Influence of aminosilane‐functionalized carbon nanotubes on the rheometric,mechanical, electrical and thermal degradation properties of epoxidized natural rubber nanocomposites

We describe the preparation, characterization and physical properties of multiwalled carbon nanotube (MWCNT)‐filled epoxidized natural rubber (ENR) composites. To ensure better dispersion in the elastomer matrix, the MWCNTs were initially subjected to aminopropyltriethoxysilane (APS) treatment to bind amine functional groups (?NH₂) on the nanotube surface. Successful grafting of APS on the MWCNT surface through Si–O–C linkages was confirmed using Fourier transform infrared spectroscopy. Grafting of APS on the MWCNT surface was further corroborated using elemental analysis. ENR nanocomposites with various filler loadings were prepared by melt compounding to generate pristine and APS‐modified MWCNT‐filled elastomeric systems. Furthermore, we determined the effects of various filler loadings on the rheometric, mechanical, electrical and thermal degradation properties of the resultant composite materials. Rheometric cure characterization revealed that the torque difference increased with pristine MWCNT loading compared to the gum system, and this effect was more pronounced when silane‐functionalized MWCNTs were loaded, indicating that this effect was due to an increase in polymer–carbon nanotube interactions in the MWCNT‐loaded materials. Loading of silane‐functionalized MWCNTs in the ENR matrix resulted in a significant improvement in the mechanical, electrical and thermal degradation properties of the composite materials, when compared to gum or pristine MWCNT‐loaded materials.© 2013 Society of Chemical Industry     

Effect of annealing treatment on the structure and properties of polyurethane/multiwalled carbon nanotube nanocomposites

The thermoplastic polyurethane/multiwalled carbon nanotube (TPU/CNT) nanocomposites with high conductivity and low percolation threshold value were prepared by melting blending and annealing treatment. The effect of annealing process on the microphase structure and the properties of TPU/CNT nanocomposites was studied. It has been shown that CNT flocculation can occur in TPU/CNT nanocomposites during the annealing process. At a critical CNT content, which defined the percolation threshold, CNTs could form conductivity network. The conductive percolation threshold value of TPU/CNT nanocomposites was decreased from 10 to 4% after annealing process, and the conductivity of TPU/CNT nanocomposites with 10 vol % of CNT could reach 1.1 S/m after an annealing time of 1 h. The significant enhancement of electrical conductivity was influenced by the annealing time and the content of CNTs. The formation of CNT networks was also verified by dynamic viscoelastic characterization. The results of X‐ray diffraction and differential scanning calorimetry indicated that annealing process reinforced the microphase separation of the nanocomposites. Mechanical properties test showed that the annealing treatment was in favor of improving the mechanical properties; however, further increase in the annealing time has negative effect on the mechanical properties. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

碳纳米管炭黑天然橡胶复合材料的制备与性能研究

碳纳米管以其特殊的结构与优异的性能成为橡胶补强的理想填料。本文中我们采用两种不同牌号的碳纳米管(分别为Flotube 7000、9011)与炭黑N660作为实验原料,制备了碳纳米管/炭黑/天然橡胶复合材料,并对其性能进行了探讨。结果发现：碳纳米管的加入能明显提高复合材料的定伸应力,具有一维取向排列且长径比较大的Flotube 7000(以下简称7000)对力学性能的提高程度最大。且我们将碳纳米管7000、9011分别与炭黑N660并用,对于提高复合材料的导热性能并没有如我们预期的一样存在所谓的“叠加关系”甚至是“协同效应”,而是对于提高复合材料导热有着一定的“负协同效应”。     

Effects of mineral fillers addition and preparation method on the morphology and electrical conductivity of epoxy/multiwalled carbon nanotube nanocomposites

This study investigated the correlation between the electrical conductivity and the micro and nanomorphology of multiwalled carbon nanotubes (MWCNTs)/epoxy nanocomposites with and without the inorganic fillers montmorillonite (MMT), sepiolite and calcium carbonate (CaCO₃). The nanocomposites were prepared by dispersing the MWCNT and fillers through ultrasonication directly in the resin or solvent. For nanocomposites without fillers, the compositions prepared with solvent demonstrated higher electrical conductivities, which correlate with a microscale morphology formed by networks of highly interconnected MWCNT agglomerates. The addition of MMT induced a deleterious effect on the electrical conductivity of the nanocomposites since this filler hinders the formation of MWCNT agglomerate networks. The effect of sepiolite on electrical conductivity is also negative, but in this case, nonmorphological effects are likely of greater importance. The addition of CaCO₃ improved the electrical conductivity of the binary nanocomposites under specific conditions. For this filler, a synergic effect was achieved for the composition prepared with solvent, which resulted in an approximately sixfold increase in electrical conductivity relative to the nanocomposite without filler.     

碳纳米管/橡胶复合材料的研究进展

介绍了碳纳米管(C NTs)的预处理方式,主要有纯化处理和表面改性2种方式,概述了CNTs/橡胶复合材料的制备方法,包括机械混炼法、溶液共混法和喷雾干燥法,以及复合材料的物理机械性能、电学性能、热学性能等性能,并根据复合材料的性能缺陷提出今后的研究方向.     

Copolyester nanocomposites based on carbon nanotubes: reinforcement effect of carbon nanotubes on viscoelastic and dielectric properties of nanocomposites

Nanocomposites based on an amorphous copolyester, poly(ethylene glycol‐co‐cyclohexane‐1,4‐dimethanol terephthalate) and carbon nanotubes were fabricated using a simple melt processing technique. The reinforcement effect of carbon nanotubes in the copolyester was investigated experimentally using different approaches based on dynamic mechanical analysis, rheology and dielectric analysis. The nanocomposites show a mechanical reinforcement effect with significant increase in the stiffness especially in the rubbery regime with increasing nanotube content. An increase in T_g and a decrease in damping are seen, which are derived from the presence of a percolating superstructure of the filler. Rheological experiments show an increase in storage modulus up to four orders of magnitude. Viscolelastic characterization shows that the percolation threshold is at 3 wt% of nanotubes. Dielectric relaxation spectroscopy confirms the presence of this percolating structure. We conclude that the responses of both rheological and electrical properties are different, although both are related to the formation of a percolating network superstructure of the filler. Copyright © 2007 Society of Chemical Industry     

Effect of carbon black loading on curing characteristics and mechanical properties of waste tyre dust/carbon black hybrid filler filled natural rubber compounds

Curing characteristics, tensile properties, fatigue life, swelling behavior, and morphology of waste tire dust (WTD)/carbon black (CB) hybrid filler filled natural rubber (NR) compounds were studied. The WTD/CB hybrid filler filled NR compounds were compounded at 30 phr hybrid filler loading with increasing partial replacement of CB at 0, 10, 15, 20, and 30 phr. The curing characteristics such as scorch time, t₂ and cure time, t₉₀ decreased and increased with increment of CB loading in hybrid filler (30 phr content), respectively. Whereas maximum torque (M_HR) and minimum torque (M_L) increased with increasing CB loading. The tensile properties such as tensile strength, elongation at break, and tensile modulus of WTD/CB hybrid filler filled NR compounds showed steady increment as CB loading increased. The fatigue test showed that fatigue life increased with increment of CB loading. Rubber–filler interaction, Q_f/Q_g indicated that the NR compounds with the highest CB loading exhibited the highest rubber–filler interactions. Scanning electron microscopy (SEM) micrographs of tensile and fatigue fractured surfaces and rubber–filler interaction study supported the observed result on tensile properties and fatigue life. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and properties of cyclic olefin copolymers multiwalled carbon nanotube nanocomposites

Nanocomposites of cyclic olefin copolymer (COC) and two types of multiwalled carbon nanotubes (MWCNTs) with different aspect ratios were prepared. The morphology, thermal behavior, and electrical conductivity of the nanocomposites were investigated by scanning electron microscopy, differential scanning calorimetry, thermal gravimetric analysis, and the DC conductivity measurement. It was found that the developed nanocomposite preparation method resulted in good nanotubes dispersion in the polymer matrix for both types of MWCNTs. No appreciable differences in glass transition temperatures were observed between the pure COC and nanocomposites. On the other hand, CNTs significantly improved the thermo‐oxidative stability of the COC. The nanocomposites showed significant delay in onset of degradation and the degradation temperature was ～ 40°C higher than that of the pure COC. The nanocomposites also showed substantially higher DC conductivity, which increased with the nanotube concentration and aspect ratio. An increase of DC electrical conductivity over 10⁹ times can be achieved by the addition of 2 wt % CNTs. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

碳纳米管预处理方法对天然橡胶/纯化碳纳米管复合材料力学性能的影响

纯化后的碳纳米管(CNT)分别经过球磨、表面活性剂十二烷基苯磺酸钠或分散-黏合体系预处理,再与100份(质量)天然橡胶(NR)混炼,可制备NR/纯化CNT复合材料。结果表明,纯化CNT直接与NR混炼,前者在NR中的分散效果不好,二者的界面结合欠佳。纯化CNT经球磨后,团聚程度增加,对复合材料力学性能影响不大。经表面活性剂十二烷基苯磺酸钠处理后的纯化CNT,内聚能下降,用差示扫描量热法(DSC)测定复合材料的DSC曲线表明,复合材料的结晶熔融峰面积增大,力学性能降低。用分散-黏合体系处理纯化CNT,可同时提高纯化CNT在橡胶中的分散效果及界面黏合性,试样结晶熔融峰变得不明显,因此该复合材料的邵尔A型硬度提高,拉伸强度、300％定伸应力和撕裂强度等优于其他试样。     

碳纳米管/天然橡胶复合材料的结构与性能

通过机械混炼法制备了碳纳米管(CNT)／天然橡胶(NR)复合材料,研究了CNT的预处理方式对复合材料结构与性能的影响。结果表明,与NR相比,CNT／NR复合材料的硫化返原现象减轻,硫化后凝胶质量分数降低,硫化剂用量应适当增加,由混酸氧化处理的CNT填充橡胶复合材料的硫化迟滞效应明显;复合材料内部存在CNT的富集区域和CNT含量很少的橡胶区域,CNT与NR之间的界面结合作用不好;由HF处理的CNT填充橡胶复合材料的整体性能最好,但受CNT在橡胶基体中的不良分散状态及界面性质的影响,其力学性能不高。     

Crack growth resistance of natural rubber reinforced with carbon nanotubes

Carbon nanotubes (CNTs)/natural rubber (NR) composites are prepared through ultrasonically assisted latex mixing combined with a two-roll mixing process, and their crack growth behavior is examined to evaluate their fatigue properties. CNTs/NR shows a reinforcement of crack growth resistance compared to unfilled NR. The measurements of the tearing energy and the hysteresis loss show that CNTs/NR exhibits more energy dissipation than NR. Also, strain-induced crystallization (SIC) around the crack tip of CNTs/NR and NR composite was examined at different fatigue strains. CNTs positioned at the crack tip led to a crack branching at low fatigue strain, which is responsible for the improvement of the crack growth resistance of CNTs/NR. However, the inclusion of CNTs renders NR higher crystallinity and larger crystallization zones in front of the crack tip at high fatigue strains, which allows more energy dissipation during crack growth. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48447.