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     

Reinforcement role of carbon nanotubes,Part I: High‐performance epoxy resin

The reinforcement role of single‐walled carbon nanotubes (SWCNT) in a high‐performance epoxy resin is studied in this article, with the emphasis on the deformation and load transfer mechanism. Tensile tests show that introducing carbon nanotubes (CNTs) into the epoxy resin changes the tensile strength of the material, and that the increase of Young's modulus is in good agreement with the increasing of glass transition temperature (T_g) measured by differential scanning calorimetry (DSC). Residual strains in CNTs induced during curing process have been investigated both experimentally and theoretically. Raman spectroscopy study shows that load transfers more efficiently in tension than in compression. The Raman shifts of deformed CNTs under repeated loading indirectly reveals that the load can be further transferred via friction after debonding fully occurs. Thin epoxy layers were observed on the pull out ends of CNTs, which implies the existence of the immobilized epoxy layer between CNTs and bulk epoxy. POLYM. COMPOS., 36:2212–2219, 2015. © 2014 Society of Plastics Engineers     

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     

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     

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。     

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     

纳米填充环氧树脂/玻璃纤维复合材料的摩擦磨损性能研究

分别将纳米三氧化二铝（Al2O3）、纳米二氧化钛（TiO2）、纳米二氧化硅（SiO2）颗粒和碳纳米管(CNTs)填充到环氧树脂(EP)/玻璃纤维(GF)复合材料中,制备了纳米填充EP/GF复合材料,GF的体积含量为30 %。用环块摩擦试验机研究了纳米填充物对EP/GF复合材料的摩擦磨损性能的影响。结果表明,1.0 %（质量分数,下同）的CNTs能够较大幅度地降低复合材料的摩擦因数和磨损率,而纳米Al2O3、纳米TiO2和纳米SiO2颗粒可以明显提高复合材料的耐磨损性能。     

Improved thermomechanical properties of carbon fiber reinforced epoxy composite using amino functionalized XDCNT

Carbon fiber‐reinforced epoxy composites (CFEC) are fabricated infusing up to 0.40 wt % amino‐functionalized XD‐grade carbon nanotubes (XDCNT) using the compression molding process. Interlaminar shear strength (ILSS) and thermomechanical properties of these composites are evaluated through short beam shear and dynamic–mechanical thermal analysis tests. XDCNTs are infused into Epon 862 resin using a mechanical stirrer followed by sonication. After the sonication, the mixture was placed in a three roll milling processor for three successive cycles at 140 rpm for uniform dispersion of CNTs. Epikure W curing agent was then added to the resin using a high‐speed mechanical stirrer. Finally, the fiber was reinforced with the modified resin using the compressive mold. ILSS was observed to increase by 22% at 0.3 wt % XDCNT loading. Thermal properties, including storage modulus, glass transition temperature, and crosslink density demonstrated linear enhancement up to the 0.3 wt % XDCNT loading. Scanning electron microscopy revealed better interfacial bonding in the CNT‐loaded CFEC. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40709.     

Comparative study on electrical properties of orientated carbon nanotubes/epoxy composites

The percolation threshold of carbon nanotubes (CNTs)/epoxy resin composites was simulated in the Bruggeman' Effective‐Medium Theory based on experiment. Both distinct percolation effect and low percolation threshold in the aligned CNTs/epoxy composites were predicted. With the CNTs loading larger than the percolation threshold, the critical exponent of CNTs/epoxy composites rises rapidly with the increase of aspect ratio of CNTs. It is shown that the electrical conductivity of composites presents distinct aeolotropism, the percolation threshold is sensitive relative to the tiny change of the orientation factor, the aspect ratio, and the structure of CNTs in the composites matrix. The simulated results are consistent with the experimental results basically, and the discrepancy between simulated results and experimental results has been interpreted reasonably. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Experimental assessment on potential for processiblity of carbon nanotubes/epoxy system used as nanocomposites

In this study, carboxylic acid functionalized carbon nanotubes (CNTs) were used to modify epoxy with intent to develop a nanocomposite matrix for hybrid multiscale composites combining benefits of nanoscale reinforcement with well‐established fibrous composites. CNTs were dispersed in epoxy by using high energy sonication, followed by the fabrication of epoxy/CNTs composites. The processibility of CNTs/epoxy systems was explored with respect to their dispersion state and viscosity. The dependences of viscosity, mechanical and thermomechanical properties of nanocomposite system on CNTs content were investigated. The dispersion quality and reagglomeration behavior of CNTs in epoxy and the capillary infiltration of continuous fiber with the epoxy/CNTs dispersion were characterized using optical microscope and capillary experiment. As compared with neat epoxy sample, the CNTs nanocomposites exhibit flexural strength of 126.5 MPa for 1 wt% CNTs content and impact strength of 28.9 kJ m^?2 for 0.1 wt% CNTs content, respectively. A CNTs loading of 0.1 wt% significantly improved the glass transition temperatures, T_g, of the nanocomposites. Scanning electron microscopy (SEM) was used to examine the fracture surface of the failed specimens. It is demonstrated that the properties of CNTs/epoxy system are dispersion‐dominated and interface sensitive. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Effect of CNT dispersion methods on the strength and fracture mechanism of interface in epoxy adhesive/Al joints

The tensile and shear strengths of adhesively bonded aluminum (Al) joints were inspected in the presence of amino functionalized multi-wall carbon nanotubes (MWCNTs). Tensile and shear tests were carried out using butt and lap-shear joints. The main goal was to compare the effects of dispersion methods of functionalized-CNT into epoxy on the mechanical performances and failure mechanisms of Al joints. Two different types of dispersion procedures, distributing CNT in the hardener (HH method) and distributing CNT in the resin (RR method), were applied. To identify the failure mechanisms, the morphology of fracture surfaces were analyzed using scanning electron microscopy (SEM). Comparing two dispersion methods against one another ascertained that following the RR method for dispersing CNTs in the adhesive displayed larger shear strength, while applying HH method offered fairly greater tensile strength. Moreover, dispersing CNTs in the resin induced more uniform dispersion of CNTs as compared to distributing nanofillers in the hardener. Following RR method, CNTs good dispersion as well as the presence of effective crack growth dissipating mechanisms, increased the shear strength of CNT reinforced adhesive joint. Incorporating CNTs using HH approach encouraged the plastic void formation of epoxy around the agglomerated CNTs, and as a consequence, promoted the plastic deformation under tension.     

Formulation and characterization of leather and rubber wastes composites

Residues from footwear roughing and carding operations represent 5–15% (w/w) of the solid wastes generated by shoe‐making companies. These wastes are mainly composed by chromium tanned leather and sole materials, and are mostly land filled. Sometimes leaching tests show these wastes as hazardous due to chromium in the leachate. This work aims at a more sustainable option for these wastes by recycling them in styrene butadiene rubber (SBR) and acrylonitrile butadiene rubber (NBR). Thus, they were charged with: (i) ≤1 mm leather waste fibers in the range of 10–25 parts per hundred parts of rubber (phr); and (ii) leather and soles industrial carding and roughing wastes in the range of 20–100 phr. The leather waste fibers‐rubber composites tear strength is increased till 25 phr and both tension and elongation at break decrease within the acceptable range till 12.5 phr for SBR and 15 phr for NBR. In the case of leather and sole carding and roughing wastes, composites tear strength increases till 100 phr, and tension and elongation decrease within the acceptable range till 20 phr. The composite materials at the end of their life cycle may be considered inert or non‐hazardous wastes. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Studies on electrically conductive composites of ethylene propylene diene monomer rubber and steel fibers

Electrically conductive composites comprised of ethylene propylene diene monomer (EPDM) rubber and steel fibers were prepared by an open mill mixing method. Fibers of two distinctly different lengths (5 mm and several meters) were used and the influence of these fibers on electrical conductivity, mechanical, thermal, and physical properties of the composites was investigated. Composites with different compositions were prepared by varying the loading levels of fibers from 20–100 phr (parts per hundred parts of rubber). Homogeneity of the composites was determined using scanning electron microscopy. Further analysis included the measurement of resistance, hardness, tensile strength, tear strength, rebound resilience, etc. The results of the analysis revealed that the addition of steel fibers rendered conductivity to the otherwise insulating EPDM rubber even at small loading levels, however, the length appears to have negligible effect on conductivity. In case of short fibers, the resistance of composites was observed to decrease from > 40 MΩ (Initial value of EPDM rubber) to 25 KΩ at a loading level of 20 phr with a further significant decrease of the order of 10³, that is around 18 Ω at 100 phr. Composites with long fibers exhibited resistance in the range of 15 kΩ–70 Ω at loading levels between 30 and 100 phr. The conductivity of the sample is observed to be altered negligibly on ageing. Mechanical properties such as hardness, tensile, and tear strength were observed to be enhanced in case of composites except resilience which decreased by 29 % in comparison to EPDM rubber. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal conductivity of natural rubber nanocomposites with hybrid fillers

Natural rubber nanocomposites filled with hybrid fillers of multi-walled carbon nanotubes(CNTs) and carbon black(CB) were prepared. CNTs were ultrasonically modified in mixture of hydrogen peroxide(H_2O_2) and distilled water(H_2O). The functional groups on the surface of CNTs, changes in nanotube structure and morphology were characterized by Fourier transform infrared spectroscopy(FT-IR), Raman Spectroscopy, and transmission electron microscopy(TEM). It shows that hydroxyl(OH·) is successfully introduced. The surface defects of modified CNTs were obviously higher than those of original CNTs, and the degree of agglomeration was greatly reduced. Thermal conductivity of the composites was tested by protection heat flow meter method. Compared with unmodified CNTs/CB filling system, the thermal conductivity of hybrid composites is improved by an average of 5.8% with 1.5 phr(phr is parts per hundred rubber) of hydroxyl CNTs and 40 phr of CB filled. A three-dimensional heat conduction network composed of hydroxyl CNTs and CB, as observed by TEM, contributes to the good properties. Thermal conductivity of the hybrid composites increases as temperature rises. The mechanical properties of hybrid composites are also good with hydroxyl CNTs filled nanocomposites; the tensile strength, 100% and 300% tensile stress are improved by 10.1%, 22.4% and 26.2% respectively.     

碳纳米管／环氧耐热复合材料性能研究

研究了碳纳米管／环氧树脂复合材料电性能、热氧老化性能和粘接性能。研究结果表明：添加量为2％时,复合材料的综合性能最优,表面电阻率和体积电阻率分别下降了9—10个数量级,剪切强度提高了12．33％,当老化时间达到200h,复合材料重量保持率仍有90％。制得的复合材料能够用于耐热胶粘剂和防静电材料。     

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.     

Effect of rubber hardness on the properties of fiber reinforced plastic composites made by the newly proposed rubber pressure molding technique

The effect of rubber hardness on the properties of fiber‐reinforced plastic (FRP) composites is investigated in order to know the optimum composition of rubber mold used in rubber pressure molding (RPM) technique. A matching die set was used in RPM method, where the die was made of hard metal like steel and the punch from the flexible rubber like material, natural rubber. The use of flexible rubber punch generates and applies hydrostatic pressure on the surface of FRP composites. The hardness of rubber mold was controlled by incorporating carbon black as a filler material in the matrix of natural rubber and varied from 0 to 75 phr (per hundred rubber) in steps of 15 phr. Burn test, tension test, interlaminar shear test and interlaminar fracture toughness tests were conducted on the FRP composites to measure the void content, presence of delamination, tensile strength, inter laminar shear strength and inter laminar fracture toughness. The results are compared with the FRP composites made by conventional technique to evaluate the performance of RPM technique. It is observed that the laminates produced by RPM technique with different filler content in natural rubber mold show significant improvement in mechanical properties except interlaminar shear strength. POLYM. COMPOS., 28:618–630, 2007. © 2007 Society of Plastics Engineers     

Experimental study on the mechanical behavior and failure mechanism of 3d MWK carbon/epoxy composites under quasi‐static loading

Quasi‐static tensile, out‐of compression, in‐plane compression, three‐point‐bending and shear tests were conducted to reveal the mechanical behavior and failure mechanisms of three‐dimensional (3D) multiaxial warp‐knitted (MWK) carbon/epoxy composites. The characterization of the failure process and deformation analysis is supported by high‐speed camera system and Digital Image Correlation. The results show that tensile, bending, out‐of‐plane compression, in‐plane compression stress–strain response exhibit obvious linear elastic feature and brittle fracture characteristics, whereas the shear response exhibits a distinct nonlinear behavior and gradual damage process. Meanwhile, 3D MWK carbon/epoxy composites have good mechanical properties, which can be widely used in the fields of engineering. In addition, the failure for tension behaves as interlayer delaminating, 90/+45/−45° interface debonding and tensile breakage of 0° fibers; the damage for out‐of‐plane compression is mainly interlaminar shear dislocation together with local buckling and shear fracture of fibers; the failure pattern for in‐plane compression is 90° fiber separating along fiber/matrix interface as well as 0/+45/−45° fiber shear fracture in the shear plane. The main failure for bending is fiber/matrix interface debonding and fibers tearing on the compression surface, 0° fibers breakage on the tension surface as well as fiber layers delaminating. Although the shear behavior is characterized by a gradually growing shear matrix damage, 90/+45/−45° interface debonding, +45/−45° fibers shear fracture, and final 0° fiber compression failure. POLYM. COMPOS., 37:3486–3498, 2016. © 2015 Society of Plastics Engineers     

Improvement of dispersion of carbon nanotubes in epoxy resin through pyrogallol functionalization

Multiwalled carbon nanotubes (MWNTs) were functionalized with pyrogallol. The functionalized MWNTs were well‐dispersed in the epoxy/curing agent/ethanol solution, as demonstrated by UV‐vis spectra and optical micrographs. Epoxy resin/MWNTs composites were prepared via solution mixing method. The cure behavior was characterized using differential scanning calorimetry. Pyrogallol‐functionalized carbon nanotubes (CNTs) reacted with the epoxy through the mediation reaction of pyrogallol with the curing agent, leading to the interfacial bonding between the functionalized carbon nanotubes (CNTs) and the resin matrix. Due to the excellent dispersion and interfacial bonding, the mechanical strength and electrical conductivity of the epoxy resin/CNTs composites have been improved. POLYM. ENG. SCI. 56:1079–1085, 2016. © 2016 Society of Plastics Engineers     

Preparation and properties of hierarchical composites based on carbon nanotubes‐coated glass babric preform

A strategy based on carbon nanotubes (CNTs)‐containing sizing dispersion has been implemented to fabricate nanocomposite preforms and their hybrid multiscale composites. The state of pristine CNTs and carboxylic acid functionalized CNTs (CNTs–COOH) in sizing dispersion was effectively monitored by on‐line measuring electrical conductivity. The effects of different CNTs coating applied onto glass fabric on wettability of nanocomposite fibrous reinforcement with epoxy matrix were evaluated using scanning electron microscopy and capillary experiment. A CNTs‐COOH loading of 0.5 wt% gave rise to 97% and 30°C increases in the storage modulus (G′) and glass transition temperature of the resulting hybrid composites, respectively. The enhanced thermomechanical properties of the CNTs hybrid composites are closely related to the stable CNTs sizing dispersion and uniform coating onto fiber reinforcement. The mechanism for reinforcing composites through toughening resin region with CNTs desorbing from primary fiber surface during impregnation has been identified. POLYM. COMPOS. 37:979–986, 2016. © 2014 Society of Plastics Engineers