High thermal conductive m‐xylylenediamine functionalized multiwall carbon nanotubes/epoxy resin composites

In this study, multiwall carbon nanotubes (MWNTs) functionalized by m‐xylylenediamine is used as thermal conductive fillers to improve their dispersibility in epoxy resin and the thermal conductivity of the MWNTs/bisphenol‐A glycidol ether epoxy resin composites. Functionalization with amine groups of MWNTs is achieved after such steps as carboxylation, acylation and amidation. The thermal conductivity, impact strength, flexural strength, and fracture surfaces of MWNTs/epoxy composites are investigated with different MWNTs. The results show that m‐xylylenediamine is successfully grafted onto the surface of the MWNTs and the mass fraction of the organic molecules grafted onto MWNTs is about 20 wt %. The thermal conductivity of MWNTs/epoxy composites is further enhanced to 1.236 W/mK with 2 wt % m‐MWNTs. When the content of m‐MWNTs is 1.5 wt %, the impact strength and flexural strength of the composites are 25.85 KJ/m², 128.1 MPa, respectively. Scanning electron microscope (SEM) results show that the fracture pattern of composites is changed from brittle fracture to ductile fracture. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41255.     

Influence of different functionalized multiwall carbon nanotubes on the mechanical properties of poly(ethylene terephthalate) fibers

Master batches with four different kinds of functionalized multiwall carbon nanotubes (MWCTs) were prepared through the mixing of MWCTs with poly(ethylene terephthalate) (PET) (0.01 : 0.99 w/w) in trifluoroacetic acid/dichloromethane mixed solvents (0.7 : 0.3 v/v) followed by the removal of the solvents in the mixture by flocculation. The results of scanning electron microscopy showed that a good dispersion of MWCTs in PET was achieved. The reinforced fibers were fabricated by the melt spinning of PET chips with small amounts of the master batch and then further postdrawing. The optimal spinning conditions for the reinforcement of fibers were a 0.6-mm spinneret hole and a 250 m/min wind-up speed. Among the four master batches, the fibers obtained from PET/master batch B made by acid-treatment had the highest enhancement of mechanical properties. For a 0.02 wt % loading of acid-treated MWCT, the breaking strength of the PET/master batch B composite fibers increased by 36.9% (from 4.45 to 6.09 cN/dtex), and the initial modulus increased by 41.2% (from 80.7 to 113.9 cN/dtex). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The role of the interphase on the shear induced failure of multiwall carbon nanotubes reinforced epoxy nanocomposites

Multiwall Carbon Nanotubes (MWCNT) with an elevated aspect ratio were chemically functionalized with amines and two types of epoxide groups. Thermogravimetric analysis and Fourier Transform‐Infrared Spectroscopy (FTIR) analysis corroborated that the functionalization degree was substantial (up to 30 wt %) and the presence of a covalent bond with the MWCNT. The functionalized MWCNT (f‐CNT) were incorporated into an epoxy matrix after its dispersion in the diglycidyl ether of bisphenol A (DGEBA) precursor. To induce a shear failure mode, a short‐beam (SB) experimental setup was implemented. The SB shear strength (SBSS) proved that the functionalization had a strong influence on its value. For the case of pristine CNT, a neutral effect was obtained. A strong detrimental effect (?17.2% ± 9.5) was measured for the amine type f‐CNT and a positive effect (up to 10.9% ± 8.9) was measured of the epoxide type f‐CNT. Fractographic analysis of each formulation was correlated with SBSS performance, proving that the surface texture of the fractured samples was strongly correlated to its value. Furthermore, dynamic mechanical analysis proved that the damping factor and the crosslink molecular weight were correlated with the SBSS performance. A lower full width at half maximum of the damping factor was associated to an improvement of SBSS. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41364.     

Development of high Tg epoxy resin and mechanical properties of its fiber‐reinforced composites

A new epoxy resin with high glass transition temperature (T_g) (～ 180°C) and a viscosity low enough for infiltration into dry reinforcements at 40°C was developed for the vacuum‐assisted resin transfer molding process. To study the curing behavior and viscosity, several blends were formulated using multifunctional resin, aromatic hardener, and reactive diluents. Effects of these components on the viscosity and T_g were investigated by thermomechanical analysis, dynamic scanning calorimetry, and rheometer. Experimental results showed that a liquid aromatic hardener and multifunctional epoxy resin should be used to decrease the viscosity to <1 Pa·s at 40°C. Moreover, the addition of a proper reactive diluent decreased the viscosity and simultaneously minimized the deterioration of T_g. Mechanical properties of the composite produced with the optimized blend were evaluated at both room‐temperature and high‐temperature conditions. According to the results, the composite showed comparable mechanical properties with that of the current commercial resin. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanical and thermal properties of functionalized multiwalled carbon nanotubes and multiwalled carbon nanotube–polyurethane composites

Multiwalled carbon nanotube (MWNT)–polyurethane (PU) composites were obtained by an in situ polycondensation approach. The effects of the number of functional groups on the dispersion and mechanical properties were investigated. The results showed that the functionalized MWNTs had more advantages for improving the dispersion and stability in water and N,N′‐dimethylformamide. The tensile strength and elongation at break of the composites exhibited obvious increases with the addition of MWNT contents below 1 wt % and then decreases with additions above 1 wt %. The maximum values of the tensile strength and elongation at break increased by 900 and 741%, respectively, at a 1 wt % loading of MWNTs. Differential scanning calorimetry measurements indicated that the addition of MWNTs resulted in an alteration of the glass‐transition temperature of the soft‐segment phase of MWNT–PU. Additionally, new peaks near 54°C were observed with differential scanning calorimetry because of the microphase‐separation structures and alteration of the segment molecular weights of the hard segment and soft segment of PU with the addition of MWNTs. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of amino‐functionalized carbon nanotubes on the properties of amine‐terminated butadiene–acrylonitrile rubber‐toughened epoxy resins

Amino‐functionalized multiwalled carbon nanotubes (MWCNT‐NH₂s) as nanofillers were incorporated into diglycidyl ether of bisphenol A (DGEBA) toughened with amine‐terminated butadiene–acrylonitrile (ATBN). The curing kinetics, glass‐transition temperature (T_g), thermal stability, mechanical properties, and morphology of DGEBA/ATBN/MWCNT‐NH₂ nanocomposites were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis, a universal test machine, and scanning electron microscopy. DSC dynamic kinetic studies showed that the addition of MWCNT‐NH₂s accelerated the curing reaction of the ATBN‐toughened epoxy resin. DSC results revealed that the T_g of the rubber‐toughened epoxy nanocomposites decreased nearly 10°C with 2 wt % MWCNT‐NH₂s. The thermogravimetric results show that the addition of MWCNT‐NH₂s enhanced the thermal stability of the ATBN‐toughened epoxy resin. The tensile strength, flexural strength, and flexural modulus of the DGEBA/ATBN/MWCNT‐NH₂ nanocomposites increased increasing MWCNT‐NH₂ contents, whereas the addition of the MWCNT‐NH₂s slightly decreased the elongation at break of the rubber‐toughened epoxy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40472.     

Isotactic polypropylene composites reinforced with multiwall carbon nanotubes,part 2: Thermal and mechanical properties related to the structure

Polypropylene nanocomposites containing multiwall carbon nanotubes (MWCNT), from 0.1 to 3 wt %, are prepared by dilution of a polypropylene based masterbatch (20% MWCNT) with isotactic polypropylene (iPP) using extrusion processing. CNT are found to enhance significantly the thermal stability of iPP in nitrogen and air atmosphere. Dynamic mechanical analysis and tensile tests confirm the reinforcement effect of small amount of nanotubes in iPP. Rheology, structure, and properties are correlated determine the optimal limits of nanofiller content required for improving the performance of nanocomposites. The rheological flocculation threshold of φ* = 0.5% is found as a critical concentration for the formation of a flocculated type of structure in the dispersions. It is proposed, that the flocculated structure is responsible for the maximal improvement of nanocomposite mechanical and thermal properties. The MWCNT additive slightly enhances the local dynamics of iPP molecules in the glass transition region and suppresses the global relaxation of the chain segments in the amorphous regions, resulting in a reinforcement effect. The fracture mechanism is discussed and associated with the hierarchy of the flocculated nanocomposite morphology and the bridging of matrix cracks by CNT. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

多壁碳纳米管／环氧树脂复合材料性能研究

采用物理机械方法与化学方法相结合的手段,制备了多壁碳纳米管（MWNTS）／环氧树脂（Epoxy）复合材料。通过力学拉伸试验测试了MWNTs/Epoxy复合材料拉伸强度和拉伸模量与MWNTS添加量的关系,利用扫描电镜（SEM）分析了MWNTS／Epoxy复合材料的拉伸断面,并用表面电阻测试仪对所制备的碳纳米管复合材料进行了电学性能测试。结果表明：经过化学酸化的方法处理后的MWNTS在复合材料中的分散得到了改善,力学性能也得到了明显的提高,但酸处理后的复合材料的电学性能明显低于未处理的复合材料。     

Pseudoreinforcement effect of multiwalled carbon nanotubes in epoxy matrix composites

The carbon nanotube possesses outstanding physical properties. Theoretically, adding carbon nanotubes into a polymer matrix can remarkably improve the mechanical properties of the polymer matrix. In the present work, a series of composites was prepared by incorporating multiwalled carbon nanotubes (MWNTs) into an epoxy resin. The influences of MWNT content and curing temperature on the flexural properties of the epoxy resin were investigated. The results showed that a very low MWNT content should be used to ensure homogeneous dispersion of MWNTs in the epoxy matrix. A higher MWNT content may lead to deteriorated mechanical properties of the composites because of the aggregation of MWNTs. A decline in the flexural properties of the neat epoxy resin with increasing curing temperature was found. However, under the same curing conditions, improvement in flexural properties was observed for the composite with the low MWNT content and a mild curing temperature. The improvement was far beyond the predictions of the traditional short‐fiber composite theory. In fact, this improvement should be attributed to the retarding effect of MWNTs on the curing reaction of epoxy matrix. Therefore, the improvement in the flexural properties was only a pseudoreinforcement effect, not a nano‐reinforcement effect of the MWNTs on the epoxy resin. Perhaps, it is better for MWNTs to be used as functional fillers, such as electrical or thermal conductive fillers, than as reinforcements. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3664–3672, 2006     

Comprehensive high‐performance epoxy nanocomposites co‐reinforced by organo‐montmorillonite and nano‐SiO2

Comprehensive high‐performance epoxy nanocomposites were successfully prepared by co‐incorporating organo‐montmorillonite (o‐MMT) and nano‐SiO₂ into epoxy matrix. Because of the strong interaction between nanoscale particles, the MMT layers were highly exfoliated, and the exfoliated nanoscale MMT monoplatelets took an interlacing arrangement with the nano‐SiO₂ particles in the epoxy matrix, as evidenced by X‐ray diffraction measurement and transmission electron microscopy inspection. Mechanical tests and thermal analyses showed that the resulting epoxy/o‐MMT/nano‐SiO₂ nanocomposites improved substantially over pure epoxy and epoxy/o‐MMT nanocomposites in tensile modulus, tensile strength, flexural modulus, flexural strength, notch impact strength, glass transition temperature, and thermal decomposition temperature. This study suggests that co‐incorporating two properly selected nanoscale particles into polymer is one pathway to success in preparing comprehensive high‐performance polymer nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Curing of DGEBA epoxy resin by low generation amino‐group‐terminated dendrimers

Low generation amino‐group‐terminated poly(ester‐amine) dendrimers PEA1.0 (NH₂)₃ and PEA1.5 (NH₂)₈, and poly(amido‐amine) dendrimer PAMAM1.0 (NH₂)₄ were used as diglycidyl ether of bisphenol A (DGEBA) epoxy resin hardeners. Thermal behavior and curing kinetics of dendrimer/DGEBA systems were investigated by means of differential scanning calorimetry (DSC). Compared with ethylene diamine (EDA)/DGEBA system, the dendrimer/DGEBA systems gradually liberated heat in two stages during the curing process, and the total heat liberated was less. Apparent activation energy and curing reaction rate constants for dendrimer and EDA/DGEBA systems were estimated. Thermal stabilities and mechanical properties of cured thermosetting systems were examined as well. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3902–3906, 2006     

Effect of non-ionic surfactants on thermomechanical properties of epoxy/multiwall carbon nanotubes composites

Epoxy/multiwall carbon nanotubes (MWCNTs) composites were investigated using three different non-ionic surfactants (BYK-110, Tween-80 and Nonidet-P40) separately as a modifier. The role of surfactants in dispersion of MWCNTs in the epoxy matrix was studied. Among three surfactants used, performance of Nonidet-P40 was found to be the best in improving the thermomechanical properties of the epoxy resin and achieving good dispersion of MWCNTs. The good dispersion of Nonidet-P40 modified MWCNT in the epoxy matrix is a result of the π–π interaction between π electrons of the Nonidet-P40 and π electron clouds of MWCNTs as well as H-bonding interaction between of Nonidet-P40 and the epoxy matrix. This type of interaction does not disturb the π electron clouds of MWCNTs as opposed to chemical functionalization strategy.     

Thermal and mechanical properties of wood‐plastic composites filled with multiwalled carbon nanotubes

Wood plastic composites (WPCs) are a new generation of green composites which can come mostly from recycled materials. This study focuses on the thermal conductivity and mechanical properties of WPCs filled multiwalled carbon nanotubes (MWCNTs). The thermal conductivity increases with increasing amount of MWCNTs and decreases with increasing temperature. By comparing the temperature changes of specimens during heating and cooling processes, WPCs with higher MWCNTs contents presents higher average temperature when heated until equilibrium temperature. From differential scanning calorimeter test, the melting temperatures of MWNTs reinforced WPCs change slightly, but the crystallinity is reduced with the increasing amount of MWCNTs. Based on a series of laboratory experiments carried out to investigate the mechanical performance, it can be concluded that the addition of the MWCNTs decreases the mechanical properties of WPCs due to the decohesion between thermoplastic matrix and MWCNTs particles under stress. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46308.     

Studies on effect of ethyl 4-amino cinnamate functionalized multiwall carbon nanotubes (f-MWCNTs) on properties of millable polyurethane rubber (MPU) nanocomposites

Multiwall carbon nanotubes (MWCNTs) were prepared using chemical vapor deposition (CVD) technique in presence of nano Co/Mo-MgO as an efficient catalyst. Further the as-synthesized MWCNTs were functionalized using ethyl 4-amino cinnamate (f-MWCNTs) to improve its wettability or compatibility with the chains of polymer. The as-synthesized MWCNTs and f-MWCNTs were subjected to various characterization techniques Raman spectroscopy, X-ray diffraction, FTIR, FESEM and TGA to investigate its size, presence of functional groups and stability. It was observed that diameter of f-MWCNTs were found to be ~ 45 nm with thermally more stable. Further, f-MWCNTs (0 to 1 %) were reinforced in MPU rubber using two roll mill and molded on compression molding machine. The dumbbell shape specimens were then subjected to mechanical and thermal study. It was observed that both the tensile strength and % elongation at break of MPU nanocomposites increases significantly up to 0.8 wt loading and decreases thereafter. This improvement in properties was due to uniform dispersion of f-MWCNTs into the chains of MPU rubber with homogeneity in bonding, while the decrement in properties at 1wt % loading was due to agglomeration of f-MWCNTs at some places. Also the functionalization using ethyl 4-amino cinnamate increases the compatibility of MWCNTs with MPU rubber chains. Besides this, functionalization makes the surface of MWCNTs smooth with enhancement in bonding between the two surfaces that is filler as well as matrix counterpart. Significant improvement in mechanical and thermal properties are achieved due to modification MPU with functionalized MWCNT.     

Improving thermal conductivity and shear strength of carbon nanotubes/epoxy composites via thiol‐ene click reaction

This study investigates the effect of the thiol‐ene click reaction on thermal conductivity and shear strength of the epoxy composites reinforced by various silane‐functionalized hybrids of sulfhydryl‐grafted multi‐walled carbon nanotubes (SH‐MWCNTs) and vinyl‐grafted MWCNTs (CC‐MWCNTs). The results of Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, thermal gravimetric analysis (TGA), and transmission electron microscopy (TEM) show that the sulfhydryl groups and vinyl groups are successfully grafted onto the surface of MWCNTs, after treatment of MWCNT with triethoxyvinylsilane and 3‐mercaptopropyltrimethoxysilane, respectively. Scanning electron microscopy (SEM), HotDisk thermal constant analyzer (HotDisk), optical microscope, and differential scanning calorimetry (DSC) are used to characterize the resultant composites. It is demonstrated that the hybrid of 75 wt % SH‐MWCNTs and 25 wt % CC‐MWCNTs has better dispersion and stability in epoxy matrix, and shows a stronger synergistic effect in improving the thermal conductivity of epoxy composite via the thiol‐ene click reaction with 2,2′‐azobis(2‐methylpropionitrile) as thermal initiator. Furthermore, the tensile shear strength results of MWCNT/epoxy composites and the optical microscopy photographs of shear failure section indicate that the composite with the hybrid MWCNTs has higher shear strength than that with raw MWCNTs. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44579.     

Improved impact strength of epoxy by the addition of functionalized multiwalled carbon nanotubes and reactive diluent

Multiwalled carbon nanotubes (MWCNTs), both oxidized and amine functionalized (triethylenetetramine—TETA), have been used to improve the mechanical properties of nanocomposites based on epoxy resin. The TGA and XPS analysis allowed the evaluation of the degree of chemical modification on MWCNTs. Nanocomposites were manufactured by a three‐roll milling process with 0.1, 0.5, and 1.0 wt % of MWCNT–COOH and MWCNT–COTETA. A series of nanocomposites with 5.0 wt % of reactive diluent was also prepared. Tensile and impact tests were conducted to evaluate the effects of the nanofillers and diluent on the mechanical properties of the nanocomposites. The results showed higher gains (258% increase) in the impact strength for nanocomposites manufactured with aminated MWCNTs. Optical microscopy (OM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were used to investigate the overall filler distribution, the dispersion of individual nanotubes, and the interface adhesion on the nanocomposites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42587.     

Influence of KOH solution on the tensile strength and chemical stability of carbon fiber‐reinforced epoxy resin composites

The effect of a relatively high concentration of KOH solution (4M) on the mechanical properties and chemical stability of carbon fiber‐reinforced epoxy resin composites, prepared with different volume fractions of reinforcement, were investigated. Upon treatment of specimens of such composites with the KOH solution at different temperature and for different durations, their tensile strengths were adversely affected to varying degrees, depending on treatment conditions and volume percent of carbon fiber reinforcement used. Surfaces of treated specimens were examined for matrix stability, fiber disruption, and debonding. Optical microscopy, scanning electron microscopy (SEM), and X‐ray photoelectron spectroscopy (XPS) were used to evaluate chemical and mechanical degradation of these composites. Results clearly showed that prolonged exposure of composite specimens to such aggressive environments markedly increased the degradation of their mechanical properties. On the other hand, these results also showed that increasing the volume fraction of the carbon fiber reinforcement reduced the severity of degradation of these composite and enhanced their mechanical stability. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1682–1690, 2005     

Microwave responsive epoxy nanocomposites reinforced by carbon nanomaterials of different dimensions

This study fabricated nanocomposites consisting of epoxy‐based shape memory polymer (ESMP) matrix and carbon nanofillers. The nanofillers include zero‐dimensional carbon black, one‐dimensional multiwalled carbon nanotubes, two‐dimensional (2D) graphene nanoplatelets, and three‐dimensional (3D) functionalized graphene sheets, which are all efficient microwave‐absorbing materials that can transform microwaves into heat energy. As a result, the temperatures of the nanocomposites increased more rapidly than pristine ESMP in microwaves. The functionalized graphene sheets were found to transform the microwaves into heat more efficiently than the other nanofillers. Possible microwave propagation paths in the nanocomposites were proposed. Moreover, the nanocomposites displayed significantly higher mechanical strengths than pristine ESMP. The low cost and strong nanocomposites with fast microwave responses may be applied as actuators or deployable devices in medical treatments. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45676.     

Roll‐to‐roll printed carbon nanotubes on textile substrates as a heating layer in fiber‐reinforced epoxy composites

The performance of wind turbines suffers from icing in regions with extreme climate. One approach is to incorporate heating elements into the most susceptible areas of the wind turbine blade as protection against icing and for de‐icing. Cost‐efficient and reproducible fabrication, as well as easy integration is important due to the large area of wind turbine blades. In this work, multi‐walled carbon nanotubes are applied on a 50% poly(ethylene terephthalate) and 50% polyamide non‐woven textile substrate by rotary‐screen printing. The printed layers function as resistive heating elements in a fiber‐reinforced composite. The heating areas are provided with flexographic or screen inline‐printed silver‐electrodes and can be integrated by means of vacuum infusion into a glass fiber‐reinforced epoxy composite laminate. These laminates, which are connected to an intelligent electrical control system, are suitable for melting ice on the surface of components or for preventing the formation of ice. The first promising experiments on heating structures in a rotor blade of a wind turbine at laboratory scale (2 m length) are the basis of studies on intelligent electrical control of heating structures and their behavior at different temperatures. The heating elements were able to melt a 3–4 mm thick ice layer within 25 min in a climate chamber at ?5 °C. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45950.     

Mechanical and thermal performances of epoxy resin/graphitic carbon nitride composites

In this paper, a series of graphitic carbon nitride (g-C₃N₄) was synthesized under different thermal oxidation etching temperatures and epoxy/g-C₃N₄ composites were prepared via solution blending. The morphology and structure of g-C₃N₄ were investigated by transmission electron microscope, X-ray diffraction (XRD), Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The tensile fracture morphology and structure of epoxy resin (EP) composites were demonstrated by scanning electron microscopy and XRD, respectively. Mechanical properties of EP composites were characterized by tensile testing, and the thermal performances were investigated by dynamic mechanical thermal analysis and thermal gravimetric analysis. The results revealed that the active groups on g-C₃N₄ sheets increased under thermal oxidation etching and the C to N ratio of g-C₃N₄ decreased from 0.94 to 0.76 with the increasing etching temperature. Noticeably, the tensile strength of EP composites was enhanced by 58% with the addition of C₃N₄-NS-500 and the thermal properties were also improved significantly, including T_0.5 (the decomposition temperature at the mass loss of 50%) increased by 21.5 °C and glass transition temperature improved by 8 °C. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48598.