Basalt fiber–epoxy laminates with functionalized multi-walled carbon nanotubes

Cross-ply laminates reinforced with basalt fibers and functionalized multi-walled carbon nanotubes (MWCNTs) were fabricated from unidirectional epoxy prepregs. MWCNTs with varied surface conditions were prepared by oxidization or esterification, and then dispersed into a DGEBA epoxy system. The dispersion of the MWCNTs in the epoxy was improved by surface modification, resulting in improved composite mechanical properties as well. Significant increases in elastic modulus and strength were observed for epoxies with functionalized MWCNTs, especially for esterified species. When MWCNT – filled epoxies were used as matrices for basalt fiber/epoxy laminates, however, the reinforcement effects of MWCNTs on the composite elastic modulus exceeded micromechanics based semi-empirical predictions and were independent of surface functionalization. SEM morphological observations and the results of the micromechanical model revealed that nanotube re-distribution and orientation during processing was responsible for the enhancement of fiber-dominated mechanical properties. This work demonstrated the feasibility of in situ alignment and dispersion of functionalized nanotubes in multi-scale composite laminates.     

功能化MWCNTs网格/环氧树脂复合材料的制备及性能

采用正压过滤法制备了多壁碳纳米管（MWCNTs）网格（巴基纸）,并采用真空辅助RTM工艺制备了MWCNTs网格/环氧树脂复合材料。通过SEM、FTIR、拉伸测试等对MWCNTs网格的微观形貌和性能进行了表征,并研究了MWCNTs网格/环氧复合材料的拉伸性。结果表明,所制备的功能化MWCNTs网格比较均匀,拉伸强度在22~32 MPa之间,拉伸模量约为1 GPa,相比未功能化处理的MWCNTs网格,强度最大提高了约167%。功能化MWCNTs网格/环氧树脂复合材料的拉伸强度和拉伸模量可达到152 MPa和6.48 GPa,相比空白环氧树脂提高了约1倍以上,拉伸试样断面SEM表明,环氧树脂对功能化MWCNTs网格的浸润效果良好,界面结合紧密,有效地提高了复合材料的力学性能。     

Fabrication and mechanical properties of well-dispersed multiwalled carbon nanotubes/epoxy composites

Multiwalled carbon nanotubes (MWCNTs)/epoxy nanocomposites were fabricated by using ultrasonication and the cast molding method. In this process, MWCNTs modified by mixed acids were well dispersed and highly loaded in an epoxy matrix. The effects of MWCNTs addition and surface modification on the mechanical performances and fracture morphologies of composites were investigated. It was found that the tensile strength improved with the increase of MWCNTs addition, and when the content of MWCNTs loading reached 8 wt.%, the tensile strength reached the highest value of 69.7 MPa. In addition, the fracture strain also enhanced distinctly, implying that MWCNTs loading not only elevated the tensile strength of the epoxy matrix, but also increased the fracture toughness. Nevertheless, the elastic modulus reduced with the increase of MWCNTs loading. The reasons for the mechanical property changes are discussed.     

DHDOPO接枝改性多壁碳纳米管及其对聚乳酸性能的影响

首先将多壁碳纳米管(p-MWCNTs)用混合浓酸氧化成羧基化MWCNTs(MWCNTs-COOH),然后与氯化亚砜(SOCl_2)反应得酰氯化MWCNTs(MWCNTs-COCl);将9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)与二乙醇胺(DEA)反应制备DOPO的衍生物DHDOPO;再将DHDOPO与MWCNTs-COCl进行接枝反应得表面功能化的MWCNTs(MWCNTs-COO-DH);最后经熔融共混法制备聚乳酸(PLA)/MWCNTs-COO-DH复合材料。用核磁共振氢谱和透射电子显微镜表征MWCNTs-COO-DH的结构和微观形貌;用电子万能试验机、扫描电子显微镜、微型燃烧量热计等测定PLA/MWCNTs-COO-DH复合材料的力学性能、冲击断面形貌、燃烧性能及残炭层形貌。结果表明,实验成功合成了目标产物DHDOPO,并将其接枝到MWCNTs表面形成了典型核-壳结构的MWCNTs-COO-DH;适量的MWCNTs-COO-DH可均匀分散在PLA基体中形成良好的界面结合;质量分数为0.1%的MWCNTs-COO-DH可显著提高PLA的力学性能,并能降低其可燃性和火灾危险性。     

混杂功能化多壁碳纳米管/环氧树脂复合材料的制备及性能

对多壁碳纳米管(MWCNTs)分别进行共价、非共价和混杂功能化改性, 然后采用溶液共混法, 将三种功能化类型的MWCNTs按不同质量分数分别加入环氧树脂(EP)制备MWCNTs/EP复合材料。通过拉伸试验和热重分析, 研究MWCNTs的功能化类型及含量对复合材料力学性能和热学性能的影响, 并对复合材料拉伸试件断面进行SEM观察分析。结果表明: 与共价功能化复合材料(MWCNTs-Epon828/EP)和非共价功能化复合材料(MWCNTs-PPA/EP)相比, 混杂功能化复合材料(MWCNTs-Epon828-PPA/EP)的力学性能和热学性能最佳。当MWCNTs质量分数为0.3%时, 其拉伸强度、弹性模量和断裂伸长率较纯EP分别提高30%, 62%和26%。      

Single-walled carbon nanotube incorporated novel three phase carbon/epoxy composite with enhanced properties

In the present work, single-walled carbon nanotubes were dispersed within the matrix of carbon fabric reinforced epoxy composites in order to develop novel three phase carbon/epoxy/single-walled carbon nanotube composites. A combination of ultrasonication and high speed mechanical stirring at 2000 rpm was used to uniformly disperse carbon nanotubes in the epoxy resin. The state of carbon nanotube dispersion in the epoxy resin and within the nanocomposites was characterized with the help of optical microscopy and atomic force microscopy. Pure carbon/epoxy and three phase composites were characterized for mechanical properties (tensile and compressive) as well as for thermal and electrical conductivity. Fracture surfaces of composites after tensile test were also studied in order to investigate the effect of dispersed carbon nanotubes on the failure behavior of composites. Dispersion of only 0.1 wt% nanotubes in the matrix led to improvements of 95% in Young's modulus, 31% in tensile strength, 76% in compressive modulus and 41% in compressive strength of carbon/epoxy composites. In addition to that, electrical and thermal conductivity also improved significantly with addition of carbon nanotubes.     

Multiscale carbon fibre–reinforced polymer (CFRP) composites containing carbon nanotubes with tailored interfaces

Pristine and functionalized multiwalled carbon nanotubes (MWCNTs) with tailored interfaces were efficiently dispersed in an epoxy matrix using a three‐roll mill and further reinforced with carbon fibres. 1.3‐Dipolar cycloaddition of azomethine ylides was used for the chemical modification of MWCNTs by a solvent‐free approach. The influence of different loadings and types of MWCNTs on the final properties of the epoxy matrix was studied. Moreover, the most promising formulations were selected for manufacturing of prepreg sheets. The transversal tensile properties and the interlaminar fracture toughness under mode I loading (G_IC) of multiscale carbon fibre–reinforced polymer (CFRP) composites were characterized. The results point out that it is not straightforward to transfer the remarkable intrinsic properties of MWCNTs to the composite level, although an overall positive trend was found. Double cantilever beam experiments showed that G_IC of CFRP composites was improved 44% at ultralow content of functionalized MWCNTs (0.043 wt%).     

改性碳纳米管处理碳纤维的效果表征

采用浓硫酸/浓硝酸氧化处理多壁碳纳米管(MWCNTs),再将氧化后的碳纳米管与硅烷偶联剂(KH560)进行接枝,制备了硅烷偶联剂表面化学修饰的MWCNTs。在此基础上,将改性前后的碳纳米管分散在环氧树脂体系中,涂覆处理碳纤维。研究处理前后碳纤维力学性能和界面性能的变化。通过红外光谱(FTIR)和透射电镜(TEM)分析,表明KH560已成功接枝到多壁碳纳米管上;通过分散性实验证明了改性后的碳纳米管分散性提高;对处理后的碳纤维进行力学性能测试,并用扫描电镜(SEM)观察分析断面形态变化,结果表明,当碳纳米管的含量为0.5%时,改性碳纳米管处理的碳纤维拉伸强度和拉伸模量分别提高23.83%和7.11%,界面性能增强。     

The significance of carbon nanotubes on styrene butadiene rubber (SBR) and SBR modified mortar

A New approach is introduced to incorporate multi-walled carbon nanotubes (MWCNTs) in cementitious materials. The MWCNTs are dispersed in styrene butadiene rubber (SBR) matrix before mixing the matrix with cement. Surfactants have been successfully applied to enhance the dispersion and functionalization of MWCNTs in SBR. The significance of using this MWCNTs–SBR nanocomposite on the mechanical characteristics including compressive and tensile strengths and microstructural features of latex modified mortar (LMM) were examined. Subsequently, the significance of the functionalized MWCNTs on surface chemistry, microstructure and thermal stability of SBR were characterized. MWCNTs were found to be a useful additive for enhancing the mechanical response and thermal stability of SBR. MWCNTs–SBR nanocomposite was observed to be able to bridge micro-cracks in the LMM which helped enhancing its mechanical properties. The ability of MWCNTs to enhance the mechanical response of SBR polymer matrix might be attributed to chemical bond that functionalized MWCNTs can establish with the SBR polymer matrix. The enhanced MWCNTs–SBR nanocomposite gave rise to improved microstructural features of the LMM. Microstructural investigations showed MWCNTs were well dispersed in and bonded to the SBR matrix.     

Concise route to styryl-modified multi-walled carbon nanotubes for polystyrene matrix and enhanced mechanical properties and thermal stability of composite

Effective functionalization of multi-walled carbon nanotubes (MWCNTs) with styryl group was carried out via the esterification reaction of the carboxylate salt of carbon nanotubes and 4-vinylbenzyl chlorides in toluene. The functionalized MWCNTs were characterized through FTIR and Raman spectra to confirm the styryl groups covalently connected to the surface of MWCNTs. The weight loss of functionalized moieties determined by thermogravimetry-differential scanning calorimertry analysis is around 36%. Nanotube-reinforced polystyrene were fabricated by mixing functionalized MWCNTs and polystyrene. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images showed that the functionalized nanotubes had a better dispersion than the unfunctionalized MWCNTs in the matrix. Moreover, styryl-modified MWCNTs/PS nanocompsite presented obvious improvements in mechanical properties and thermal stability.     

不同官能化碳纳米管对MWCNTs-碳纤维/环氧树脂复合材料力学性能的影响

为研究加入不同官能化碳纳米管对环氧树脂力学性能的影响,通过对羧基化多壁碳纳米管(MWCNTsCOOH)进行化学处理,得到表面接枝乙二胺的碳纳米管(MWCNTs-EDA)。分别将MWCNTs-COOH和MWCNTs-EDA分散在环氧树脂中,通过热熔法制备环氧树脂中含有碳纳米管的T700碳纤维预浸料,并热压成准各向同性复合材料层合板。结果表明:MWCNTs-EDA在环氧树脂中的分散性优于MWCNTs-COOH,MWCNTsEDA本身具有固化反应活性,加入后对基体的交联密度影响较小。与MWCNTs-COOH相比,MWCNTs-EDA可以有效改善环氧树脂及碳纤维/环氧树脂复合材料的力学性能。当MWCNTs-EDA含量为1.0wt%时,MWCNTs-碳纤维/环氧树脂准各向同性复合材料层合板的压缩性能、弯曲性能和冲击后压缩强度分别提高了14.7%、40.9%和20.6%。     

石墨烯-多壁碳纳米管协同增强环氧树脂复合材料的低温力学性能

为了提高环氧树脂的低温力学性能,采用石墨烯与多壁碳纳米管(MWCNTs)协同改性环氧树脂,系统研究了石墨烯-MWCNTs/环氧树脂复合材料的室温(RT)和低温(77K)力学性能。结果表明:当石墨烯的质量分数为0.1wt%,MWCNTs的质量分数为0.5wt%时,纳米填料的加入可同时改善环氧树脂的低温拉伸强度、弹性模量和冲击强度;在此最佳含量下,石墨烯-MWCNTs/环氧树脂复合材料在RT和77K时的拉伸强度皆达到最大值,比纯环氧树脂的拉伸强度分别提高了11.04%和43.78%。石墨烯和MWCNTs能协同提高环氧树脂的低温力学性能。     

Reduction of thermal residual stresses of laminated polymer composites by addition of carbon nanotubes

This paper studies the effects of multi-walled carbon nanotubes (MWCNTs) on the thermal residual stresses in polymeric fibrous composites. Reinforced ML-506 epoxy nanocomposites with different amounts of homogeneously dispersed MWCNTs (0.1 wt.%, 0.5 wt.% and 1 wt.%) were fabricated using the sonication technique. Thermo-mechanical analysis and tensile tests of the specimens were carried out to characterize the thermal and mechanical properties of MWCNTs/epoxy composites. Due to the negative thermal expansion and high modulus of MWCNTs, addition of MWCNTs resulted in a great reduction of the coefficient of thermal expansion (CTE) of epoxy. The MWCNTs also moderately increased the Young’s modulus of the epoxy. Then, the effects of adding MWCNTs on micro and macro-residual stresses in carbon fiber (CF)/epoxy laminated composites were investigated using the energy method and the classical lamination theory (CLT), respectively. The results indicated that the addition of low amounts of MWCNTs leads to a considerable reduction in thermal residual stress components in both micro and macro levels.     

Pristine and amino functionalized carbon nanotubes reinforced glass fiber epoxy composites

Multi-phase composites have been studied by incorporating carbon nanotubes (CNTs) as a secondary reinforcement in an epoxy matrix which was then reinforced with glass fiber mat. Different types of CNTs e.g. amino functionalized carbon nanotubes (ACNT) and pristine carbon nanotubes (PCNT) were homogeneously dispersed in the epoxy matrix and two-ply laminates were fabricated using vacuum-assisted resin infusion molding technique. The issues related to CNT dispersion and interfacial bonding and its affect on the mechanical properties have been studied. An important finding of this study is that PCNT scores over ACNT in composites prepared under certain conditions. This is a very significant finding since PCNT is available at a much lower cost than ACNT.     

Cryogenic mechanical behaviors of carbon nanotube reinforced composites based on modified epoxy by poly(ethersulfone)

Cryogenic mechanical properties are important parameters for epoxy resins used in cryogenic engineering areas. In this study, multi-walled carbon nanotubes (MWCNTs) were employed to reinforce diglycidyl ether of bisphenol F (DGBEF)/diethyl toluene diamine (DETD) epoxy system modified by poly(ethersulfone) (PES) for enhancing the cryogenic mechanical properties. The epoxy system was properly modified by PES in our previous work and the optimized formulation of the epoxy system was reinforced by MWCNTs in the present work. The results show that the tensile strength and Young’s modulus at 77 K were enhanced by 57.9% and 10.1%, respectively. The reported decrease in the previous work of the Young’s modulus of the modified epoxy system due to the introduction of flexible PES is offset by the increase of the modulus due to the introduction of MWCNTs. Meanwhile, the fracture toughness (K_IC) at 77 K was improved by about 13.5% compared to that of the PES modified epoxy matrix when the 0.5 wt.% MWCNT content was introduced. These interesting results imply that the simultaneous usage of PES and MWCNTs in a brittle epoxy resin is a promising approach for efficiently modifying and reinforcing epoxy resins for cryogenic engineering applications.     

Preparation,characterization and properties of polycaprolactone diol-functionalized multi-walled carbon nanotube/thermoplastic polyurethane composite

Multi-walled carbon nanotubes (MWCNTs) were chemically functionalized to prepare thermoplastic polyurethane (PU) composites with enhanced properties. In order to achieve a high compatibility of functionalized MWCNTs with the PU matrix, polycaprolactone diol (PCL), as one of PU’s monomers, was selectively grafted on the surface of MWCNTs (MWCNT–PCL), while carboxylic acid groups functionalized MWCNTs (MWCNT–COOH) and raw MWCNTs served as control. Both MWCNT–COOH and MWCNT–PCL improved the dispersion of MWCNTs in the PU matrix and interfacial bonding between them at 1 wt% loading fraction. The MWCNT–PCL/PU composite showed the greatest extent of improvement, where the tensile strength and modulus were 51.2% and 33.5% higher than those of pure PU respectively, without sacrificing the elongation at break. The considerable improvement in both mechanical properties and thermal stability of MWCNT–PCL/PU composite should result from the homogeneous dispersion of MWCNT–PCL in the PU matrix and strong interfacial bonding between them.     

静电植绒法处理多壁碳纳米管改性玻纤织物/环氧树脂复合材料的制备及力学性能

为提高玻纤增强环氧树脂复合材料的力学性能,采用静电植绒法将多壁碳纳米管(MWCNTs)附着在玻纤织物表面,得到改性的玻纤织物。利用一种低黏度的环氧树脂和所制得的改性织物,采用真空辅助成型工艺(VARI)制备了MWCNTs改性格玻纤织物/环氧树脂复合材料层合板,表征了层合板的力学性能。对进行力学实验后的MWCNTs改性玻纤织物/环氧树脂复合材料试样断口进行了SEM和OPM观察。结果显示:与未添加MWCNTs的玻纤织物/环氧树脂复合材料层合板相比,添加了MWCNTs的层合板的拉伸强度降低了10.24%,弯曲强度降低了13.90%,压缩强度降低了17.33%,拉伸模量和弯曲模量分别提高了19.38%和16.04%,压缩模量提高了13%;MWCNTs与玻纤织物之间的结合较弱,在拉伸作用下,存在明显的脱粘和分层;将改性玻纤织物在200℃下热压处理2h后,制备的MWCNTs改性玻纤织物/环氧树脂复合材料层合板的力学性能均有所提高,热压处理后树脂与玻纤织物之间的界面结合得到改善。     

Mechanical performance of epoxy matrix hybrid nanocomposites containing carbon nanotubes and nanodiamonds

A novel class of epoxy matrix hybrid nanocomposites has been developed containing multiwalled carbon nanotubes (MWCNTs) and nanodiamonds (NDs) to explore the combined effect of nanoreinforcements on the mechanical performance of nanocomposites. Both the nanofillers were functionalized before incorporating into epoxy matrix to promote interfacial interactions. The concentrations of both MWCNTs and NDs in the nanocomposites were increased systematically, i.e. 0.05 wt.%, 0.1 wt.% and 0.2 wt.% while composites containing individual nanoreinforcements were also manufactured for comparison. The developed nanocomposites were characterized microstructurally by scanning electron microscopy (SEM) and mechanically by tensile, flexural, impact and hardness tests. Homogeneous dispersion of MWCNTs and NDs was observed under SEM, which resulted in the enhancement of mechanical properties of nanocomposites. The composites containing 0.2 wt.% MWCNTs and 0.2 wt.% NDs showed 50% increase in hardness while tensile strength and modulus enhanced to 70% and 84%, respectively. Flexural strength and modulus also showed a rise of 104% and 56%, respectively. Interestingly, fracture strain also increased in both the tensile and flexural testing. The impact resistance increased to 161% showing a significant improvement in the toughness of hybrid nanocomposites.     

Comparison of cytotoxicity of pristine and covalently functionalized multi-walled carbon nanotubes in RAW 264.7 macrophages

Carbon nanotubes may be applied in different fields including biomedicine and mechanical engineering. It is important to understand the potential hazards of carbon nanotubes. In the present study, the toxicological effects of the pristine multi-walled carbon nanotubes (p-MWCNTs) and taurine functionalized multi-walled carbon nanotubes (tau-MWCNTs) were assessed on RAW 264.7 macrophages. We tested cell viability, GSH/GSSG ratio, apoptosis, intracellular calcium concentration, ultrastructural changes of cell morphology, and the release of IL-8. We observed the loss of cell viability, decline in the cellular GSH/GSSG ratio, increase of IL-8, and the increase of intracellular calcium concentration in RAW 264.7 macrophages when exposed to p-MWCNTs at high dosage. Additionally, exposure to p-MWCNTs resulted in ultrastructural and morphological changes in RAW 264.7 macrophages. In contrast, the RAW 264.7 macrophages exposed to the tau-MWCNTs did not exhibit altered morphology. Our results conclude that the tau-MWCNTs show lower toxicity than that of p-MWCNTs.     

Effect of matrix glass transition on reinforcement efficiency of epoxy-matrix composites with single walled carbon nanotubes,multi-walled carbon nanotubes,carbon nanofibers and graphite

This study compares the mechanical and thermal properties of glassy and rubbery epoxy–matrix composites reinforced with 1 and 4 wt.% single-walled carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs), graphite, and carbon nanofibers (CNFs). The tensile modulus of most glassy composites was higher than that of the epoxy and increased with higher filler concentration and 4% graphite/epoxy and 4% SWCNT/epoxy exhibited approximately the same highest tensile modulus. The elongation of glassy composites was significantly lower than that of the epoxy and decreased with increasing filler loading. Most rubbery composites showed a higher tensile modulus and elongation than the epoxy and the modulus increased with rising filler content and 4% SWCNT/epoxy showed the highest tensile modulus and tensile strength. In the rubbery regime, glassy and rubbery composites displayed a higher storage modulus than the corresponding epoxy and 4 wt.% SWCNT/epoxy composites showed a 300% improvement in storage modulus compared to the epoxy.