Thermo-physical properties of epoxy nanocomposites reinforced with amino-functionalized multi-walled carbon nanotubes

The modification of multi-walled carbon nanotubes (MWNTs) with amine groups was investigated by FTIR, Raman spectroscopy and XPS after such steps as carboxylation, acylation and amidation. Nanotube-reinforced epoxy polymer composites were prepared by mixing amino-functionalized MWNTs with epoxy resin and curing agent. DSC, TGA, SEM and flexural test were used to investigate the thermal and mechanical properties of the composites. The results showed that amino-functionalized MWNTs could enhance the interfacial adhesion between the nanotubes and the matrix, thus greatly improve the thermal and mechanical properties of the resin epoxy bulk material.     

Mechanical and thermal properties of epoxy nanocomposites reinforced with amino-functionalized multi-walled carbon nanotubes

The functionalized multi-walled carbon nanotubes (MWNTs) with amino groups were prepared after such steps as oxidation, the addition of carboxyalkyl radicals, acylation and amidation. Besides oxidated-MWNTs/epoxy nanocomposites, amino-functionalized MWNTs/epoxy nanocomposites, in which MWNTs with amino groups acted as a curing agent and covalently attached into the epoxy matrix, were fabricated. Subsequently, the effects of MWNT content on the mechanical and thermal properties for the two systems were investigated. It is found that both the tensile strength and impact strength enhance with the increase of MWNT addition, and the most significant improvement of the tensile strength (+51%) and especially impact strength (+93%) is obtained with amine-treated MWNTs at an 1.5 wt.% content. Moreover, the thermal stability of the nanocomposites also distinctly improves. The improvement of the properties of the amine-treated MWNTs system is more remarkable than those of o-MWNTs system. The reasons for these changes were discussed.     

纳米碳管/环氧树脂复合材料的制备及力学性能

报道了利用催化裂解法制备的纳米碳管合成环氧树脂复合材料的技术及工艺条件。利用透射电子显微镜(TEM)对制备的复合材料进行观察表征;通过拉伸及压缩实验对纳米碳管/环氧树脂复合材料的力学性能进行了测试。实验结果表明:纳米碳管的加入可以明显地改变环氧树脂基体材料的力学性能。      

Effects of amino group on the properties of carbon nanotubes

The surfaces of multi-walled carbon nanotubes were grafted with amino functional groups by reacting acyl-chloride-functionalized carbon nanotubes (CNTs) with hexamethylene diamine, which improves the surfactivity of CNTs. The dispersity, surface morphology, and thermogravimetry of acid-treated and amino-functionalized CNTs were investigated. Amino-functionalized CNTs were added into epoxy resin to analyze the effects of amino functional groups on the properties of resin composites. It was found that the properties of CNTs, such as morphology and scale, were not affected by amino functional groups, but the dispersity in water was highly improved. Amino-functionalized CNTs are better dispersed in resin matrix, and the mechanical properties of composites are improved significantly, whereas the conductivity of composites is not enhanced as expected.     

The impact of fluorinated MWCNT additives on the enhanced dynamic mechanical properties of e-beam-cured epoxy

Multi-walled carbon nanotubes were embedded into e-beam-cured epoxy resin to improve the mechanical properties of epoxy resin. The surfaces of these carbon nanotubes were modified using a fluorination treatment to improve their dispersion and adhesion in epoxy resin. The dynamic mechanical properties of epoxy/carbon nanotube composites were investigated at various heating rates and frequencies. As an effect of fluorination treatment, the semi-ionic bond of C–F on the surface of multi-walled carbon nanotubes played an important role in the improved dispersion and adhesion of carbon nanotubes into the epoxy resin. The storage modulus and loss modulus of the composites increased with higher applied frequency. The activation energy of the composites was increased by the effects of a higher heating rate due to the slow heat transfer in the epoxy/carbon nanotube composites. Eventually, the dynamic mechanical properties of the investigated epoxy were significantly improved by the carbon nanotubes dispersed therein via the fluorination treatment.     

Improvements in mechanical and thermo-mechanical properties of e-glass/epoxy composites using amino functionalized MWCNTs

The prime objective of this work is to optimize the mechanical and thermo-mechanical properties of e-glass/epoxy composites by utilizing amino-functionalized multi-walled carbon nanotubes (MWCNTs–NH₂) through a combination of dispersion method. At first, 0.1–0.4 wt.% of MWCNT–NH₂ was integrated into SC-15 epoxy suspension using a combination of ultra-sonication and calendaring techniques. E-glass/epoxy nanocomposites were than fabricated at elevated temperature with the modified resin using hand layup and compression hot press. 3-Point flexural and dynamic mechanical analysis (DMA) results demonstrated a linearly increasing trend in properties from 0 to 0.3 wt.% loading. Micrographs of MWCNTs incorporated epoxy and e-glass/epoxy samples revealed uniform dispersion of MWCNTs in epoxy, good interfacial adhesion between CNTs and polymer, and improved interfacial bonding between fiber/matrix at 0.3 wt.% loading. An improved dispersion and hence an improved crosslink interaction between MWCNT–NH₂ and epoxy lead to the stronger shift of the mechanical and thermo-mechanical properties of the composites.     

表面官能团化多壁碳纳米管/环氧树脂复合材料的制备及性能

本文首先将多壁碳纳米管(MWNT)进行表面化学修饰,接入羧基、胺基等官能团,采用红外光谱进行了表征.以纯化后的MWNT和表面化学修饰的MWNT作为填料,制备了MWNT /环氧树脂复合材料,研究了MWNT的加入对环氧树脂的力学性能、电学性能、热稳定性和玻璃化转变温度等的影响,并利用场发射电镜观察了胺基化MWNT在环氧树脂基体中的分散情况.     

Improving the flexural and thermomechanical properties of amino-functionalized carbon nanotube/epoxy composites by using a pre-curing treatment

A prior thermal (pre-curing) treatment of mixtures of epoxy monomer and amino-functionalized carbon nanotubes (CNTs) was used to promote a chemical reaction between the matrix and the reinforcement, favouring the formation of a strong interface. Samples of epoxy resin and different weight percentages of amino-functionalized multi-walled CNTs were prepared with and without the pre-curing treatment (150 °C, 1 h). The degree of dispersion of the nanofiller was better when this pre-curing treatment was used. This allowed a higher CNT content while keeping a high sample homogeneity. Without the pre-curing step, the addition of CNTs increases both the flexural strength and strain to failure by 45%. Moreover, with the pre-curing step, the nanocomposite with 0.25 wt.% CNTs presents an increase of flexural strength by 58% and strain to failure by 68% regard to neat epoxy resin.     

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.     

Effect of chemical functionalization of multi-walled carbon nanotubes with 3-aminopropyltriethoxysilane on mechanical and morphological properties of epoxy nanocomposites

Nanocomposites based on epoxy resin and different weight percentages of unmodified, oxidized, and silanized multi-walled carbon nanotubes (MWCNTs) were prepared by cast molding method. Effects of MWCNTs content on the flexural properties were examined. The results showed that as the loading of the MWCNTs increased, improved flexural strength and flexural modulus were observed. The mechanical properties decreased when the MWCNTs content exceeded 0.2 wt.% due to agglomeration of MWCNTs. These results prove the effect of functionalization on the interfacial adhesion between epoxy and MWCNTs. This was further confirmed by morphology study of fractured surfaces of nanocomposites by SEM and TEM.     

多壁碳纳米管/聚醚砜环氧树脂复合材料的制备及力学性能

环氧树脂具有优异的热性能及力学性能,但本身脆性较大。为制备低成本、高性能的环氧树脂体系,使用聚醚砜（PES）和多壁碳纳米管（MWCNT）对环氧树脂进行增韧,制备了不同PES含量的PES-环氧树脂共混物,讨论了PES含量对环氧树脂力学性能的影响;采用熔融法,并配合使用机械搅拌、高剪切分散和超声分散制备了MWCNT/PES-环氧树脂复合材料,测试了其拉伸性能及断裂韧性,用SEM观察了MWCNT在树脂中的分散状态以及拉伸试样的断口形貌。结果表明：MWCNT的加入能够提高PES-环氧树脂体系的综合力学性能,且当MWCNT含量为0.7wt%时,树脂体系的综合力学性能最好;低PES含量下,小于1.0wt%的MWCNT的加入使材料力学性能超过用20.0wt%PES改性的环氧树脂;PES与MWCNT对环氧树脂具有协同增韧作用。     

Influence of functionalization on properties of MWCNT-epoxy nanocomposites

The effects of various functionalized multi-walled carbon nanotubes (MWCNTs) on morphological, thermal, and mechanical properties of an epoxy based nanocomposite system were investigated. Chemical functionalization of MWCNT by oxidation (MWCNT-COOH) and direct-fluorination (MWCNT-F) were confirmed by FTIR, Raman spectroscopy, and TGA. Utilizing in situ polymerization, 1 wt% loading of MWCNT was used to prepare epoxy-based nanocomposites. Compared to the neat epoxy system, nanocomposites prepared with MWCNT-COOH showed 25.5% increase in ultimate flexural strength and 54.8% increase in flexural modulus. A decrease in strength was observed for the MWCNT-F nanocomposites. The premature degradation was attributed to a presumable catalyzation by hydrofluoric acid, HF, which evolved from the MWCNT-F during the curing process. However, only the MWCNT-F nanocomposites showed 22% increase in thermal properties (T_g). All nanophased systems showed increase in storage modulus.     

Modeling and mechanical performance of carbon nanotube/epoxy resin composites

The effect of multi-walled carbon nanotube (MWCNT) addition on mechanical properties of epoxy resin was investigated to obtain the tensile strength, compressive strength and Young’s modulus from load versus displacement graphs. The result shows that the tensile strength, compressive strength and Young’s modulus of epoxy resin were increased with the addition of MWCNT fillers. The significant improvements in tensile strength, compressive strength and Young’s modulus were obtained due to the excellent dispersion of MWCNT fillers in the epoxy resin. The dispersion of MWCNT fillers in epoxy resin was observed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analysis.Also, Halpin–Tsai model was modified by considering the average diameter of internal/external of multi-walled nanotube and orientation factor (α) to calculate the Young’s modulus of multi-walled carbon nanotubes (MWCNTs)/epoxy resin composite. There was a good correlation between the experimentally obtained Young’s modulus and modified Halpin–Tsai model.     

The matrix stiffness role on tensile and thermal properties of carbon nanotubes/epoxy composites

In this study, randomly oriented single-walled carbon nanotubes (SWCNTs)/epoxy nanocomposites were fabricated by tip sonication with the aid of a solvent and subsequent casting. Two different curing cycles were used to study the role of the stiffness of the epoxy matrix on the tensile and thermal behavior of the composites. The addition of a small amount of SWCNTs (0.25 wt.%) in rubbery, i.e., soft matrices, greatly increased Young’s modulus and tensile strength of the nanocomposites. The results showed that the tensile properties of soft epoxy matrices are much more influenced by the addition of carbon nanotubes than stiffer ones. The significant improvement in tensile properties was attributed to the excellent mechanical properties and structure of SWCNTs, an adequate dispersion of SWCNTs by tip sonication, and a stronger SWCNT/matrix interfacial adhesion in softer epoxy matrices. A slight improvement in the thermal stability of the nanocomposites was also observed.     

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%。     

Improving the mechanical properties of multiwalled carbon nanotube/epoxy nanocomposites using polymerization in a stirring plasma system

Uniform treatment of multiwalled carbon nanotubes by plasma treatment has been investigated using a custom-built stirring plasma system. A thin plasma polymer with high levels of amine groups has been deposited on MWCNTs using a combination of continuous wave and pulsed plasma polymerization of heptylamine in the stirring plasma system. Scanning electron microscopy showed that the plasma polymerization improved the dispersion and interfacial bonding of the MWCNTs with an epoxy resin at loadings of 0.1, 0.3 and 0.5 wt%. The flexural and thermal mechanical properties of plasma polymerized MWCNT/epoxy nanocomposites were also significantly improved while untreated MWCNT/epoxy nanocomposites showed an opposite trend. The epoxy with 0.5 wt% plasma polymerized MWCNTs had the greatest increase in flexural properties, with the flexural modulus, flexural strength and toughness increasing by about 22%, 17% and 70%, respectively.     

Thermo-mechanical properties of randomly oriented carbon/epoxy nanocomposites

The thermo-mechanical properties of epoxy-based nanocomposites based on low weight fractions (from 0.01 to 0.5 wt%) of randomly oriented single- and multi-walled carbon nanotubes were examined. Preparation methods for the nanocomposites, using two types of epoxy resins, were developed and good dispersion was generally achieved. The mechanical properties examined were the tensile Young's modulus by Dynamic Mechanical Thermal Analysis and the toughness under tensile impact using notched specimens. Moderate Young's modulus improvements of nanocomposites were observed with respect to the pure matrix material. A particularly significant enhancement of the tensile impact toughness was obtained for specific nanocomposites, using only minute nanotube weight fractions. No significant change in the glass transition temperature of SWCNT/epoxy nanocomposites was observed, compared to that of the epoxy matrix. The elastic modulus of the SWNT-based nanocomposites was found to be slightly higher than the value predicted by the Krenchel model for short-fiber composites with random orientation.     

Improving the mechanical properties of epoxy using multiwalled carbon nanotubes functionalized by a novel plasma treatment

Achieving both uniform dispersion and good interfacial adhesion have been long-term challenges in optimizing the properties of carbon nanotube reinforced polymer nanocomposites. A novel and effective plasma method, which combines continuous and pulsed plasma modes in a nitrogen and hydrogen gas mixture (15% H₂), has been developed to better meet this need. It has yielded high levels of primary amines on the surface of multiwalled carbon nanotubes which improved their dispersion and interfacial bonding with an epoxy resin. By adding just 0.1 wt% of these nanotubes to Bisphenol F epoxy resin, the mechanical properties of the nanocomposites, from nano to macro, were significantly improved. Nanoindentation tests showed that the hardness and elastic modulus increased by 40% and 19%, respectively, using the functionalized nanotubes. Macro-mechanical properties from thermo-mechanical and flexural analysis were also enhanced, with a nearly 40% improvement in toughness.     

Study on thermal and mechanical properties of nano-calcium carbonate/epoxy composites

A study on evaluating the effect of nano-CaCO₃ particles on thermal and mechanical properties of epoxy resin cast was performed by TGA and mechanical tests. A silane coupling agent KH550 as an interfacial modifier was introduced into nanocomposites through preparing KH550/nano-CaCO₃ master batch. It is revealed that epoxy resin cast filled with nano-CaCO₃ particles represents higher thermal stability and mechanical strength. The improvement of thermal and mechanical properties is attributed to the surface modification of nano-particles, which can enhance the interfacial properties between nano-CaCO₃ fillers and epoxy resin. The mechanical properties of nano-CaCO₃/epoxy/carbon fibres composites based on the modified epoxy matrix are also enhanced.     

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.