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.     

The effects of CNT alignment on electrical conductivity and mechanical properties of SWNT/epoxy nanocomposites

The single-walled carbon nanotubes (SWNTs) filled nanocomposite SWNT/epoxy resin composite with good uniformity, dispersion and alignment of SWNTs and with different SWNTs concentrations was produced by solution casting technique. Subsequently, the semidried mixture was stretched repeatedly along one direction at a large draw-ratio of 50 for 100 times at ambient atmosphere manually to achieve a good alignment and to promote dispersion of SWNTs in the composite matrix. Composite showed higher electrical conductivities and mechanical properties such as the Young’s modulus and tensile strength along the stretched direction than perpendicular to it, and the electrical property of composite rise with the increase of SWNT concentration. The percolation threshold value of electrical conductivity along the stretching direction is lower than the value perpendicular to the SWNTs orientation. In addition, the anisotropic electric and mechanical properties results, SEM micrograph and the polarized Raman spectra of the SWNT/epoxy composite reveal that SWNTs were well dispersed and aligned in the composites by the repeated stretching process.     

Incorporation of liquid-like multiwalled carbon nanotubes into an epoxy matrix by solvent-free processing

Covalent attachment of 2,2'-(ethylenedioxy)-diethylamine to multiwalled carbon nanotubes (MWCNTs) produced amino-functionalized MWCNTs which behaved like liquids at ambient temperature. These liquid-like MWCNTs (l-MWCNTs) could be homogeneously dispersed and chemically embedded in an epoxy matrix by solvent-free processing. In contrast, solid MWCNTs (s-MWCNTs) functionalized by 1,8-diaminooctane were poorly dispersed in epoxy although they possess chemical structures and functionalization comparable to l-MWCNTs. An epoxy composite filled with pristine MWCNTs (p-MWCNTs) was also fabricated in the absence of a solvent at the same loading for comparison. The molecular level coupling of l-MWCNTs and epoxy provided significant improvements in overall mechanical properties relative to those composites containing p-MWCNTs and s-MWCNTs. The Young's modulus, storage modulus, tensile strength, failure strain and toughness of neat epoxy were increased by 28.4, 23.8, 22.9, 24.1 and 66.1%, respectively, by adding 0.5?wt% of l-MWCNTs. Thus, functionalized carbon nanotubes in liquid form contributed to better dispersion and superior interfacial bonding with the epoxy matrix, thereby facilitating greater mechanical reinforcement efficiency.     

Solvent-free preparation of high-toughness epoxy--SWNT composite materials

Multicomponent nanocomposite materials based on a high-performance epoxy system and single-walled carbon nanotubes (SWNTs) have been prepared. The noncovalent wrapping of nitric acid-treated SWNTs with a PEO-based amphiphilic block copolymer leads to a highly disaggregated filler with a boosted miscibility in the epoxy matrix, allowing its dispersion without organic solvents. Although direct dispersion of acid-treated SWNTs results in modestly improved epoxy matrix mechanical properties, the incorporation of wrapped SWNTs produces a huge increase in toughness (276% improvement at 0.5 wt % loading) and impact strength (193% at 0.5 wt % loading) with no detrimental effect on the elastic properties. A synergistic effect between SWNTs and the block copolymer is revealed on the basis of tensile and impact strength results. Atomic force microscopy has been applied, obtaining stiffness mappings that identify nanostructure features responsible of the dynamic mechanical behavior. The electrical percolation threshold is greatly reduced, from 0.31 to 0.03 wt % SWNTs when block copolymer-wrapped SWNTs are used, and all the measured conductivity values increased up to a maximum of 7 orders of magnitude with respect to the baseline matrix (1 wt % wrapped-SWNTs loading). This approach provides an efficient way to disperse barely dispersible SWNTs without solvents into an epoxy matrix, and to generate substantial improvements with small amounts of SWNTs.     

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%。     

Curing effects of single-wall carbon nanotube reinforcement on mechanical properties of filled epoxy adhesives

Enhancing epoxy adhesives using nanoscale fillers requires understanding processing-structure–property relationships as a function of nanoscale filler loading. In particular, the effects of adding nanoscale reinforcement to filled epoxies, such as those qualified for space applications, have yet to be characterized. In this effort, the addition of single-walled carbon nanotubes (SWNTs) to Hysol 9309.2 epoxy was investigated using a multi-scale mechanical characterization approach. Effects of SWNTs on the kinetics of epoxy curing were characterized and modeled using macromechanical dynamic mechanical analysis (DMA). Adhesion between SWNTs and microfiber reinforcement was identified with scanning electron microscope (SEM), and effects of SWNTs on mechanical properties of the filled epoxy were quantified using micromechanical tensile testing. Effects of SWNT reinforcement on mechanical behavior of the epoxy matrix were also characterized using nanomechanical characterization. This multi-scale mechanical characterization enabled the effects of SWNTs to be isolated from the epoxy and filler phases inherent in the adhesive.     

Tuning the mechanical properties of SWNT/nylon 6,10 composites with flexible spacers at the interface

We have prepared nylon 6,10 nanocomposites using functionalized single wall carbon nanotubes and our interfacial in situ polycondensation method. The specific functional groups -(CH2)nCOCl [n = 4 and 9] on the sidewalls of SWNT were designed to covalently link nanotubes to the nylon matrix via alkyl segments. The composites with functionalized SWNT show significant improvements in tensile modulus, strength, and toughness relative to nylon and nylon modified with non-functionalized SWNT. The alkyl linkages at the SWNT/nylon 6,10 interface contribute significantly to improving the toughness of the composites.     

The reinforcement role of different amino-functionalized multi-walled carbon nanotubes in epoxy nanocomposites

Functionalization with different amino groups of multi-walled carbon nanotubes was achieved and nanotube-reinforced epoxy nanocomposites were prepared by mixing amino-functionalized multi-walled carbon nanotubes with epoxy resin. Differential scanning calorimetry, thermogravimetric analysis and bending tests were used to investigate the thermal and mechanical properties of the nanocomposites. The results showed that different kinds of amino-functionalized multi-walled carbon nanotubes would have different effects on the thermal and mechanical properties of the nanocomposites. The reinforcement mechanism of amino-functionalized multi-walled carbon nanotubes in epoxy resin was discussed.     

Molecular design of strong single-wall carbon nanotube/polyelectrolyte multilayer composites

The mechanical failure of hybrid materials made from polymers and single-wall carbon nanotubes (SWNT) is primarily attributed to poor matrix-SWNT connectivity and severe phase segregation. Both problems can be successfully mitigated when the SWNT composite is made following the protocol of layer-by-layer assembly. This deposition technique prevents phase segregation of the polymer/SWNT binary system, and after subsequent crosslinking, the nanometre-scale uniform composite with SWNT loading as high as 50 wt% can be obtained. The free-standing SWNT/polyelectrolyte membranes delaminated from the substrate were found to be exceptionally strong with a tensile strength approaching that of hard ceramics. Because of the lightweight nature of SWNT composites, the prepared free-standing membranes can serve as components for a variety of long-lifetime devices.     

碳纳米管类型对CNTs/Lyocell复合纤维结构与性能的影响

分别采用单壁碳纳米管（SWNTs）和多壁碳纳米管（MWNTs）这两种碳纳米管（CNTs）制备不同的CNTs/Lyocell复合纤维,探讨了碳纳米管类型对复合纤维的结构与性能的影响。结果表明,碳纳米管类型并未影响CNTs/Lyocell纤维的结晶结构,质量分数为1%的SWNTs或MWNTs在Lyocell基体中分布都比较...     

The effect of two neighboring defects on the mechanical properties of carbon nanotubes

The tensile behavior of single-walled nanotubes (SWNTs) having two defects (vacancy or Stone-Wales) positioned next to each other was simulated in this study to investigate the influence of the spatial arrangement of defects on the mechanical properties. The simulations were performed using classical molecular dynamics (MD) at the atomic scale. Two neighboring vacancy defects reduced the failure strength as much as 46% and the failure strain as much as 80% in comparison with those of pristine SWNTs, while two neighboring Stone-Wales defects reduced them as much as 34% and 70% respectively. SWNTs having two defects in the loading (axial) direction showed higher failure strength than SWNTs with defects perpendicular to the loading direction. For both types of defect, the closer the defects, the weaker the SWNTs. As result, the defect arrangement in the SWNT structure must be one of the key factors in determining its mechanical properties, as well as the population of defects.     

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.     

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。     

Measurement of strain distributions near the steel/epoxy interface by micro-Raman spectroscopy under tensile load condition

Micro-Raman spectroscopy was applied for evaluating the stress distributions in the vicinity of the interface of the steel/epoxy bonded joint under tensile loading condition. Herein, single-walled carbon nanotubes (SWNTs) embedded in a polymer can be used as a mechanical sensor, in which the position of the D* Raman band varies with the strain or stress transferred to SWNTs from the surrounding matrix. In order to evaluate the strain distributions, however, it is required to elucidate the effect of the multiaxial stress on the D* band shift, because a multiaxial stress field appears in the vicinity of the interface and, the validity of this method has been confirmed only under uniaxial loading condition. Hence, at first, the D* band shift of a bulk epoxy/SWNT composite was measured under biaxial loading condition using a cruciform-type specimen. It was found that the D* band shift could be standardized in terms of the strain in the polarized direction even though under the biaxial condition. Then, on the basis of the result, this method was applied for evaluating the strain distributions of the steel/SWNT composite bonded joints under uniaxial tensile loading condition. The observation indicated that the strain singularity appeared in the vicinity of the interface, similar to the results of the finite-element analysis, and the observed strain almost agreed with calculated one in the range of 0.03–10 mm distance from the interface.     

Morphological and mechanical properties of bile salt modified multi-walled carbon nanotube/poly(vinyl alcohol) nanocomposites

Non-covalently functionalized carbon nanotubes are more attractive for multifunction composites because they preserve nearly all the nanotubes’ intrinsic properties and enhance the electroconductivity of polymer composites. However, It is seldom reported that they make dramatic improvement in mechanical properties. In this paper we have successfully prepared a poly(vinyl alcohol) (PVA) nanocomposite with a non-covalently functionalized carbon nanotube (DOC-MWNTs) using a simple method, which achieve a significant enhancement in mechanical properties. The tensile modulus and tensile yield strength of the PVA composite film containing 5 wt% DOC-MWNTs increased by 140% and 65%, respectively, comparing to the pure PVA film. FT-IR, TEM, SEM, and DSC were used to investigate the MWNTs and PVA/MWNTs nanocomposites. The results show that the separately dispersed DOC-MWNTs filler throughout the PVA matrix and the strong adhesion between the DOC-MWNTs filler and the PVA matrix are responsible for the significant reinforcement of the mechanical properties of the composite prepared.     

Single wall nanotube and vapor grown carbon fiber reinforced polymers processed by extrusion freeform fabrication

Single wall carbon nanotubes (SWNTs) and vapor grown carbon fibers (VGCFs) were compounded with poly(acrylonitrile-co-butadiene-co-styrene) (ABS) to create composite materials for use with Extrusion Freeform Fabrication (EFF). The composite materials possessed homogeneously dispersed fibers that were oriented with EFF processing. The VGCF and SWNT reinforced materials processed by EFF displayed improved tensile modulus compared to similarly processed ABS and composite material with isotropic fiber orientation, and the SWNT reinforced material displayed the highest properties, strength and modulus, of the materials studied. The materials containing oriented VGCFs and SWNTs showed modulus improvements of 44 and 93%, respectively.     

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.     

MWCNT reinforced Polyamide-6,6 films: preparation,characterization and properties

Composite films of Polyamide-6,6 (PA66) and multi-walled carbon nanotubes (MWCNTs) were prepared by a combination of solution casting followed by compression molding techniques. Both unfunctionalized (u-MWCNTs) and functionalized nanotubes (f-MWCNTs) were used in this study. The functionalization involved direct solvent-free amination of MWCNTs with hexamethylenediamine. Thermogravimetric analysis was used to observe the changes in the nanotubes upon functionalization and morphological features of the resulting composite films were studied using scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. The crystallinity changes by incorporation of the u-MWCNTs and f-MWCNTs in the PA66 matrix were studied by wide angle X-ray scattering and differential scanning calorimetry. The f-MWCNT/PA66 film showed an improvement of ∼43% in maximum tensile stress (MTS) and ∼32% in Young’s modulus over pristine PA66 film, while at a similar loading of 0.5 wt%, the f-MWCNT/PA66 film showed ∼15% increase in MTS and ∼16% increase in modulus over the u-MWCNT/PA66 film. Dynamic mechanical analysis indicated significant difference in the small-strain mechanical properties between the MWCNT-filled and unfilled PA66 at the very low MWNT loadings that were tested and supported the tensile results. The water absorption trend of the composite films showed dramatic improvement over the neat film.     

Evaluation of SOCl2 doping effect on electrical conductivity of thin films of SWNTs and SWNT/PEDOT-PSS composites

Transparent conductive thin films of single-walled carbon nanotubes (SWNTs) and their nanocomposites with an organic conductive polymer, poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS) with different CNT loadings ranging from 20 to 90 wt% were prepared and doped by exposing them to thionyl chloride (SOCl2) vapors. After exposure to SOCl2 vapor for 1 h, the SWNT film showed about 15-18% increase of electrical conductivity, while on the other hand pristine polymer film showed a decrease of electrical conductivity. The SWNT-polymer composite films showed a drastic increase in conductivity by doping with SOCl2 vapor, most interestingly, the doping effect was much higher for composite films with less CNT weight fraction and it was linearly decreased with increasing CNT loading. For instance, composite film with 10% and 90% CNT loading demonstrated about 65% and 10% increase of electrical conductivity, respectively. The interaction of SOCl2 vapors on SWNTs and composite films is investigated by UV-visible absorption and Raman spectroscopy.     

Electrophoretic deposition of aramid nanofibers on carbon fibers for highly enhanced interfacial adhesion at low content

Here, an anodic electrophoretic deposition was adopted to facilitate the large-scale uniform coating of nano-fillers onto carbon fibers to enhance the interfacial properties between carbon fibers and epoxy matrix. As interface–reinforcing materials, aramid nanofibers were introduced because of their superior mechanical properties and epoxy matrix-friendly functional groups. Furthermore, aramid nanofibers can be readily coated on carbon fibers via electrophoretic deposition because they are negatively-charged in solution with high electrical mobility. Finally, aramid nanofiber-coated carbon fibers showed significantly improved interfacial properties such as higher surface free energy and interfacial shear strengths (39.7% and 34.9% increases, respectively) than those of a pristine carbon fiber despite a very small amount of embedding (0.025 wt% of aramid nanofibers in a carbon fiber), and the short beam strength of the laminated composite prepared with the aramid nanofiber-coated carbon fibers was also improved by 17.0% compared to a non-modified composite.